Copyright is owned by the Author of the thesis. Permission is given for a copy to be downloaded by an individual for the purpose of research and private study only. The thesis may not be reproduced elsewhere without the permission of the Author. THE MINERALOGY OF THE TOKOMARU SILT LOAM AND THE OCCURRENCE OF CRISTOBALITE AND TRIDYMITE IN SELECTED NORTH ISLAND SOILS A thesis presented in partial fulfilment of the requirements for the degree of Doctor of Philosophy in Soil Science at Massey University ROBERT CLELAND WALLACE 1987 i ABSTRACT The origin of cristobalite has been invest igated in a selection of soils from North Island . These include Tokomaru silt loam in the Manawatu , and Hamilton clay loam, Naike clay and Te Kowhai silt loam in the Hamilton basin . The occurrence of cristobalite , in conjunct ion with associated sand and silt mineralogy, has been used to interpret both the provenance of soil parent materials and aspects of soil genesis . Cristobalite isolated from the soils is a-cristobalite (opal-C) and is invariably accompanied by tridymite (tridymite-M structure ) . SEM data suggest that rather than discrete phases , cristobalite and tridymite usually occur intergrown with each other . Together they constitute up to 15% of the soils examined and usually occur in higher concentrations in upper soil horizons . Oxygen isotope abundances for cristobalite and tridymite range from 7 . 5-8 . 4 °/00 and are independent of grain size and relative proportions of cristobalite and tridymite. These data , together with the highly ordered crystal structure and subhedral morphologies of grains , indicate that cristobalite and tridymite formed at high temperature . Both are shown to occur in a number of the rhyolitic tephras from the Taupo Volcanic Zone (e . g . Aokautere and Okareka ashes) and leucocratic lavas from the Egmont cent re . Cristobalite and t ridymite in the soils therefore probably originated from volcanic sources . Various forms of amorphous silica were also identified in the soils of the Hamilton basin . In upper soil horizons, microfossils and phytoliths dominate but at depth the Naike c lay and Hamilton clay loam contain two inorganic forms of amorphous silica . These comprise ii microspheres similar to those described in precious opal . Oxygen i sotope data ( 2 6 . 6-2 6 . 9 °/00) are consistent with their being of low t emperature origin . In the Tokomaru silt loam, although the mineralogy is dominant ly quart zofeldspathic , variat ions in sand mineralogy and sand chemistry identify tephric additions at specific depths in the loess . Microprobe data on pyroxenes, amphiboles , glasses and titanomagnetites at these depths and in reference tephras f rom the Egmont cent re and the Taupo Volcanic Zone demonstrate that it is possible to ident ify the sources o f the tephras in the soil and so place some t ime constraints on the age of the loess : 0-5 0 cm 1 . 1 -1 . 2 m 1 . 2- 1 . 3 m c . 1 . 6 m c . 2 . 0 m 2 . 2 1 -2 . 34 m Mixed rhyolitic and andesitic tephras from the Egmont centre and the Taupo Volcanic Zone . These have accumulated during the last 1 1 ka . Rhyolitic ash, tentatively correlated with the Rerewhakaaitu Ash ( 1 4 . 7 ka B . P . ) from the Okataina centre . Andesit ic tephra from the Egmont centre . Andesit ic tephra from the Egmont centre . Andesitic tephra from the Egmont centre . Aokautere Ash ( 2 0 ka B . P . ) from the Taupo centre . The distribution of phytolith types in this soil demonstrate a change at c . 50 cm depth which is interpreted a s resulting from post­ glacial afforestation . This is inferred to have occurred at 11-12 ka B . P . Quartz accumulation rates demonstrate that there are markedly increased rates of loess accumulation from 1 4 . 7 ka to 12 ka , after which t ime there was a dramatic reduction . The loess that accumulated between these dates may not be so directly related to �old climate condit ions as to an increased supply of suitable material £rom local source s . iii ACKNOWLEDGEMENTS Dur ing the course of th i s research projec t I have rece ived suppor t and encouragemen t from many peop le and I wou l d like to expre s s m y grati tude t o the f o l lowing for thi s as s is tance . Dr . V . E . Nea l l , my princ ipal s upervisor , for h i s en thus iasm , patience and wise counse l when I dr i f ted into areas w i th which I was unfam i l iar and who a l lowed new and interesting avenues of inquiry to be free ly pursue d . T o the "Quaternary team" i n the Departmen t of S o i l Sc ience, Drs . R . B . S tewar t ( la t te r ly also as eo- s upervisor ) and A . S . Pa lmer , and Messrs C . G . Vuce t i c h and B . V . A l loway for he lp f u l d i s cuss ion dur ing the course of the project . Members o f the Depar tme n t o f Soi l Science , particularly Drs . J .A . P o l lok , M . A . Turner , A . N . Macgregor and J . H . K irkman encourage d and ass i s ted me in res o lving m inor prob lems o r i n learn ing new techn iques . To Drs . C . M . Lee s , J . P . S k ipwor th , R . N . Pate l and Mr . A . G . Robertson for i n i t i a l ass is tance w i th the inquiry into phyto l i ths . Drs . H . S . Gibbs and D . J . Lowe , Waikato Univers ity provided informa t ive as s i s tance and gu i dance when co l le c t ing the soi ls from the Hami l ton Bas in . Messrs D . H . Hop croft and R . Benne t , App lied Biochemis try Divis ion , D . S . I . R . and Dr . J . D . Co llen , V ictoria Univers i ty , are thanke d for s upp lying their techn ical s k i l ls and assis tance in producing the e le c tr on micrographs . Dr . P . Blattne r and Miss C . Hous ton , Geo logical Survey , introduced me to oxygen iso tope ana lys is technique s and s upp lied the oxygen isotope data . Mr . K . Pa lmer, V i c toria Un iversi ty, ass i s ted wi th the XRF ana ly ses and faci l i t a te d ready access to the e lec tron microprobe . Dr . C . W . Chi lds unde r took s ome pre liminary mossbauer s tudies and, together with Dr . J . D . G . Mi lne, made unpublishe d chemica l data avai lable . iv To the "produ c tion team", particu lar ly Glenys, Mar tin Egge ls and Anne Rouse for g i v ing of the ir t ime and expe r tise so free ly . Fina lly to my main suppor t team ( G lenys, Kerry, Hea ther and C le land ) for encouragemen t, support and patience dur ing a l l phases of the project . For s haring the "highs " w i th me and he lp ing me through the " lows" - Than k you . V TABLE OF CONTENTS ABST RACT . . . . • . . . . . . . . • • . • • . . . . . . . . • . . . . • . • . • . • . . . . • • . . . . . . . • . • . . . • . . . i ACKN OWLEDGEMENTS • • • . • . • . . . . . . . . . . . • . . . . • . • . . . . . . • . • . . . • . . . . • . . . • • . • i i i L I S T O F FIGU RES . . • . . . • • • • • . • . . . . • . . . • • . . • • • . • . . . . . . . • . . . . • . • • . • • . . • . ix L I S T O F T.ABLES . . . . . . • • . . • . . . . . . • . . . . . . . • • • . . • • • • . . . . . . . . . . • . . . . . . x i i i CHAPTE R 1 I n troduc t i on • . • . • • • . • . • • . • . . • . . . . . . • • • • • . . . . • • . • • . . • . . . . • . . . . . . . • . 1 A im s . . • . . • . • • • . • . . • . • . . • . • . . . . • . • . • . . • • • . . . • • . • • • . . • . • • . . . • . • . . . . . 3 CHAPTE R 2 Me thods and Technique s . • . . . . . . . . • • • • . • • . • • . • . . . . . . . . . . . . . . • . . . . . • • 4 Sample Preparation • . . . . . . . . . . . • • • . . • • . • • • • • • • • • . • • . . . . • . . • • . • • . • . . 4 Prepara t i on for Minera logica l Analy s i s • . • . . . • • • . . . • • . . . . . . • . • . . . . . 4 I s o lation of Cris tob a l i te . . . • • . • • . • • • • • . • . . . • • . • . . • . • . . • . . . . • . . . . • 5 I s o lation of Quar t z • . . • . . . . . . . . . . . . . • . • • . • • • . . . • . . . . . . • . . . . . • • . . . . 6 I s o la t i on of Phy to l i ths . . . . . • . • • • • • • • • • • . . • • . • . . . . . • . . • . . . . • . . . . . . 7 E lectron Microprobe Ana lysis . . . . . . • • . • • • • • . . • • . • . . . • • • • . . . . • . . • . . • 8 X-Ray F luorescence Ana ly s is . . . . • • • • • . • • • • . . . . • . • . • . . . . . • • • • • • • • • . . 9 Infrared Ana lys i s . • • . . . . • . . . • . . . . • . • • • . . . • • • . . • • . . • . • . • • . • • . . . . • • . 9 Phosphorus An a ly s i s • . . . • . . . . • . • • . • . • . • • • • . • • . . . • . . • • • • • . • • • . . • • . • . 9 Carbon Analys is • • • • • . . . • • • . . • . . • • • • • • • • • . • • • • . • . . • . . . . • . • • • • • • . . . . 9 Oxygen I s otope An a lys is . • . . . . • • • • • • • • • • • • . • • . • • • . • . • . . • . • . . • • . • • • 1 0 CHAPTER 3 The Dis tr ibution and Or igin o f Cris tobal i te and Tridym i te in some New Zea land S o i ls vi I n troduction . . . . . . . . . . . . . . . . . . . . . . . • . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 N omenclature . • . . • . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . • . . . . . 12 S tructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . • . . . . . . . 15 T herma l S tabi l i ty . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 I s o topes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 0 Occurrence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 1 Resu lts : Grain S i ze Dis tribut ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 Grain Morpho logy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35 Opa l-C and Tr i dym i te-M Nomenc lature . . . . . . . . . . . . . . . . . . 46 Crys ta l l i ni ty of Cris toba l i te and Tridym i te in the Soi ls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 9 Distribut ion o f Cris toba l i te and Tridym i te in the Soi ls . • . . . . . . . . • . . . . . . . . . . . . . . . . . . . . 62 Isotopes . . . . . . . . . . . . • . . . . . . • . . . . . . . . . . . . . . • . . . . . . . . . . 7 0 Igneous S ource s of Cris toba l i te and Tridymi te . . . . . . . . 7 3 Other Components in the S o i l • . . . . . . . . . . . . . . . . . . . . . . . . 7 6 D i s cu s s ion : T r i dym i te in New Zea land S o i ls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84 S o i l S tratigraphy and Parent Mate r i a l . . . . . . . . . . . . . . . . . . . . . . . . . . 85 O r i g in of Cris toba l i te and Tridymi te in Soi ls . . . . . . . . . . . . . . . . . . 95 C r i s toba l i te a s a Tracer for Tephras . . . . . . . . . . . . . . . . . . . . . . . . . . 1 0 1 Amorphous S i lica i n Hami l ton Bas in S o i ls . . . . . . . . . . . . . . . . • . . . . . l02 CHAPT E R 4 Sand and S i lt Minera logy and Geochemis try of the Tokomaru S i l t Loam I n troduction : Previous Work . . . . . . . . . . • . . • • . • • • . . . . . . . . . . . . . . • . • . • • 107 The Prese n t S tudy . • . • • • • • • . • . • • • • • • • • . . • . . . • . . . . . . . . 1 14 Res u lts : Grain S i ze Data . . • • . • • • • • • • • • • • • • • • . . . . • • • • • • . . . . . . . 1 17 Optica l Minera logy . . . • . • . . . • • . • . . • . • . . . . • • • • • • • • • • • • 12 0 Miner a 1 Chemistry . . . . . . • . . . • • • • • • • . • . . . • . • • . . • • • . • . • 1 3 5 Dissolution Techn iques • • • • • • • • • • • • • . . • . • • • • • • • . . . . • . 1 4 9 Major and Trace E lement C hemis try o f the Soi l . . • . • • . 15 1 Phyto l i ths . . . • • . . • . . . . • • • .• . • • • . . • • • • . . • . • . . • • • . • • • . . 1 6 0 v i i D i s cuss ion : Tephra i n the Ohakea Loe s s in the Manawa tu . . . . . . . . . . . . . . . . . . . . 172 I den t i f i c a t ion of Tephra S ources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 5 Tephra Corre lat ion . . . . . . . . . . . . . . . . . • • . . . . . . • . . . . . . • . . . . . . . . . . . 177 The S i gni f i cance of Biogen i c S i lica in the Tokomaru Soi l . . . . . . 182 Loe s s Provenance . . . . . . . . . . . . . . . . . . • . . . . . . . . . . . . . . . . . . . . . . . . . . . 184 Pos t-Glac i a l Loess Source . • . . . . . . . . . . . • . . . . . . . . . . . . . . . . . . . . . . . 1 9 0 The Pa laeosol in the Ohake a Loess . . . . • . . . . . . . . . . . . . . . . . . . . . . . . 1 92 Fragipan Genesis . . . . . . . . . . . . . . . . . . . . . . . . • . . . . . . . . . . . . . . . . . . . . . 19 5 Ye l low- Grey Earth and Ye l low-Brown Earth/Ye l low- Brown Loam I n tergrade Re lationships . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 03 Sedime n ta tion History of t he Tokomaru S o i l . . . . . . . . . . . . . . . . . . . . 2 0 9 Accumulation and Sedimen ta tion Rates . . . . . . . . . . . . . . . . . . . . . . . . . . 2 1 1 CHAPTER 5 Summary and Conc lus ions : C r i s toba l i te Genesis . . . . . . . . . . . . . . . . • . . . . . . . . . . . . . . . . . . . . . . . . . 2 1 6 Tokom aru Soil . . . . . . . . . . . • . . . • . . . . . . . . . . • . . . . . . . . . . . . . . . . . . . . . . 2 1 8 APPENDIX 1 Grain s i ze d i s t r i bu t i on in the Waiareka, Ham i l ton , Naike and Te Kowhai s o i ls . . • . • . • . • • . . . . . • . . . . . . . . . . . . . . . . . . . . 2 2 2 APPENDIX 2 Cris tobalite and quar t z in the s i l t and clay fractions of the Hamilton , N a i ke and Te Kowhai s o i ls . . • . . . . . . . . . . . . . 2 2 3 APPENDIX 3 Description o f m inerals iden t i f ie d in the Tokomaru s o i l . . . . . . . . . . . . . . . . • . . • • • . . . . • . . . . . . . . . . . 2 2 4 APPENDIX 4 Tokomaru s o i l - grain s ize dis tr ibution . • • . • . • . . . . . . . . . 2 2 9 APPENDIX 5 Mineral frequency data from the Tokom aru s o i l • • • . • . . . . . 23 0 APPENDIX 6 Geochem ical data from the Tokomaru s o i l . • • . . • • . • . . . . . • . 23 8 APPENDIX 7 Electron m i crop robe analyses of tephra m inerals . • • . . . . • 242 APPENDIX 8 Proportion of the Tokomaru soi l fract ions r emoved dur in g the dissolu t i on treatments • • • . • • • • • . . • . . . • • • . . • • • • • • • •. • 275 v i i i APPENDIX 9 Key to samp le depths . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 7 6 APPENDIX 10 Ana lyses of P and C in the Tokomaru s o i l . . . . . . . . . • . . . . . 2 7 7 APPENDIX 1 1 Heavy mine r a l conte n t o f the Hami lton , Naike and Te Kowhai s o i ls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . • 2 7 8 APPENDIX 12 Microprobe ana lyses o f minerals from the Tokomaru s o i l . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 7 9 REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 9 3 ix L:IST OF F:IGURES Figure Page 3 . 1 : Diffraction t races of forms of silica . . . . . . . . . . . . . . . . . . . . . . . . . 1 3 3 . 2 : Summary of the thermal transitions of some silica phases . . . . . . 1 8 3 . 3 : Location map of part of the Hamilton basin . . . . . . . . . . . . . . . . . . . . 2 8 3 . 4 : Variations in the grain size distribut ion in the Hamilton clay loam . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33 3 . 5 : Variat ions in the grain size dist ribut ion in the Naike clay . . . 3 4 3 . 6 : Variations in the grain size distribution in the Te Kowhai silt loam . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 6 3 . 7 : Typical form of cristobalite in the soils studied . . . . . . . . . . . . . 37 3 . 8 : Less common forms of c ristobalite in the soils studied . . . . . . . . 38 3 . 9 : Less common forms of cristobalite in the soils studied . . . . . . . . 3 9 3 . 1 0 : Electron micrograph of cristobalite from pumiceous xenoliths in Tarawera Basalt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40 3 . 1 1 : Electron micrograph of the lepisphere form of cristobalite . . . . 4 1 3 . 12 : Electron micrograph of the hexagonal tabular form of cristobalite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 3 3 . 13 : Infra-red spectra o f some silica phases from soils in the Hamilton basin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 4 3 . 1 4 : Morphology o f the concentric form o f opal-A . . . . . . . . . . . . . . . . . . . 45 3 . 1 5 : Morphology of the dusty opal-A . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 7 3 . 1 6 : XRD patterns of tridymite and cristobalite . . . . . . . . . . . . . . . . . . . . 4 8 3 . 17 : XRD patterns for opal-C, tridymite-M and quartz in the silt fractions of the Hamilton, Naike and Te Kowhai soils . . . . . . . . . . 5 1 3 . 1 8 : XRD patterns of the clay fractions in the Hamilton soil . . . . . . . 6 0 3 . 1 9 : XRD patterns of the clay fractions in the Naike soil . . . . . . . . . . 6 1 3 . 2 0 : XRD patterns of the clay fractions in the Te Kowhai soil . . . . � . . 63 3 . 2 1 : Hamilton soil - Abundance of cristobalite and tridymite in the silts and clay fractions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64 3 . 22 : Naike soil - Abundance of cristobalite and tridymite in the silts and c lay fractions . • . • . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 6 X Figure Page 3 . 2 3 : Te Kowhai soil - Abundance of cristobalite and tridymite in the silt and clay fractions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68 3 . 2 4 : Typical XRD spectra of silica phases in Egmont loam and andesitic lavas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 1 3 . 2 5 : XRD spectra of silica phases in the Aokautere Ash . . . . . . . . . . . . . 7 4 3 . 2 6 : XRD spectra of cristobalite and tridymite in erupt ives associated with the Okataina Volcanic Centre . . . . . . . . . . . . . . . . . . 7 5 3 . 2 7 : Quart z distribution in the silt and clay fract ions o f the Hamilton and Naike soils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 7 3 . 2 8 : Quart z distribut ion in the silt and clay fract ions o f the Te Kowhai soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 9 3 . 2 9 : Distribut ion of the heavy fraction in the sand fract ions of the Hamilton soil . . • . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 0 3.3 0 : Distribution o f the heavy fraction in the sand fract ions of the Naike soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 1 3 . 31 : Dist ribution o f the heavy fraction in the sand fractions of the Te Kowhai soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82 3 . 32 : Correlation diagram for the Naike and Hamilton soils and the Te Kuiti and Welches Road sections . . . . . . . . . . . . . . . . . . . . . . . . 8 6 4 . 1 : Location map of part of central New Zealand . . . . . . . . . . . . . . . . . . 1 0 8 4 . 2 : Variat ion in grain size dist ribution for the Tokomaru silt loam . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1 8 4 . 3 : Tokomaru soil - Abundance of volcanic plagioclase , volcanic lithic, and glass in the non-magnetic fraction of the fine sands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122 4 . 4 : Distribution of the illite greywacke lithic and quartz + sedimentary plagioclase as a proportion of the sedimentary fract ion in the non-magnet ic fraction of the fine sand in the Tokomaru soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123 4.5 : Variation in the total volcanic component of the non­ magnetic very fine sand and fine sand fractions of the Tokomaru soil . . • . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 4 x i Figure Page 4 . 6 : Distribution of mineral phases in the magnetic fraction of the fine sand of the Tokomaru soil (hornblende, orthopyroxene , clinopyroxene and plagioclase) . . . . . . . . . . . . . . . . 125 4 . 7 : Tokomaru soil - Further abundance of volcanic components in the magnetic fract ion of the fine sand (opaques , plagioclase volcanic lithic , obs idian , and plagioclase- opaque volcanic l ithic ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126 4 . 8 : Abundances of the total volcanogenic component in the magnetic fract ions of the fine and very fine sands in the Tokomaru soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . : . . . . . . 127 4 . 9 : Tokomaru soil - Mineral distribution in the non-magnetic fraction of the very fine sand . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129 4 . 10 : Abundances of minerals in the magnetic fraction of the very fine sand in the Tokomaru silt loam . . . . . . . . . . . . . . . . . . . . . . . . . . 130 4 . 11 : Tokomaru soil - Mineralogical variat ions within the very fine sand as determined on grain counts . . . . . . . . . . . . . . . . . . . . . . 132 4 . 12 : Variation in the mineralogy of the coarse silt in the Tokomaru soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134 4 . 13 : Comparison of the chemistries of the amphiboles from the Tokomaru soil with those from the Taupo and Egmont centres . . . 140 4 . 1 4 : Bi-variant plot of MnO and enstatite content for orthopyroxenes from the Taupe , Tongariro and Egmont centres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141 4 . 1 5 : Distribution of orthopyroxene from the Tokomaru soil on an MnO - enstatite plot . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 4 4 4 . 1 6 : Comparison between the chemistry of the clinopyroxenes from the soil and those from possible source regions . . . . . . . . . . . . . . 145 4 . 17 : Harker diagrams demonstrating the discrete nature of the chemical trends between Egmont centre and the Taupe Volcanic Zone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 7 4 . 1 8 : Chemical variation diagrams demonstrating the s imilarity between the compositions of glas ses in the Tokomaru soil and possible sources . . . . . . . . . . . . . • . . . . . . . . . . . . . . . . . . . . . . . . . . . 148 4 . 1 9 : P roportion of the Tokomaru soil removed during the acid dissolution sequence . . . . . . . . . . . . . . . . • . . . . . . . . . . . . . . . . . . . . . . . . 150 x i i Figure Page 4 . 2 0 : Distribution o f the maj or elements in the sand fraction and total soil in the Tokornaru silt loam . . . . . . . . . . . . . . . . . . . . . . . . . 1 5 5 4 . 2 1 : Distribution of V , Mn , Ba , Y and Z r i n the sand fraction and total soil of the Tokornaru silt loam . . . . . . . . . . . . . . . . . . . . . 161 4 . 22 : Typical phytoliths extracted from the Tokomaru soil . . . . . . . . . . 165 4 . 2 3 : General view of the low density fraction from samples T2 3 and T 1 8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166 4 . 2 4 : Relative dist ribut ion of the more common forms of biogenic silica between 1 0 and 90 cm depth in the Tokomaru silt loam . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . : . . . . . . . . . . . . . . 167 4 . 2 5 : Phytoliths extracted from vegetation . . . . . . . . . . . . . . . . . . . . . . . . . 168 4 . 2 6 : Typ ical phytoliths extracted from peats . . . . . . . . . . . . . . . . . . . . . . 1 7 1 4 . 2 7 : Post-glacial loess unconforrnably overlying older loess units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193 4 . 2 8 : Well developed columnar structure formed in loess near the Tokomaru sit e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199 4 . 2 9 : Columnar structures developed in a spoil heap . . . . . . . . . . . . . . . . 2 0 4 4 . 3 0 : Quartz accumulation rates in the fine and coarse silts in the Tokomaru soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 1 3 xiii LIST OF TABLES TABLE Page 3.1 Summary of oxygen isotope data for cristobalite . . . • . . . • . . . . . . . • 22 3 .2 Cristobalite content of the Tokomaru and Onaero soils . . . . . . . . • . 69 3.3 Oxygen isotope data from silica phases in soils from the Hamilton basin . • . . • . . . . . . . . . . . . • . . . . • . • . . . • • . • . . . . . . . . . . . . • 72 4.1 Mineralogy of some volcanic centres in the North Island . . . . . . �136 4 .2 Relative proportion of biogenic silica in the Tokomaru soi1 . . • 1 69 4 . 3 Chronology of major eruptions from the North Island in the last 20 ka . . . . . . . • • . . . . . . • . . • . . . • . . . • . • between pp. 178-179 1 CHAPTER ONE INTRODUCTION During weathering silica is released to the soil solution and while much of this is lost from the soil (e . g . Stevens and Vucet ich 1 9 84 ) the occurrences of ' s ilica ' cements in duripans , silans and "silcretes" indicates that some silica, probably as amorphous coatings , remains in the soil . Investigation of the transformation of amorphous silica to cristobalite ( in deep sea sediments , and precious opal ) has demonstrated that cristobalite could form from amorphous opal under temperatures and pres sures similar to those in the pedosphere . It has been suggested (e . g . see McKeague and Cline 1 9 6 3 ; Lowe 1 9 8 6 ) that cristobalite in soils is pedogenic . The present study was undertaken to carry out a detailed investigation of the mineralogy of selected North Island soils , using oxygen isotope analysis and optical techniques to determine the validity of the pedogenic origin hypothesis for cristobalite in soils . Applicat ion of thermodynamic principles to isotopic systems predicts that temperature and initial 18o;1 6o ratio of a system are the ma j or factors determining the fractionation of 18o and 1 6o between a hydrous fluid or melt and phases crystallising from such a system (Urey 1 947 ) . The amount of 1 8o and 1 6o entering a mineral st ructure during formation is dependent on molecular vibrations which are in turn proportional to the mass of the atoms involved. Increased thermal energy at higher temperatures minimises the effect of mass difference , and the fractionation factor is therefore lowered . The temperature dependent nature of the fract ionation has been used to establish marine palaeotemperature scales . These methods use the fractionation of 1 8o and 1 6o between calcareous or siliceous organisms and sea water ( see Urey et al . 1 9 5 1 ; Epstein et al . 1 95 3 ; Emiliani 1 9 6 6 ; Shackleton 2 and Opdyke 1 97 3 ) and this technique is now commonly used in palaeoenvironmental studies . Invest igation of oxygen isotopes in s ilicate systems (e . g . Taylor and Epstein 1 9 62 ; Garlick and Epstein 1 9 6 7 ; Savin and Epstein 1 97 0 ) demonstrated that the re was considerable isotopic fractionation between mineral/mineral and mineral/melt pairs and that these were shown to vary systemat ically with inferred t emperature of formation (Clayton and Epstein 1 9 58 ; Engel et al. 1 9 5 8 ) . Subsequent calibrat ion of the fractionations between specific mineral pairs has led to their use as geothermometers (e . g . O ' Neil and Epstein 1 9 6 6 ; O' Neil and Taylor 1 9 67 ; Epstein and Taylor 1 9 67 ; Bottinga and Javoy 1 9 7 3 ; Blattner and Bird 1 9 7 4 ) . The isotopic composition of a mineral is therefore a function of temperature and the composition of the system from which the mineral forms . While in many instances the isotopic composition of the system is poorly known , in general low o18o f ractionat ion indicates high temperature of formation and high f ractionat ion values indicate low temperatures of formation . As part of developing improved techniques for soil sand mineralogical identification an investigat ion of the Tokomaru silt loam was undertaken (Wallace and Neall 1 9 8 4 ) and thin section techniques suitable for investigating the internal morphologies of grains developed . With these techniques it is now possible to ident ify phases within pumiceous fragments and to differentiate lithic grains of sedimentary origin from those of igneous origin . During this developmental stage minor amounts of cristobalite were identified in the Tokomaru silt loam, so a detailed investigation of this profile was also undertaken . 3 The primary aims of the present invest igation were : ( 1 ) To determine the occurrence , distribution and origin of cristobalite and associated phases in North I sland soils using oxygen isotopes as a principal tool . ( 2 ) To ident ify the nature and distribution of silica phases other than quart z and cristobalite in the soils . ( 3 ) To tabulate the principal mineral constituents of the sand and silt fractions of the Tokomaru silt loam and to quant ify the tephra input . ( 4 ) To ident ify the source ( s ) of the tephric additions to the Tokomaru silt loam . ( 5 ) To interpret the pedogenesis of the soils studied . 4 CHAPTER TWO METHODS AND TECHNIQUES SAMPLE PREPARATION This investigation was concerned with detailed studies of selected soils to ascertain the provenance of their soil stratigraphic unit s . A continuous channel sampling method was used . Sampling involved excavating a channel up to 15 ern deep and covering a 1 0 ern vertical interval ( or t o horizon boundaries where they were convenient or sharp) . Samples were taken to a depth of one metre in the Hamilton s ilty clay, Naike clay and Te Kowhai silt loam and to 2 . 5 m in the Tokornaru silt loam . Where there were prominent vertical joints these were avoided to minimise contaminat ion from illuvial materials . The samples were air dried, gently crushed to pass through a 2 mm sieve and subdivided using a Jones splitter into approximately 1 0 0g samples . Large samples were obta ined because it was ant icipated that most of t he work would be done on the coarser fractions and these were relatively minor constituents in all the soils . The soil samples were treated with NaOAc-HOAc (pH 5 ) , H2o2 and s odium citrate-sodiurn bicarbonate-sodium dithionite (CBD ) to remove carbonates , organic matter and cementing materials respectively ( Jackson 1 9 5 6 ) . They were then fractionated into various s i zes by s ieving ( >63 �) , sedimentation ( 63-2 0 �) and centrifugation ( 2 0-5 �, 5-2 �, <2 J.lrn) after Jackson ( 1 9 5 6 ) . PREPARATION FOR MINERALOGICAL ANALYSIS The soils have a low rnafic content so concentration of this f raction was achieved using either a Franz Isodynarnic Magnetic Separator to separate magnetic and non-magnetic fractions or 5 bromoform (specific gravity of 2 . 8 ) to produce a heavy and light fract ion . Prelimina ry investigation of the coarser fractions involved opt ical investigat ion of grain mounts for each particular size f raction . Volume percentages of the various phases were determined using a ribbon point count method (Galehouse 1 9 6 9 ) with between 5 0 0 and 1 0 0 0 points (depending on the required accuracy, Pett i j ohn et al . 1 9 7 2 ) being counted . Duplicates of some fract ions indicated that the various trends are significant . For detailed investigations thin sections and polished thin sections of the various light and heavy, magnetic and non magnet ic fractions were prepared (Wallace et al . 1 9 8 5 ) . The categories of mineral frequency are : abundant , 5 0 -30% ; very common, 29-10% ; common, 9-5%; scarce , 4 - 1% and rare <1% . The mineral categories are briefly described in Appendix 3. XSOLATXON OF CRXSTOBALXTE To carry out the oxygen isotope investigation of cristobalite it was necessary to obtain a pure concent rate and a method us ing chemical dissolution and density separation was employed . Chapman et al . ( 1 9 6 9 ) describe a method involving a fusion with sodium pyrosulphate ( Na2s2o7 ) followed by t reatment with fluoros ilicic acid (H2SiF 6 ) to determine the amount of quartz in a soil quantitatively . Henderson et a l . ( 1 97 2 ) modified this technique by subst ituting an HCl /NaOH cycle for the sodium pyrosulphate treatment because fusion with Na2s2o7 t ends to enrich the 1 8o content of cristobalite (Henderson et al . 1 9 7 1 ) . Subsequent work (Pisciotto 1 97 8 ) however, has shown that the pyrosulphate step minimally depletes the 1 8o ( <1 °!00 ) . This apparent contradict ion was not investigated during the present study and the method of Henderson et al . ( 1 9 7 2 ) has been used here with minor modifications . Most previous workers used highly weathered material or relatively pure samples (mainly geological and not pedological ) which were free of volcanic glass . The glass present in the soils of this s tudy caused problems as it is of a variable density and is relatively unreactive to the HCl /NaOH/H2SiF6 (ABFS ) t reatment . Rather than subject the sample to excessive ABSF treatments to remove 6 the glass , and therefore perhaps preferent ially remove low temperature cristobalite , an ext ra density separation ( SG c . 2 . 25 Mg m-3 ) was used . Init ial work showed that the cristobalite in the coarse fractions of the soils studied occurs as cristobalite aggregated with clay or as intergrowths (e . g . with feldspar ) . It was therefore necessary that , after the init ial cleaning of the sample and division into size fract ions , the samples be given a 2 4 hour ABSF treatment to remove most of the impurities and any coat ings or intergrowths associated with the cristobalite . The samples were then mixed with polyvinylpyrrolidone (PVP ) using the ultrasonic probe for dispers ion , transferred to test tubes containing the tet rabromoethane nit robenzene solution ( SG 2 . 38 ) with an eye dropper and centrifuged for the prescribed t ime . This step was repeated unti l X-ray diffraction (XRD ) indicated that quart z was absent . Most o f the light fraction contains significant amounts of biogenic silica and glass so rather than sub ject the cristobalite to repeated ABFS t reatments to remove the biogenic material a second density separat ion ( SG c . 2 . 25 Mg m-3 ) was undertaken . This concentrate was given a final ABFS treatment , treated overnight with boric acid (Sridhar et al . 1 97 5 ) and given an XRD and scanning electron microscope ( SEM) purity check . The amount of cristobalite was determined by quantitat ive XRD techniques. After ABFS treatment to remove t he feldspars and ferromagnesian minerals , cristobalite , quart z and glass remained . A method intergrating the area under the peaks was used to determine the amount of cristobalite and quartz and these were corrected to account for the ABFS-soluble fraction and the amount of glass . ISOLATION OF QUARTZ While the quart z content of the coarser fractions was determined by optical methods this was not appropriate for the finer fractions and dissolution techniques were employed . The samples were given repeated HCl /H2SiF6 treatments (Henderson et al . 1 972 ) until XRD showed that only quart z remained . Samples were repeatedly washed, then dried and weighed. Where there was significant cristobalite in a sample the amount of quartz was determined, together with the cristobalite by the XRD techniques described above. XSOLATXON OF PHYTOLXTHS 7 In an attempt to investigate the vegetative history of the Tokomaru silt loam, opal phytoliths were separated from various depths in the soil, and for comparison, from tree species and two peats. Separation of Phytoliths from the Soil: The technique for isolation of phytoliths from the soil is similar to that of Rovner (1971) . The process was modified to account for lower yields at depth and to split off the coarse fraction (mainly coarse organic matter) and fine fractions (Jackson 1956) to reduce the bulk. The procedure is as follows: ( 1 ) Acidify 60 grams of soil with HOAc and treat overnight with H2o2 to remove most fine organic matter, then disperse ultrasonically. {2) Wash into test tubes through a 250 � sieve {to remove the coarse fraction, commonly dominated by organic matter) and centrifuge, discarding the <5 � fraction. ( 3 ) Add dilute HCl to the test tubes and heat in a water bath, avoiding excessive heat, to remove remaining cementing materials. ( 4 ) Repeatedly wash, ultrasonically disperse and spin down until the supernatant is clear. (5) If required for ease of handling, split the sample into required grain size fractions by adjusting the centrifuging time and speed (Jackson 1956), then dry. (6) A suitable mixture of nitrobenzene and tetrabromoethane to give a density of 2.3 is used to separate off the light (phytolith-bearing) fraction (Rovner 1 9 7 1 ) . Remove the light fraction and repeat density separation on the sample until the yield is negligible. Wash the light fraction repeatedly with acetone, dry, weigh and mount. 8 Separation of Phytoliths from Vegetation: Early investigators commonly used high temperature oxidation to concentrate the phytoliths in vegetation (Beavers and Stephen 1 9 5 8 ; Lanning et al. 1 9 5 8 ; Twiss et al. 1 9 6 9 ) but this method produced distorted or fused material that had frequently been transformed to cristobalite (Jones and Handreck 1 9 6 7 ) . Jones and Milne ( 1 9 63 ) used a nitric/perchloric acid digestion mixture at relatively low temperatures and preserved the phytolith outlines more faithfully. This method, as refined by Rovner ( 1 97 1 ) was used to prepare material for the current study. In many cases the acid digest produced a waxy cake so the samples were finally heated in acetone to remove the wax. ELECTRON MICROPROBE ANALYSES Although the sand mineralogy preserves a record of volcanic additions to the mainly quartzofeldspathic Tokomaru silt loam (Wallace and Neall 1 9 82 ) , the Aokautere Ash is the only macroscopic indicator of tephric additions. Thus bulk sampling methods (e. g. Kohn 1 9 7 0 ) are inappropriate for determining the chemistries of the volcanic additions. The fully automated JEOL JXA7 33 superprobe at Victoria University was used to determine the mineral chemistries and so help elucidate the origins of the volcanic materials. After separation of the required grain size fraction, polished thin sections (Wallace et al . 1 9 85 ) were prepared and the minerals analysed for the major elements using 1 5 Kv, 12 nano-amps and a focussed beam counting for three ten second periods (Watanabe et al . 198 1 ) . The analysis of glasses, particularly alkali loss, is a problem with a microprobe (Wallace 1 9 7 4 ; Froggatt 1 9 8 3 ) . To analyse glasses the beam current was lowered to 8 nano-amps, beam diameter increased to 1 0 � and a fresh area of glass chosen for each of the 10 second counts. 9 X-RAY FLUORESCENCE ANALYSES Major element chemistry was determined by using the fused disc method (see Roser 1983), after the samples had been ground in a tungsten carbide mill. Loss on ignition is determined by the weight loss on heating to 1000°C. Trace elements were analysed on borate­ backed pressed pellets (Roser 1983) . INFRA-RED ANALYSIS For infrared analyses one milligram of sample was ground with 170 milligrams of KBr and pressed under vacuum into a glass disc. After overnight drying at 55°C the sample was analysed in a Pye Unicam Sp3-300 infrared spectrophotometer. PHOSPHORUS ANALYSIS As well as being determined by XRF methods the phosphorus content of the Tokomaru silt loam was determined colorimetrically after ignition at 550°C and 16 hours of end over end shaking in 1N H2 so4 (Walker and Adams 1958). CARBON ANALYSIS Carbon was determined with a LECO induction furnace using the standard LECO method. The carbon is converted to co2 which is then adsorbed onto ascarite (NaOH + asbestos) which is weighed. 10 OXYGEN ISOTOPE ANALYSIS The oxygen isotope analyses were carried out on a NAA 6-60 RMS , 15 cm radius, 60° sector double collecting mass spectrometer at the Institute of Nuclear Sciences. Oxygen is liberated by reaction with BrF5 at high temperature (Clayton and Mayeda 1 9 6 3 ) and then using a Toepler pump (Blattner and Bird 1974 ) is converted to co2 which is the feed stock to the mass spectrometer. The data is reported as parts per thousand, 0!00, relative to standard mean ocean water (SMOW of Craig 1 9 6 1 ) . CHAPTER THREE THE DISTRIBUTION AND ORIGIN OF CRISTOBALITE AND TRIDYMITE IN SOME NEW ZEALAND SOILS INTRODUCTION 11 Cristobalite, tridymite and quartz, together with opaline silica are the silica phases of significance in soils (Wilding et al. 1977). One of the initial aims of the present project was to both investigate the source (s) of cristobalite in selected New Zealand soils and to determine its significance in soil genesis. Preliminary tests showed, however, that cristobalite is intimately associated with tridymite in the soil so the project was expanded to include studies of tridymite as well. In siliceous deep sea sediments biogenic silica (also referred to as amorphous silica or opaline silica) is transformed during diagenesis to cristobalite-tridymite phases (Wise and Hsu 1971; Hein 1981; Iijima and Tada 1981) . Opaline silica in soils is thus a potential precursor of cristobalite and/or tridymite so forms of opaline silica in soils are therefore also included in this review. NOMENCLATURE Cristobalite forms either during diagenesis (here referred to as the low temperature pathway) or under conditions such as those associated with ,igneous processes (here referred to as the high temperature pathway) . (a) Low Temperature Pathway: Studies of the "low temperature" pathway (e.g. Florke 1955; Jones et al . 1963) showed that there were two broad groupings of "opaline silica": Type-1: specimens that gave x-ray patterns indicative of a well- ordered crystal structure, Type-2: samples that were almost amorphous, giving only a few diffuse x-ray bands (see Fig. 3.1). Florke (1955) also showed that there were some tridymite reflections in x-ray scans of "opaline silica". A comprehensive examination of gem opal and a-cristobalite by Jones et al . (1963, 12 1964) showed that the opal structure could vary from highly crystalline (a-cristobalite) to x-ray amorphous (opal) . They produced x-ray diffraction ( XRD) traces that showed opals corresponding to type-2 had only a broad peak at 4. 1A while type-1 opals showed XRD patterns with sharper and more numerous peaks corresponding to a­ cristobalite. Electron microscope scans of fracture surfaces of opals indicated a distinct difference in surface morphology between the two types of opal (Jones et al . 1964). Type-1 opaline silica had a fine grained featureless surface while the surface of type-2 opaline silica comprised closely packed silica spheres (individual spheres were 1500-35Q� in diameter and uniform for a specific sample, see also Jones et al . 1964; Wenk et al . 1976; Klein and Hurlbut 1985). Jones and Segnit (1971) subdivided the low temperature silica phases into three groups based on XRD patterns: (1) Opal-C: considered to be the equivalent of a-cristobalite. It is recognised that minor tridymite may be present as tridymite subdomains in a dominantly cristobalite structure. Opal-C is identified by having at least a full range of XRD peaks (4. 05, 3.14, 2.85, 2. 48, 2.12, 2.02, 1. 93, 1. 87A - see also Brown 1980; Carpenter and Wennemer 1985), (2) Opal-CT: having only two peaks present, 4.1A and 2. 48A. These peaks are broad reflecting various degrees of structural disorder. There is often considerable interstratified.tridymite, and (3) Opal-A: which includes varieties of hydrous silica with a broad diffuse XRD band at c . 4. 1A. Most precious opals occur in this group. In experiments in which opal-A was heated Jones and Segnit (1971) showed that, with time and temperature, the 4. 1A cristobalite peak developed out of the broad opal-A band. This confirmed earlier 01( CO 'Oil' N 01( 01( 01( 01( 01( 01( 1/') ..,. r-- M NN CO .-4 CO 0\ 0 .-4 . N ('() .-4 .... NN so 40 30 Degrees 29 01( .-4 ..,. 20 A) D) E) F) Figure 3. 1: Diffraction traces of forms of s i l ica . A is a lpha-cristobalite: B is opal-C: C, D and E are opa l-CT: F is opal-A . Adapted from Jones and Segnit ( 1971). Q is quartz . T i s tridymite. 1 3 data from Florke (1955) and Frondel (1962) from which they concluded that the sequence opal-A opal-CT opal-C was a continuum. On heating, the tridymite disorder diminishes but tridymite may still be present in opal-C, suggesting that the tridymite domains are large enough to resist thermal conversion to cristobalite. 14 From the above studies it is concluded that during early diagenesis there is a relatively low temperature discontinuous transition from poorly crystalline hydrous silica to cristobalite and that, based on XRD characteristics, this can be divided into three forms: Opal-A (highly disordered, near amorphous), opal-CT (disordered cristobalite with tridymite subdomains) and opal-C (ordered a-cristobalite). The considerable structural disorder of opal-CT, manifest as tridymite stacking, can persist through the transition to opal-C. (b) High Temperature Pathway: Opal-C is usually referred to as a-cristobalite when it forms in high temperature environments. Studies involving reactions of a-cristobalite show that it has a similar structure to opal-C (e. g. Brown 1980; Carpenter and Wennemer 1985) and also highlight the complexity of the relationship between cristobalite and tridymite (Hill and Roy 1958a, 1958b; Sato 1963a, 1963b, 1963c; Roy and Roy 1964; Rockett and Foster 1967; Tada and Iijima 1983; Carpenter and Wennemer 1985). In a detailed study of synthetic tridymite, Hill and Roy (1958a, 1958b) identified metastable (tridymite-M) and stable (tridymite-S) varieties, each of which had its characteristic x-ray pattern and therefore structure. Sato (1963a, 1963b, 1963c) further developed the nomenclature of these structural states and introduced a third form, tridymite-MS. Sato identified the various forms of tridymite according to the degree of development of minor peaks and the.presence or absence of doublet peaks. Tridymite-S Doublet peaks at 3. 85, 3. 0, 2. 5, 2.3A and only a very weak peak at 3.25A. Tridymite-M No doublets but a strong 3.25A peak. Tridymite-MS Doublet peaks at 3.85, 3. 0, 2. 5, 2. 3A and a strong peak at 3.25A. The complex nature of the tridymite structure makes XRD identification of tridymite difficult, not just because there is considerable variability in the presence or absence of peaks but because the major peaks (4.33, 4.10 and 3.83A) show a considerable range of relative intensities (see Hill and Roy 1958b; Sato 1963a, 1963c; Roy and Roy 1964; Rockett and Foster 1967; Carpenter and Wennemer 1985) . It was also shown that these tridymites might be interstratified with cristobalite . The terminology used in the present report is based on the criteria established by Jones and Segnit (1971) and Sato (1963a, 1963c). The term opal/cristobalite is used to denote the whole group opal-A, opal-CT and opal-C. STRUCTURE 15 Cristobalite and tridymite are tectosilicates comprising a three dimensional framework of Sio4 tetrahedra although the precise nature of the structure is not well understood. The tetrahedra combine in relatively regular 6-sided rings with the apical oxygen of the tetrahedra pointing alternately up and down. Kihara (1978, 1980) reports that in some tridymite the rings are deformed into "D" shapes. The rings form sheets which are stacked perpendicular to the (111) axis in cristobalite and the (0001) axis in tridymite. In tridymite the basal oxygens are positioned directly above those in the underlying sheets while in cristobalite the Sio4 tetrahedra in each additional sheet are rotated by 60°. To make up a unit cell the sheets of Sio4 tetrahedra are stratified in an ABC-ABC-ABC sequence (see Deer et al . 1967-) in cristobalite ( i . e . 3 sheets repeated) and AB-AB-AB pattern in tridymite (a 2 sheet repeat sequence) . Commonly tridymite domains and cristobalite domains occur within the one unit, i.e . mineral grains often contain interstratified sequences of tridymite and cristobalite. A comprehensive examination of the transformation of opal to c.ristobalite (Jones et al. 1963, 1964) showed that there was a continuous variation from amorphous opal to poorly ordered cristobalite with tridymite domains (opal-CT) and finally a-cristobalite (opal-C) . Similarly tridymites have been shown to contain cristobalite (opal-C) domains (Hill and Roy 1958a, 1958b; Roy and Roy 1964; Carpenter and Wennemer 1985) . 16 The structural relationship between the Sio4 tetrahedra in cristobalite and tridymite produces a comparatively open, low density structure with relatively large channels or openings (1. 7A in cristobalite and 1. 3A in tridymite, Holmquist 1961) in which foreign ions might be trapped (e.g. Na, K, Li, Al). It may be that these ions are necessary to stabilise the structure under surface conditions. Tridymite can only be synthesised in the presence of mineralisers and some authors (e. g. Florke 1955; Holmquist 1961) have suggested that tridymite may not be a polymorph of silica but rather a binary system with alkali oxides. Mason (1966) suggests tridymite may be isomorphous with feldspathoids. Hill and Roy (1958b) and Rockett and Foster (1967) however, argue that tridymite is a polymorph of silica. A distinct morphology of opal-CT was described from deep sea sediments and coastal plain sediments of the eastern United States (Rex 1969; Calvert 1971a, 1971b; Weaver and Wise 1972; Wise and Hsu 1971). This consisted of small, spherulitic rosettes 3-10 � in diameter and comprising thin, radiating blades between 300-500A thick. The term lepisphere was proposed by Wise and Kelts (1972) for opal-CT with this morphology (see also Oehler 1973; Wilson et al. 1974; Jones and Segnit 1975; Florke et al . 1975, 1976). Opal-A is amorphous to x-rays so investigations of its structure have been largely by direct observation with the electron microscope rather than by XRD . Studies of silica in the form of petrified wood (e.g. Segnit et al. 1970; Stein 1982; Scurfield and Segnit 1984; Senkayi et al . 1985) have identified microspheres, spherulites and more structureless varieties of silica which have invaded woody material, often faithfully reproducing the cellular structure. Australian studies of precious opal (mineralogically opal-A) have shown that it is composed of uniformly sized microspheres (1500-3500A diameter) -arranged in a cubic or hexagonal packing pattern (Jones et al . 1964, 1966; Darragh et al . 1966; Sanders 1968; Jones and Segnit 1969; Wenk et al . 1976; Klein and Hurlbut 1985). These microspheres themselves comprise smaller particles c. 300-400A in diameter (Darragh et al . 1966; Jones et al . 1966). It is diffraction of white light by planes of the microspheres that is thought to produce the iridescence seen in opals (Sanders 1968; Darragh et al . 1966). THERMAL STABILITY 17 Based on energy considerations quartz should be more stable than cristobalite and tridymite under surface conditions. These three phases however, are related to each other by slow transformations that involve reconstruction of the Si-0 bond, requiring considerable energy to convert from one polymorph to another. This, together with the stabilising influence of traces of chemical impurities, allows cristobalite and tridyrnite to exist metastably under surface conditions. Within each polymorph type there is a series of high and low temperature structures ( i . e . a and � forms, Fig. 3. 2) that involve displacive transitions (lattice re-orientation) without breaking bonds. Because this occurs spontaneously within a specific temperature range the lowest temperature form should be stable under surface conditions. There is, however, some evidence that �-cristobalite may persist under low temperatures in special circumstances. Greig (1932) and Sosman (1932) have described this phenomenon where �-cristobalite is enclosed in glass and suggest that the rigidity of the glass which "sets" above the cristobalite inversion temperature inhibits the re-orientation of the crystal during inversion. The inception of the Deep Sea Drilling Projects (DSDP) created an impetus for researching the relationship between biogenic silica (opaline silica), cristobalite-tridymite and quartz. It has been shown that with increasing depth of burial, biogenic silica (opal-A) in siliceous sediments is replaced by opal-CT which may in turn be replaced by quartz. In siliceous deposits the neoformation of cristobalite is thought to be a step in a sequence from biogenic opal HIGH TEMPERATURE PATHWAY Heating cycle 57 5°c 870°C 147 0°c 162 5°C �-quartz � 8-quartz � 82- tridymite � 8-cristobalite � melt �-quartz 5 7 5°C ----�•• 8-quartz I cristobalite Cooling cycle �-quartz 8-quartz 1 17°c 163oc «- tr idymite � 81-tridymite � 82 - tr idymite �-cristobalite 8-cr istoba lite t Reaction proposed by Florke ( 19 56 ) in the absence of mineralisers . LOW TEMPERATURE PATHWAY * + opaline s i l ica ------��� cristobalite/tr idymite quartz * * opal-A opal-CT quartz * occurs in 5 - 1 0 ma at 40- 50°C or 3 0- 40 ma at 20-30°c 1 8 + occurs a t approximately 70-85°C and the time constraint i s unknown except that cr istoba lite-tridymite is not found in rocks o lder than the Cretaceous . Figure 3 . 2 : Summary of the thermal transitions of some s ilica phases . to cristobalite (with or without tridyrnite) i.e. equivalent to opal-CT, then quartz during diagenesis (Iijima and Tada 1981; Hein et al . 1978). These workers (see also Isaacs 1982; Murata and Nakata 1974; Kastner et al . 1977; Keller and Isaacs 1985) have shown that the reaction is partially dependent on host rock composition in that it occurs at lower temperatures in the purer diatomites compared with siliceous/argillaceous mixtures . Isaacs (1982) also showed that the presence of carbonate did not dictate whether the reaction proceeded but Kastner et al . (1977) have shown that although carbonate was not 19 required directly, it was important in that it increased the alkalinity of the water and so stimulated the reaction. Other factors influencing the reaction rate include pore water chemistry [Kastner et al . (1977) demonstrated that Mg and possibly Al, Fe and Mn hydroxides assisted nucleation] and surface area (Hein et al . 1978), but the primary factors are time and temperature (Jones and Segnit 1971; Mizutani 1977; Iijima and Tada 1981). The transformation of opal-A to opal-CT is a dissolution/precipitation reaction (Murata and Nakata 1974; Stein and Kirkpatrick 1976) . Heydemann (1964), Florke et al . (1975) and Jeans (1978) have suggested that another phase (the so called silica-X) was a transitional phase between opal-A and opal-CT and Hein et al . (1978) ' recognised an intermediate phase, opal-A , which was composed of thin blades 20-27A thick which they suggested was a proto opal-CT. Estimates of the temperature of the opal-A to opal-CT transition include 35-50°C (Hein et al . 1978), 40-50°C (Aoyagi and Kazama 1980), 38-54°C (Pisciotto 1981) and 44-48°C (Keller and Isaacs 1985) . Hein et al . (1978) suggested that while the transition occurred in 5-10 ma at 40-S0°C along continental and island arc margins (where sedimentation rates were higher and there was increased diagenesis) it took 30-40 ma at 2 0-30°C in open oceans with low sedimentation rates (Fig. 3.2). The nature of the opal-CT to quartz transition is more enigmatic. There are few sections where the transition is exposed, either through lack of suitable lithologies or from marine cores not reaching deep enough. Opinions are divided as to whether the transformation is due to solution/precipitation or solid/solid inversion (Ernst and Calvert 1969; Heath and Moberly 1971; Greenwood 1973; Murata and Larsen 1975; Stein and Kirkpatrick 1976). Aoyagi and Kazama (1980) suggested that the transition occurred at 70°C; Pisciotto (1981) suggested 55-110°C and Keller and Isaacs (1985) suggested 70-85°C, depending on the composition of the enclosing sediments. Precious opal (opal-A) comprises amorphous silica microspheres c . 1500-3500A in diameter. This form of opaline silica is thought to develop by dehydration of silica gels (Jones et al . 1966; Darragh et a� . 1966). Detailed observation of the rnicrospheres has shown that they consist of smaller particles ( c . 300-400A diameter) and Darragh et al . (1966) suggest that they are produced by evaporation from silica-bearing waters under near surface conditions. Under relatively static conditions these particles settle as loose floes to produce a thin gel. With additional aggregation and desiccation they develop into the 1500-3500A rnicrospheres seen in precious opal. ISOTOPES The development of techniques to isolate opal/cristobalite (Henderson et a� . 1972) have now made it possible to determine the oxygen isotopic composition of these phases. Henderson et a� . (1971, 1972) determined that there was a broad correlation of s18o with temperature of formation similar to that for quartz . High o18o values are found for poorly crystalline opal-A (including diatoms) and low o18o values for opal-C from hydrothermal deposits. Oxygen isotope relations between diagenetic silica minerals (Murata et al . 1977) indicated decreasing o18o (37.4°/00 to 23.8 °/00) with increasing crystallinity and they determined that opal-CT formed at approximately 48°C while "rnicroquartz" formed at about 79°C . These temperatures are in good agreement with those determined by Hein et a� . (1978) and Aoyagi and Kazana (1980). In a study of opal/cristobalite from hydrothermal springs in Japan, Jackson et al . (1977) showed, using the electron microscope, that those phases from 20 low temperature springs (high o18o) were "spheroidal and spongey" compared with those formed at higher temperatures (low o18o) which formed irregular plates or prisms. Cristobalite in a podzol from Northland, New Zealand was concluded to be of hydrothermal or volcanic origin (Henderson et al . 1972) while in a recent investigation cristobalite in Ando soils from Japan, Indonesia and Guadalupe and a podzol from Japan was shown to be inherited from a primary volcanic source (Mizota et al . 1987). 2 1 These data (Table 3.1) indicate that opal-C (a-cristobalite) from a high temperature environment can clearly be differentiated from opal-CT or opal-A from low temperature diagenetic environments similar to conditions prevailing in soils. OCCURRENCE Geo1ogica1 Environments (1) In sedimentary environments opal/cristobalite has been identified in a wide range of rock types such as bentonite (Brindley 1957; Guven and Grim 1972; Henderson et al. 1971); shales (Davis 1970); claystones (Reynolds 1970; Weaver and Wise 1974); interbedded argillite/porcellanite sequences (Aoyagi and Kazama 1980; Iijima and Tada 1981; Murata and Nakata 1974; Pisciotto 1981; Isaacs 1982) and greensand/chalk sequences (Jeans 1978). In all of these examples none of the rocks are older than Upper Cretaceous. These authors describe some or all of the sequence: biogenic silica --- opal-A --- opal-CT --- quartz. With the initiation of DSDP (e.g. JOIDES 1967) there has been considerable work undertaken on silica in deep ocean sediments (see Hein 1981) . In North Atlantic deep sea sediments Calvert (1971a, 1971b) identified opal-CT and found that while siliceous deposits older than the Cretaceous were cherts (i.e . quartzitic) all younger deposits were porcellanites (containing opal-CT) . Since this initial work opal/cristobalite has been shown to be extensive in ocean sediments (e.g. South Atlantic, Wise and Hsu 1971; Antarctic and Mid-Pacific, Weaver and Wise 1972; North Pacific, Hein et al. 1978). Tab l e 3 . 1 : Summary of oxygen i s o t ope data for c r i s toba l ite . Env i ronment D ia toms D i a t oms Miocene diatoms Porc e l l a n i t e Por c e l l a n i t e Porce l l a n i t e Ben t o n i t e S o i l s So i l s Hydro thermal M i n e r a l type ( opa l-A ) ( opa l -CT ? ) ( opa l -A ? ) ( opa l -CT ) ( opa l -CT ) ( opa l-CT ) ( opa l-CT ) 3 6 . 2 , 37 . 4 N o . Ref . 3 4 . 0 * 2 3 2 . 2 * 3 2 7 . 9 - 3 3 . 8 ( 1 0 ) . 1 3 0 . 2 - 3 2 . 1 ( 6 ) * 4 3 5 . 7 , 3 5 . 9 ( 2 ) . a 2 5 . 5 - 2 9 . 9 ( 4 ) * 2 l ow c r i s toba l i te ( opal-C ) 8 . 3 � 9 . 1 ( 3 ) ( 4 ) opa l - C and/or tr idymt e 5 . 3 - 1 1 . 0 l ow c r i s tobal ite Terr e s t r ia l volcanics opa l - C + tr idymite ( ? ) 8 . 8 , 9 . 3 6 . 8 - 1 1 . 4 7 . 2 ( 4 ) Lunar v o l canics ? Qua r t z in chert s assoc i a t e d w i th porce l lanites 2 4 . 5 - 2 7 . 1 ( 1 3 ) . 4 2 3 . 8 + 0 . 3 * 1 2 a - 3 6 ( 1 0 ) . a * 1 - Murata e t a l . ( 1 9 7 7 ) : 2 - Henderson e t a l . ( 1 9 7 1 ) : 3 - Henderson et a l . ( 1 9 7 2 ) : 4 - P is c i o t to ( 1 9 8 1 ) : 5 - Jackson e t a l . ( 1 9 7 7 ) ; 6 - Tay l o r and Eps tein ( 19 7 0 ) ; 7 - Miz ota e t a l . ( 1 9 8 7 ) ; 8 - H e in and Y eh ( 1 9 8 1 ) . 2 2 Various forms of silica (opal-A, opal-CT and tridyrnite) also form as precious to semi-precious opal and wood opal, usually in terrestrial deposits. Here the minerals form lepispheres, microspheres and massive varieties that fill joints and cavities or form pseudomorphs after woody tissue (Mitchell 1967; Buurman 1972; Mitchell and Tufts 1973; Stein 1982; Scurfield and Segnit 1984; Senkayi et al . 1985). Opal-A is also precipitated in South Australian lakes (Skinner 1963; Peterson and von der Borch 1965) in association with magnesite and dolomite under extremely alkaline conditions (pH up to 10. 2). (2) As well as forming in a diagenetic environment, cristobalite is also reported from environments with demonstrably higher temperatures, e . g: Zones of hydrothermal alteration (Tokuda 1960; Jackson et al . 1977; Murray et al . 1977; Sarna-Wojcicki et al . 1981; Hampton and Bailey 1985), 2 3 Lavas e. g. lunar basalts (Applernan et al . 1971; Champness et al . 1971; Christie et al . 1971; Kei1 and Prinz 1971; Klein et al . 1971; Sippel et al . 1971), Japanese lavas (Kuno 1933), Ignirnbrites (Mahood et al . 1985), Volcanic mudflows (Mullineaux and Crandell 1962, see also Verhoogen 1937), and Tephras - in Indonesia (Hardjosoesastro 1956), Nevada (Moncure et al . 1981), Japan (Mizota and Aomine 1975; Yarnada and Shoji 1977), Chile (Wada and Kakuto 1984) and in the 1980 eruptions from Mount St. Helens (Fruchter et al . 1980; Dethier et al . 1981; Gage et al . 1981; Kuntz et al . 1981; Lofgrens 1981; Bernard and Guern 1986). This type of cristobalite is equivalent to opal-C. Tridymite, which often occurs with cristobalite, is commonly associated with zones of hydrothermal alteration (Frondel 1 9 62 ) and silicic volcanics such as rhyolites, obsidian, trachyte, dacite and andesites (Frondel 1 9 62 ; Klein and Hurlbut 1 9 8 5 ) . Fruchter et al . ( 1 9 8 0 ) and Dethier et al . ( 1 9 8 1 ) report tridymite in ash from the 1 9 8 0 eruption of Mount St. Helens. Tridymite is also described from stony meteorites (Klein and Hurlbut 1 9 85 ) and lunar lavas (Appleman et al . 1 9 7 1 ; Keil and Prinz 1 9 7 1 ) . It forms in cavities and vesicles, apparently during the latter stages of magmatic activity and Rogers ( 1 92 8 ) considered it to be pneumatolytic. Trace amounts of tridymite have often been described in the fine microlitic mesostasis which crystallises last as a lava cools (Frondel 1 9 62 ; Appleman et al. 1 97 1 ; Keil and Prinz 1 9 7 1 ) . ( 3 ) In New Zealand, cristobalite has been described from ( 1 ) 2 4 the devitrified matrix of the Whakamaru Ignimbrite (Ewart 19 65 , 1 9 7 1 ) , ( 2 ) dacites from the Taupe Volcanic Zone (Cole 1 9 7 9 ; Worthington 1 9 8 5 ) , ( 3 ) hydrothermal deposits e. g. Northland (Murray et al . 1 97 7 ; Harvey 1 9 8 0 ) , and ( 4 ) pumice xenoliths thermally metamorphosed by the 1 8 8 6 Tarawera basalt (identified during the present study) . This type of cristobalite is similar to opal-C. In geological environments opal-A and opal-CT occur in rock types that are associated with the low temperature pathway while opal­ C and tridymite occur in rock types associated with the high temperature pathway. Pedological Environments ( 1 ) Opal/cristobalite is common in soils developed in parent materials associated with volcanism, e.g. in Indonesia (Hardjosoesastro 1 9 5 6 ; Sjarif and Gilkes 1 9 8 6 ) , Japan (Mizota and Aomine 1 9 7 5 ; Mizota et al. 1 9 8 7 ) , South America (Cortez and Franzmeier 1 972 ) , Israel (Yaalon 1 9 62 ) and New Zealand (e.g. Swindale . and Jackson 1960 ; Lowe 1987). The very sharp nature of the XRD peaks, together with the coarse nature of the cristobalite (it occurs in clay to sand size grains), led Mizota and Aomine (1975) to conclude that it was of primary volcanic origin (see also Wi1ding et al . 1977). Recently determined oxygen isotope ratios of cristobalite/tridymite from some Japanese soils supports this conclusion (Mizota et al . 1987). 2 5 (2) In New Zealand soils cristobalite is scarce and tridymite has only rarely been identified. Fieldes and Williamson (1955) refer to cristobalite in the Okaihau gravelly clay, but the first significant report on cristobalite in the pedosphere was by Swindale and Jackson (1960) who described· opal/cristobalite from the silt fractions of soils with a rhyolitic provenance. It is not possible to determine the crystallinity of this opal/cristobalite from their data but they do refer to some as being of the "stuffed" structure (Buerger 1954), indicating that some may have been opal-CT or opal-C plus tridyrnite. Oxygen isotope analysis of the opal/cristobalite (Henderson et al . 1972) indicated that it was of a relatively high temperature origin, i. e. hydrothermal or volcanic. Reconnaissance soil mineralogical studies (Fieldes and Weatherhead 1968; New Zealand Soil Bureau 1968 ; Claridge and Weatherhead 1978) indicated that cristobalite could be up to 9% of the silts in some New Zealand soils. More detailed recent investigations (e. g. McQueen 1975; Davoren 1976 ; Jessen 1977; Bruce 1978; Hogg 1979; Lowe 1981, 1986; Shepherd 1984) report significant cristobalite in the volcanic ash soils of the Hamilton Basin, particularly the brown granular loams. Benny (1982) identified cristobalite and tridyrnite in a study of the Okareka Ash and overlying tephric loess in the vicinity of Lake Rotorua (see also Birrell and Pullar 1973) , and Stewart (1982) reports minor amounts of cristobalite in soils developed on basalts in Northland. These occurrences appear to correlate closely with siliceous tephric material. Tridyrnite, where identified, (New Zealand Soil Bureau 1968; Claridge and Weatherhead 1978) is also associated with soils developed from tephric materials. ( 3 ) Opal-A occurs in both biogenic and inorganic forms in soils (Wilding et al . 1 9 7 7 ) . Biogenic opal is minor though ubiquitous in most soils either as plant phytoliths (Bartoli and Guillet 1 9 7 7 ; Beavers and Stephen 1 9 5 8 ; Jones and Beavers 1 9 6 4 ; also see chapter 4 ) or from aquatic environments (sponge spicules, diatoms and radiolaria). Laminar opaline silica (Parfitt 1 9 75 ; Shoji and Saigusa 1 97 8 ; Shoji et al . 1 9 8 6 ) is another form of opaline silica which is commonly associated with humic horizons and soils rich in volcaniclastic materials. Inorganic silica serves as a cement in some indurated soil horizons (duripans) in areas of Mediterranean and arid climate. The occurrence of biogenic silica as phytoliths or microfossils is relatively common in New Zealand soils (New Zealand Soil Bureau 1 9 6 8 ; see chapter 4 ) . This is due to ( 1 ) the nature of the rocks that are the soil parent materials - many contain radiolaria, sponge remains and diatoms, (2) the ubiquitous plant cover prior to relatively recent human settlement and ( 3 ) the relatively stable nature of biogenic opal (Bartoli and Wilding 1 9 8 0 ) . Laminar opaline silica has also been reported in New Zealand soils (Fieldes and Furkert 1 9 6 6 ; Henmi and Parfitt 1 9 8 0 ; see also Lowe 19 8 7 ) . PRESENT INVESTIGATION Cristobalite in soils has been postulated as being either inherited or pedogenic (see Hardjosoesastro 1 956 ; Henderson et al . 1 9 7 1 ; Lowe 1 9 8 1 , 1 9 8 6 ; Mitchell ( 1 97 5 ) ; Wada 1980 ; Wilding and Drees 1 9 7 4 ; Wilding et al . 1 97 7 ) . In a study of soils in the Waikato region where cristobalite is relatively common in some soils with poor drainage, Lowe ( 1 9 8 1 , 1 9 8 7 ) suggested that cristobalite was 2 6 authigenic. He suggested that cristobalite formed in soils where drainage was poor because the soil solution became enriched in Si. This Si precipitated to form hydrogels which crystallised as cristobalite during dry periods. If this pathway is correct then any cristobalite so formed should have a high o18o commensurate with its low temperature of formation and poor crystallinity ( i . e . opal-CT) . To characterise the form of cristobalite present in these soils four soil types were chosen for detailed analysis. Three are from the Hamilton basin (Hamilton clay loam, .Naike clay and Te Kowhai silt loam) and have formed from volcaniclastic parent materials while the fourth (Waiareka clay) is formed from mixed loess-calcareous basaltic tuff near· Oamaru (Fig. 3 . 3 ) . The profiles were continuously channel sampled over 1 0 cm intervals down to a depth of one metre. After particle size analysis cristobalite and tridymite in various fractions were separated. During this process concentrates of a very low density fraction (opal-A) and a heavy fraction (opaques, ferromagnesian silicates and zircons) were produced. 2 7 During initial x-ray investigation the cristobalite in the soil was shown to be closely associated with tridymite and to be of a well­ ordered variety (opal-C) . It was therefore deduced that the cristobalite was probably of a high temperature origin and introduced into the soil along with the volcaniclastic materials. Accordingly representatives of possible volcanic sources were processed to isolate cristobalite. Tephras sampled included ( 1 ) the Rotoma Ash, Rotoehu Ash, Okareka Ash (from which cristobalite and tridymite had been previously reported, Benny 1 9 82 ) , and the Rotomahana Mud, all from the Okataina Volcanic Centre, and ( 2 ) the Aokautere Ash, Waimihia Lapilli and Taupe Pumice from the Taupe Volcanic Centre . Andesitic lavas and tephra from Mt . Egmont were also processed to isolate cristobalite. Two extra soils were processed: (1 ) the Tokomaru silt loam, the detailed mineralogy of which is presented in chapter 4 , and ( 2 ) a profile through peaty beds at Onaero near the edge of the Mt . Egmont ring plain in northeastern Taranaki. • WELCHES ROAD HAIKE SITE. HAML TOH SITE_. • TE KOWHAI SITE (Rototuna Rd . ) 0 e TAPAPA lhu eKAKEPUKU N f 0 10 eTE KUITI Figure 3 . 3 : L oca tion map of part of the Hamilton basin showing the sites mentioned in the tex t . TVZ in the i n s er t is Taupe Volcan ic Zone . 28 20 30km 2 9 Soil description (1) The Hamilton clay loam is a brown granular loam (New Zealand Soil Bureau, 1968) . The sampling site (Rototuna Road; S14/1028301) was on a flat terrace tread at an altitude of 50 m. Annual rainfall is 1200 mm . A detailed soil description is given in Lowe (1981) . The soil profile can be divided into two units. The underlying clay-rich unit (here referred to as the lower unit) is part of the Hamilton Ash Group (Ward 1967; Pain 1975; Shepherd 1984) while the overlying sandier unit (upper unit) is a composite unit of loess, and andesitic and rhyolitic tephric accretions (McCraw 1967; Pullar 1967; Vucetich and Pullar 1969) . The Hamilton Ash Group comprises clay-rich, highly weathered tephra, which mantle the low ridges and isolated hillocks that are erosion remnants of Lower-Middle Pleistocene sediments. It contains numerous palaeosols (Shepherd 1984) and is the result of continuous accretion of numerous rhyolitic and andesitic tephra that have been reworked and rapidly weathered (Ward 1967; Stevens and Vucetich 1984; 1985) . The ash is now dominated by clay minerals but there are small amounts of residual sand-sized grains, mainly quartz, magnetite, ilmenite and zircon (Shepherd 1984) . At Rototuna Road the clays are predominately halloysite with less allophane (Lowe 1981) but near Te Kuiti they are dominantly allophane (Stevens and Vucetich 1984; 1985) . A minimum age for the ash is c. 70 ka (Gibbs 1980) . In a detailed study of the Hamilton Ash Group at Welches Road where it is c. 3. 8 m thick, Shepherd (1984) identified numerous palaeosols and eight members (H1 - H8) . Member H2, a prominent pale horizon at the base of the Group, is the Ohinewai Tephra Formation (Vucetich et al . 1978). Mairoa Ash (68 cm thick) overlies the Hamilton Ash Group. At Rototuna Road the top of the Hamilton Ash Group (i. e. the top of the lower unit) is correlated with the Hs or H6 member �Lowe 1981) . The upper unit is much less weathered and contains more weatherable minerals (e.g. glass, feldspars, ferromagnesian silicates) and less clays compared with the lower unit (Lowe 1981; Shepherd 1984; Grid references are based on the metric 1 : 50 000 series (NZMS 260) . Stevens and Vucetich 1984; 1985; Joe 1986). Based on mineralogical evidence, Lowe (1981) identified the Rotoehu, Aokautere, Okareka and Tuhua tephras in the upper unit. These do not form discrete bands because they have been mixed. The presence of the Rotoehu Ash indicates that there have been tephra additions to the upper unit for at least the last c . 42 ka. 30 Cristobalite has been frequently reported from the Hamilton clay loam. New Zealand Soil Bureau (1968), Lowe (1981) and Joe (1986) report up to c . 30% cristobalite in the clays from the upper unit while Lowe (1981), Shepherd (1984) and Joe (1986) report up to c . 15% cristobalite in the sands or silts. Generally, larger amounts of cristobalite have been reported from the upper unit compared with the lower unit. (2) The Naike clay is a brown granular loam. The sampling site (S14/934975) was on an 11° slope of a hill spur at an altitude of 100 m. Annual rainfall is 1240 mm. The parent material is the Hamilton Ash Group and details of the soil site are given by New Zealand Soil Bureau (1968) and Anon (1981). These reports indicate that there is a marked change in properties at c . 20 cm. Above 20 cm there is an increased sand content and these sands comprise more weatherable minerals (feldspars and Fe-Mg silicates) compared with deeper horizons where quartz, magnetite, ilmenite and muscovite are more common. The clay content of the top 20 cm is lower and contains more vermiculite, kaolinite and allophane (with halloysite) compared with deeper levels where the clay content is higher (>88%) and is totally dominated by halloysite. The total element chemistry (e. g. Mn, K, Si, Al, Zn, Rb, Y and Ba) and soil solution chemistry ( e . g . K, Na, Al) also demonstrate a marked change at c . 20 cm depth (Anon 1981). New Zealand Soil Bureau (1968) and Anon (1981) both record minor cristobalite in the clay fraction of the top of the profile while the New Zealand Soil Bureau (1968) record a trace of tridymite in the sand fraction of the C horizon. 31 (3) The Te Kowhai silt loam is a gleyed yellow-brown pumice soil on a flat, poorly drained site (514/120819), adjacent to a sand quarry. Altitude is 30 m and the site receives 1270 mm annual rainfall. The soil has formed in a swale of an old channel on a gently undulating plain developed in the Hinuera Formation. The Hinuera Formation (Schofield 1965; Hume et al . 1975) is a low angle fan of volcanogenic alluvium that was deposited by the braided river system of the Waikato River during several phases of fan building (McCraw 1967; Hume et al. 1975). It is composed of gravelly sands and silts which are reworked rhyolitic volcanic debris (mainly pumiceous) from the central North Island. It also contains localised peats. The youngest phase of fan building (Hinuera-2) has been dated at 20 - 15 ka (Hume et al . 1975; McGlone et al . 1978; Green and Lowe 1985) and the final phase of alluvial sedimentation in the region of the gravel pit ceased approximately 15. 5 ka ago (Green and Lowe 1985; Lowe 1987) . Details of the soil at the sand quarry are given by Anon (1981) while McQueen (1975) presented a detailed study of the Horotiu-Te Kowhai soil complex. The Horotiu silt loam is a yellow-brown loam with a clay fraction dominated by allophane, and forms on well drained sites in pumiceous alluvium (Hinuera Formation) . It forms a soil complex with the Te Kowhai silt loam, a gley soil with a clay fraction dominated by halloysite and found in poorly drained sites on the Hinuera Formation (McQueen 1975; Joe 1986) . The mineralogy of the Te Kowhai silt loam is dominated by glass (Joe 1986) . Cristobalite is common (up to 5% of the clay and 15% of the sand fractions) . Quartz and feldspar are relatively constant components of the sand fraction (c. 20 %) except below one metre depth where there is a marked increase with a concomitant decrease in glass content (Joe 1986). Heavy minerals are rare in the sands except for the top 20-30 cm where there is a significant rise in this fraction (mainly orthopyroxene, magnetite and hornblende) . (4) The Waiareka clay is a brown granular clay (New Zealand Soil Bureau - 1968). The sampling site (J41/419602) was on a bench at an altitude of c. 3 0 m. Annual rainfall is 600 mm. 3 2 This soil has developed on the Eocene Waiareka Volcanic Formation (Gage 1957; Suggate et al . 1978). In the region of the railway cutting this comprises calcareous basaltic tuffs. The clay fraction is dominated by montmorillonite and the sand fraction is mainly quartz, feldspar, cristobalite and epidote group minerals (New Zealand Soil Bureau 1968) . There is a change in the components of the sand fraction at c . 55 cm with chlorite abundant, and many of the scarcer phases absent, below this depth. Similarly, the soil chemistry (Fe, P , Na, K and Ca) indicates that there is a significant change at 55 cm. This change is taken to reflect the transition to the relatively unweathered Waiareka Volcanic Formation. RESULTS GRAIN SIZE DISTRIBUTION Although different grain size divisions were used in previous work on the soils of the present study (New Zealand Soil Bureau 1968; Lowe 1981; Anon. 1981), published results are in good agreement with those of the present investigation. The Hamilton soil is a silty clay (Fig. 3.4) with horizons above 50 cm being coarser than those in lower horizons. The top 30 cm has a uniform and sandier texture while between 30 and c . 60 cm there is a transition to clay-rich lower horizons. The Ap horizon of the Naike soil has a coarser texture than the 2Bt1 horizon (30-80 cm depth) which has a very high clay content (Fig. 3.5). Below 80 . cm is a 3Bt2 horizon in which the sand content is similar to the Ap horizon. The Bw horizon (20-30 cm depth) is transitional between the sandy Ap and clay-rich 2Bt1 horizons. The coarse nature of the 3Bt2 horizon is mainly due to authigenic halloysite nodules whereas the coarse A horizon is due to coarse grained primary minerals. A1 R2 R3 A4 AS R& R7 AB RI A10 V N 1.1'1 0 0 . i Ah Bt1 2Bt2 , I 2Btg 1m 0 N CJ1 ..... 0 N I CJ1 ..... I N 0\ CJ1 w t: t: 3 3 . 5 1 0 0 % 1 0 % 0\ N w 0 I I N 1.1'1 0 t: t: 3 3 2 0 3 0 CJ1 I N t: I 3 0 1 0 1\ N t: 3 30 50 % 7 0 9 0 Figure 3 . 4 : Variat ions i n the grain s i z e dis tr ibu tion for var ious s i z e fractions o f the Ham i l ton c lay loam . vu vu N1 N2 N3 N4 N5 N6 N7 N8 N9 N10 0 I Ap - Bw 2Bt1 3Bt2 ' ' lm ..... ggs 00 I I U'l N OU'l 00 t: t: 3 3 0 N U'l ..... 0 N I U'l ..... I N 0\ U'l w t: t: 3 3 5 0 % 5 % 0\ w I N 0 t: 3 1 0 U'l I N t: 3 0 1 0 % N 0 I U'l t: 3 2 0 5 0 " N t: 3 60 7 0 % Figure 3 . 5 : Var iat ions in the grain s i z e dis tr ibution for var ious s i z e fract ions of the Naike c l ay . 80 w .t:" The Te Kowhai soil has a variable texture as would be expected from an alluvial parent material (Fig. 3 . 6 ) . It is stratified and there is an increase in the very fine sand and coarse silt towards the base of the profile. The medium and fine silt fractions increase towards the top of the profile. Particle size parameters show the Waiareka soil to be a silty clay. The upper 30 cm (A and B horizons) are uniform in texture while the BC horizon ( 3 0-40 cm depth) is transitional to the C horizon. Towards the base there is an increasing abundance of blocks of the Waiareka Volcanic Formation (up to 10 cm in diameter) . These blocks have coatings of clays, presumably translocated down joints in the welded tuffaceous parent material. 35 Cristobalite was not identified in this soil profile. During the XRD scans however, quartz was observed to be abundant in the top 30 cm but absent below 4 0 cm. Quartz has not been previously identified in the Waiareka Volcanic Formation and its presence in the soil is interpreted as resulting from aerosolic additions to the profile. Although such additions could be derived from volcanic sources as a component of airfall tephra (e. g. Stewart 19 82 ; Stewart et al . 1 9 8 4 ; 1 9 8 6 ) there is no apparent volcanic source of an appropriate age or composition in the region . The quartz therefore probably results from loess additions to the profile. Due to the absence of cristobalite this soil is not considered further. GRAIN MORPHOLOGY An electron microscope study showed that there were a variety of morphologies in the cristobalite concentrates. The dominant form (Fig. 3 . 7 ) is of blocky material with euhedral pits. This type of grain often has striations on its surface (Fig. 3 . 7 ) . Various forms of residual cristobalite and tridymite (Figs. 3 . 8 , 3 . 9 ) are interpreted as remnants of mesostasis intergrowths from which silicates and glass have been removed. A morphology which comprises clusters of striated euhedral crystals occurs in pumiceous xenoliths in the 1 8 8 6 Tarawera Basalt (Fig. 3 . 10 ) . Also rare are forms that are apparently composed of florets of very thin blades (Fig. 3 . 1 1 ) which are similar to lepispheres. TK1 TK2 TK3 TK4 TK5 TKI TK7 TK8 TKI TK10 U'I N g � ..... N I I U'l N _.. I U'l N en O U'I w 0 i i i Ap "" Bg 2Br 2Cr1 2Cr2 2Cr3 lm 0 1 0 en w I N 0 i 20 % 3 0 0 U'l I N � 3 1 0 2 0 % N 1\ 0 N I U'l � i 3 30 0 1 0 2 0 % Figure 3. 6 : Var iat ions in the grain s i z e distribut ion for var ious s i z e fractions of the Te Kowha i s i l t loam . -- 30 w � A B 37 Figure 3 . 7 : ( A ) Typical blocky cristobalite with euhedral pits and surface striations . ( B ) Surface striations enhanced by acid treatment . S cale bar represents 10 microns . Figure 3 . 8 : Less common forms of cristobalite . Remnants of mesostasis type intergrowths . Scale bar represents 1 0 microns . 38 A B Figure 3 . 9 : ( A ) Cristobalite remnants from a spherulitic intergrowth . ( B ) Cristobalite which i s thought to represent material crystal lised from an interstitial l iquid phase . Scale bar represents 30 microns . 39 Figure 3 . 1 0 : S triated cristobalite from pumiceous xenoliths in Tarawera basal t . S ca le bar represents 3 0 microns . 40 Figure 3 . 1 1 : An unusual form of cristobalite which is s imilar to lepispheres . Scale bar represents 10 microns . 4 1 The XRD traces of most samples contain tridymite peaks but it is not possible to determine if the tridymite is discrete. Grains with wedge-shaped twins similar to those described for tridymite have been observed optically in some samples and it is thought that the hexagonal grains illustrated in figure 3 .12 may be tridymite. This phase appears to be uncommon. Frondel (1962; see also Wilson et al . 1974) reports that "high-tridymite", which has hexagonal symmetry, is found as thin plates with hexagonal outlines but Jones and Segnit (1975) and Florke et al . (1976) also describe opal-CT with a platy hexagonal morphology. Based on this electron microscope study the evidence for discrete tridymite is equivocal. During sample preparation a low density fraction ( <2 . 25 Mg m-3) was separated. This included volcanic glass shards, phytoliths, diatoms, sponge debris and two distinct forms of what has been interpreted as opal-A (Fig. 3 . 13). One of these distinct forms occurs in the Hamilton soil while the other is from the Naike soil. Although their distributions were not systematically studied some general observations can be made. 4 2 The opal-A from the Hamilton soil is composed of rounded equidimensional to prismatic, or platy forms (Fig. 3 . 14) . In grain mounts these forms are concentrically zoned (up to 5 zones per grain) and SEM investigation shows that the outer shells of some grains are cracked and appear to have "exfoliated" from the grain core. This exfoliation phenomenon only occurs with the samples prepared for the electron microscope and is thought to be due to ultra-desiccation under high vacuum during sample preparation. Although the outer surfaces of the grains are reasonably smooth, close examination of the surface revealed by the "exfoliation" indicates that it comprises equidimensional particles c. 1600A in diameter . This form is referred to as concentric opal-A and occurs in samples R6, R9 and R10 but not in R1, R2 or R3, i . e . it occurs in the lower unit of the Hamilton soil . The opal-A from the Naike soil is composed of irregular subangular to subrounded grains which contain a high density of micron-sized inclusions. These give the grains a dusty appearance, so this form is 4 3 a b Figure 3 . 12 : Tridymite or cristobalite in the form of hexagonal p lates . S cales are 5 0 microns ( a ) and 1 0 microns ( b ) . ( b� ( c ) ( d ) --3-8�0-0----����J-------,�6�00-------,�2o_o ______ B_OL0------�4�00�c -m--1r WAVE NUMBER Figure 3 . 13 : Infra-red spectra of some s i lica phases from the soils studied . ( a ) Quartz . ( b ) Phytoliths . ( c ) Concentric opal- A . ( d ) Dus ty opal-A . ( e ) Wave number 9 6 0 cm- 1 is referred to in the text . 4 5 A B c Figure 3 . 1 4 : Morphology of the concentric opal-A . ( A ) Opt ica l zoning ( transmitted l ight , scale is 4 0 microns ) . ( B ) SEM image showing exfoliation ( s cale is 2 0 microns ) . ( C ) High magnification SEM ( scale is 1 micron ) . 46 referred to as dusty opal-A . In rare cases the inclusions are anisotropic and appear to represent minerals incorporated in the grains during growth . The inclusions invariably have a higher refractive index than their host . Electron microscope study indicates that this form has a very porous surface (Fig . 3 . 15 ) . The dusty opal-A occurs in samples NB and N10 but not in the top 2 0 cm of the Naike soil . OPAL-c AND TRIDYMITE-M NOMENCLATURE Identification of the low density silica polymorphs based on x-ray diffraction is complicated because ( 1 ) cristobalite and tridymite may occur as both intergrown or discrete phases , ( 2 ) the I1 0 0 peaks for tridymite and cristobalite overlap, and ( 3 ) the relative intensities of peaks in the same phase are variable depending on the structural state . Further, �-cristobalite which has an XRD pattern s imilar to a-·tridymite (Brown 1 9 8 0 ) may occur at surface temperatures and pressures (Greig 1 932 ; Sosman 1 932 ) . These problems may be compounded in soils due to mixing . To facilitate better identification and discrimination between cristobalite and tridymite , selected samples were given an additional density separation ( S . G . of 2 . 3 gm cm-3 ) to separate cristobalite and tridymite . Although the resultant concentrates were not monomineralic the one with the lower density shows enhanced tridymite XRD peaks while the other shows fl enhanced cristobalite peaks ( Fig . 3 . 1 6 ) . Based on this x-ray data , electron microscopy and optical data, it is concluded that at least some of the tridymite reflections are due to discrete tridymite . The multiplicity of cristobalite peaks in the concentrate heavier than 2 . 3 Mg m-3 (Fig . 3 . 1 6 ) indicates that the phase present is opal-C ( i . e . a-cristobalite) . Tridymite peaks also occur and this tridymite may either be present as discrete grains or as subdomains in cristobalite . In the t ridymite concentrate the absence of doublet reflections at 3 . 85A, 3 . 0 0A and 2 . 50A and a relatively strong reflection at 3 . 25A indicate that the tridymite phase is tridymite-M . P-cristobalite is also a possible component in the soil but the absence from the diffractograms of major reflections at 2 . 53 , 1 . 6 4 and 1 . 4 6A (Brown 1 9 8 0 ) suggests that it is not common in these soils . 4 7 A B F igure 3 . 15 : Morphology of the dusty opal-A showing the rough nature of the surface ( A ) and the microspheres within the grains ( B ) . S ca les bars are 20 microns for ( A ) and 1 micron for ( B ) . A c B I 80 7 0 c c 60 t 5 0 Degrees 29 c 4 0 t t t c t c t c 3 0 8 A Figure 3 . 1 6 : XRD patterns of concentrates o f tridym ite ( A ) and cris toba l i t e ( B ) a f ter repeated den s i ty s epara tions at 2 . 3 Mg m- 3 . The deta i l of the I 1 0 0 ref lections between 2 5° and 2 6° 29 is a ls o shown . Di agnos tic ref lections a r e marked , c for cris toba l i te and t for tr idym i t e . .::­ CD Furthermore , optical investigation indicates that the concentrates are dominated by grains which are weakly anisotropic , thus precluding �-cristobalite (cubic) as a dominant phase . High cristobalite ( i . e . �-cristobalite ) has recently been reported from soils (Mizota et al . 1 9 8 7 ) but the d-spacings of the reflections they have indexed, together with close examination of their diffractograms , suggest that this phase is probably tridymite ( reflections at 4 . 3 , 4 . 1 , 3 . 82 , 2 . 97 and 2 . 4 8A) . Although the relative intensities of the reflections of their �-cristobalite do not fit t ridymite as documented by Brown ( 1 9 8 0 ) , neither do they fit the relative intensities of �-cristobalite . Hill and Roy ( 1 95 8a ) , Roy and Roy ( 1 9 6 4 ) and Tada and I i j ima ( 1 9 8 3 ) show that the relativity of peak intensity is quite variable . The �-cristobalite identified by Mizota et al . ( 1 9 8 7 ) is therefore probably t ridymite . 4 9 I n the standardised XRD traces (Fig . 3 . 17 ) the cristobalite type is identified using the 3 . 1 4A and 2 . 85A reflections . If they are present the phase is identified as opal-C whereas if they are absent opal-CT is indicated . The tridymite phase present is tridymite-M and this has been identified using the form and presence of the reflections at 3 . 8 5 , 3 . 25 and 3 . 0 0A . The relative proportions of opal-C and tridymite-M are difficult to determine because the I1 0 0 peaks ( c . 4 . 05A and 4 . 1 1A respectively) overlap considerably . This ratio may be meaningless because each phase may occur as subdomains in the other, but as an approximate measure of the maximum concentration of these two phases the height above background of their I 1 0 0 peaks (or the level of a shoulder peak if one is very dominant ) is taken as a measure of the amount present . CRYSTALLrNITY OF CRISTOBALITE AND TRIDY.MITE rN THE SOILS To investigate possible variations in the types of cristobalite and t ridymite present , plagioclase and mafic minerals were removed from t he samples by the ABFS treatment (chapter 2 ) . The final concentrates were dominated by quartz , cristobalite and or tridymite with additional minor phases which were resistant to the pre-treatment ( e . g . z ircon, rutile , anatase ) . XRD analyses of these concentrates , standardised so that the traces are comparable, were prepared from a selected grain size for each profile . Cristobalite has been reported from the sand fractions of the soils being studied (e . g . Shepherd 1 98 4 ; Joe 1 98 6 ) but in the present study , after ABFS t reatment , cristobalite and tridyrnite were found to be rare in the very fine sands and absent in the coarser fractions . During washing after the ABFS treatment , fines ( < c . 2 0 �) were released by the sands and subsequent investigation of this material revealed that it was dominated by opal-C and t ridyrnite . The sand fractions of the soil contain abundant pumice grains and volcanogenic lithic fragments and it is here suggested that the cristobalite and tridyrnite in this f raction occurs either as fine crystals attached to, or t rapped in pumice , or as components in lithics . Much of the cristobalite reported from the sand fractions of the soils probably has a s imilar origin . Opal-C and t ridyrnite-M are common in the silt and clay fractions . 5 0 (A) Coarse Silt : In the Hamilton soil (Fig . 3 . 17a ) the top 40 ern are dominated by t ridyrnite-M with only minor opal-C . Below 4 0 ern the reflections are more uniform and indicate that opal-C and tridyrnite-M are present in approximately equal amounts . The XRD patterns for the Naike soil (Fig . 3 . 17b) demonstrate that there is an approximately uniform distribution of opal-C and tridyrnite-M down the profile . In the Te Kowhai soil the XRD pattern of the minor peaks reflect the distribution of relatively uniform amounts of opal-C and tridyrnite-M down the profile ( Fig . 3 . 17c ) . (B) Medium Silt : In the Hamilton soil there are well developed peaks for opal-C in all samples except the bottom two where the 3 . 1 4 , 2 . 8 5 and 4 . 48A reflections are greatly reduced . This i s attributed to the much lower cristobalite and tridyrnite contents of sample RlO . Like opal-C, tridyrnite-M appears to be uniformly distributed down the profile except for the two basal samples where the 3 . 8 5 , 3 . 25 and 3 . 0A reflections are greatly reduced . Expanding the scan range to higher angles for these two samples produces a s ignificant reflection at 2 . 0 4A, i . e . consistent with t ridyrnite . In the Naike soil opal-C and tridyrnite-M are comparatively uniformly distributed down the profile (Fig . 3 . 17e ) although in sample NB they a re both much reduced . The medium silt fraction of the Te Kowhai soil also has uniformly distributed opal-C or t ridyrnite-M (Fig . 3 . 17f ) . A 5 1 B Q 0 c:t[. 0 T3 T2 Rl � - R2 � : R3 R4 R5 �: ____.,�_ R6 � : R7 RB �: � : R9 0 T 1 � · T2 RlO c l �40 Figure 3 . 17a : Hamilton coarse s i lt fraction . Figure 3 . 1 7 : Forms of the XRD patterns between 2 4° and 4'0 29 for opal-C , tr idymite-M and quartz in the s i lt fractions of the Hami lton , Na ike and Te Kowhai soils . Q des ignates quartz ref lections . C 1 , C2 , C3 , C4 are the 4 . 0 5 , 3 . 14 , 2 . 85 and • 2 . 4 8A ref lections of opal-C . T 1 , Tz , T3 , T4 and T5 refer to the 4 . 33 , 4 . 1 1 , 3 . 85 , 3 . 2 5 and 3 . 0A ref lections of tridymite . ( A ) shows the smal ler ref lections , ( B ) shows the detail of the reflections between 2 4° and 2 60 2e . These are repeated for each samp le down the prof i les . Rl R 2 R3 R4 liS R6 R7 RB R9 RlO 52 A B Figure 3 . 17 b : Naike coarse s i lt fraction . A TIO TK8 TK9 . c : T Figure 3 17 2 40 e Kowhai B T2 cl T2 cl coarse s i lt fraction . 5 3 TKl TK2 TIO TK4 TK5 TK6 TK7 � --=·-_;;;;;,.. -, TK8 � TK9 TKlO 5 4 Q A B 0 C4 0 Tl Rl cl Tz =5 Rl ----- R2 $ R2 � R3 R3 � 114 R4 5 115 RS 5 116 R6 5 117 R7 Ill � 118 lt!l R9 l Q � RlO T2 cl 1110 44° 240 Figure 3 . 1 7 d : Hamilton medium s i lt fraction . 55 A Q B 0 c• Tl c l T2 0 � Nl Nl N2 s 112 N3 =s 113 N4 � •• NS � liS N6 � N6 N7 5 lf7 NB � 88 -s--N9 � 119 T2 0 T1 s NlO c l 1110 f40 �40 Figure 3 . 17e : Na ike medium s i lt fraction . 56 A Q B c4 CJ c2 0 TJ TU cl T2 0� Tll:l � Tll:2 TK2 =s TKJ TII:J � TK4 � TJ(5 TK5 � TU Tll:6 5 TJ(7 Tl<7 TJI:8 � TU TK9 � TU Tlrmed by this pathway . The morphologies of the opal-A grains in ( 1 ) the A and upper Bt 1 horizons of the Hamilton soil, ( 2 ) the A and Bw horizons of the Naike soil , and ( 3 ) the Te Kowhai soil, a re of phytoliths and microfossils , consistent with a biogenic origin . The dusty and concentric opal-A have morphologies consistent with inorganic origins and they are here thought to have formed in the soil . IR spectra for the dusty and 1 0 3 concentric opal-A ( Fig . 3 . 1 3 ) are both s imilar t o those from opal (Yoshida et al . 1 95 9 ; Kamatani 1 9 7 1 ) except for a pronounced inflection at app roximately wave number 9 6 0 cm-1 probably related to a Si-OH bond . Knauth and Epstein ( 1 9 82 ) have shown that oxygen isotope analysis of opal-A is difficult because of the differential release of adsorbed, occluded and structural water ( see also Jones and Segnit 1 9 6 9 ; Bartoli 1 9 8 5 ) . This may be further complicated by ( 1 ) the evaporation effect , where o1 6 is preferentially lost during evaporat ion (Stewart and Taylor 1 9 8 1 ) so 51 8o increases in the remaining water , ( 2 ) the temperature effect , S1 8o decreases with increasing temperature , and ( 3 ) post-deposit ional exchange with younger ambient wate r . These problems , together with the possibility that oxygen isotope equilibrium may deviate from linearity at low temperatures (Kawabe 1 97 8 ) suggest that only broad generalities arising from differences in S18o should be made , particularly considering the s i ze of the data set . Comparison of the S1 8o values of the four samples of opal-A analysed indicates that there is a significantly wide range of values . Equilibrium temperatures calculated using different calibrat ions (Clayton et al . 1 97 2 ; Knauth and Epstein 1 9 7 5 ; Kita et al . 1 98 5 ) range from 9°C to 37°C with estimated temperatures from the same sample being highly variable , depending on the particular calibration used . This range is too broad to warrant detailed interpretation but in general the calibrations predict that the soil phytoliths formed in an environment approximately 1 0°C cooler than the concentric and dusty opal-A (assuming that all formed in equilibrium with waters that had s imilar isotope chemistry) . The factors which are thought to lead to the formation of hydrogels and opal -A include high temperature , low pH, and silica supersaturation . As the dusty and concentric opal-A content appears to be stratified in the soil, changes in the controlling factor ( s ) should occur at the boundaries of the opal-A-bearing zone . There are no signi ficant contrasts of pH in the profiles . pH values in the soils range from 5 . 6 in t opsoil to � . 3_ at one metre depth in the Naike soil (Anon . 1 9 8 1 ) and f rom 5 . 7 in topsoil to 5 . 2 at one metre depth in the 1 0 4 Hamilton soil ( Joe 1 9 8 6 ) . At depths greater than 5 0 cm the temperature differential and variability of the two soils would be minimal, so current pH and temperature are not considered critical factors in the occurrence of inorganic opal-A in the soil . Silica supersaturation of the soil solution is probably most readily induced where water table fluctuat ions and desiccation are most marked i . e . in the topsoil , but the distribut ion of acid oxalate-soluble silica indicates that there is no marked change in silica distribution down the profile (Anon . 1 9 8 1 ; Joe 1 9 8 6 ) . These factors , taken together with the contrasting morphologies of the opal-A in two soils which have similar phys ical and chemical environments, suggests that opal-A is either an art ifact of, or · at least initially developed during, an earlier weathering cycle . If the correlation of the st ratigraphy of the Hamilton and Naike soils to the Hamilton Ash Group is correct then the concentric and dusty opal-A-bearing zones occur in parent materials that are of considerably different ages . The beds in which the dusty opal-A is found have been correlated with the upper Ohinewai Tephra Formation + H3 beds and with the 250 ka Mount Curl Tephra . Shepherd ( 1 9 8 4 ) describes a palaeosol developed i n the H3 bed and Ohinewai Tephra Formation, so it is concluded that the middle and lower zones of the Naike soil ( i . e . those zones containing the dusty opal-A) were initially weathered during this period . The concent ric opal-A occurs in horizons which are overlain by the Rotoehu Ash so they are at least 50 ka old . If the correlation between the Hamilton soil s ite, the Welches Road section and the Te Kuiti section is tenable then the Hamilton soil lower zone ( i . e . the zone containing the concentric opal-A) is tentatively correlated with the upper horizons of the " older beds" at Te Kuit i . Stevens and Vucetich ( 1 9 8 4 ) , assuming a uniform ac�umulation rate, inferred these horizons to have been depos ited c . 8 0-110 ka BP . If it can be assumed that opal-A formed (or began to form) during weathering soon after deposition of the associated parent materials (Ward 1 9 6 7 ; Stevens and Vucetich 1 9 8 4 ) then the dusty opal-A is considered older than the concentric opal-A . 1 0 5 Although the dusty and concentric opal-A have significant morphological differences and have been interpreted to be of markedly dif ferent age s , the �1 8o and IR data suggests that they comprise s imilar materials and that they formed at low temperatures . An ordered internal structure was not observed in the dusty opal-A but the concent ric opal-A comprises particles that are c . 1 6 0 0A in diameter and which appear to be very s imilar to the microspheres identified in precious opal s (Jones et al . 1 9 6 4 , 1 9 6 6 ; Darragh et al . 1 9 6 6 ; Sanders 1 9 6 8 ) . These are thought to form by the aggregat ion of floes in thin hydrogels with subsequent desiccat ion "setting" the st ructure (Darragh et al . 1 9 6 6 ) . The same proces s probably produced the dusty and ·concentric opal-A . The marked contrast in refract ive index between zones probably reflects a significant change in either the size of the individual floes or in the water content . Darragh et al . ( 1 9 6 6 ) considered that the presence o f open cavities was a significant prerequisite for the formation of opal and the form of inorganic opal­ A identified here is consistent with this . Although the dusty opal-A has fine inclusions throughout the grains they a re not in sufficiently high concentrations to demonstrate that the opal -A had enclosed a soil aggregate . It is concluded that these grains developed in pores within the soil . The concentric structure of the opal-A suggests a rhythmic deposition sequence . Of the three main factors identified with the formation of opal-A it is improbable that pH by itself would be cyclic so the main factors involved with the deposition of opal-A are probably related to temperature and silica saturation . If they are related to temperature these cycles could be climatic , on a scale of a decade , a millennium or perhaps of stadial propo rtions . It is improbable that they could be annual cycles unless the growth period of the grains was very short , as the grains have only five zones at most . Aridity was considered a ma j or factor in the format ion of opal in Australia (Darragh et al . 1 9 6 6 ) and it may be that a similar factor, either as droughts or stadials produced the desiccation required to form the opal-A . Judging by the variations in the numbers of zones not all grains have undergone the same number of cycles . 1 0 6 Variable sil ica supply i s another factor which could be cyclical . Studies of recently erupted ashes showed that there may be large increases in the silica leached from an ash soon after erupt ion (White and Claasen 1 9 8 0 ) . It is poss ible therefore that immediately after an eruption a sudden increase of silica in solut ion produces silica supersaturat ion and given the appropriate desiccating environment this may produce opal-A . While this pro ject has demonstrated that the cristobalite identified in the soils studied is derived from igneous sources it has also identified a low temperature form of inorganic opal-A in the soil . It is thought that weathering of andesitic and rhyolitic tephras provided a re latively continuous source of silica in solut ion which with polymerisation produced hydrogels . These accumulated at specific sites in the soil and subsequent dehydration produced opal-A . Repetition of this process produced the concentric zoning . PREVIOUS WORK CHAPTER FOUR SAND AND SILT MINERALOGY AND GEOCBEMISTRY OF THE TOKOMARU SILT LOAM INTRODUCTION 1 0 7 The Tokomaru s i lt loam i s a soil developed on the high terrace of the east bank of the Manawatu River (Fig . 4 . 1 ) near Palmerston North . It has formed in the youngest of a sequence of silty units which overlie interdigitating gravels and sands that were deposited on a marine bench (Te Punga , 1 9 62 ) . This is the Tokomaru marine bench (Hesp and Shepherd 1 97 8 ) which was cut during a period of higher sea level . One of the earliest geological descriptions of the area (Crawford 1 8 8 6 ) noted that "the drift gravels form terraces" and suggested that the gravels were raised beaches . Park ( 1 8 87 ) included the surficial deposits in a "Drift Formation" . In 1 9 10 he included the surficial deposits in the "Rangitikei fan" ( still part of the Drift Formation ) , a "maritime" fan built from material transported down the larger rivers between the Manawatu and "Wangaehu" ( sic) Rivers . Marshal! and Murdock ( 1 92 0 ) noted that there were large muscovite flakes (unknown in the local North Island basement rocks ) in the. Plio­ P leistocene "papa" underlying the Drift Formation and described extra­ regional pebbles with granitic and schistose affinities in the raised beach deposits . They suggested that these ext ra-regional pebbles were evidence for a late Pleistocene land bridge with northwest Nelson and that a climatic cooling had occurred at that t ime . ONAERO• EGMONT CEN�e � \ • I ,_ IIANGATOKI • CAPE FAREWELL 0 I 50km 100km I Figure 4 . 1 : Location map of part of central New Zealand showing the location of the Tokomaru s i te . TVZ refers to Taupe Volcani c Z one . 1 0 8 1 0 9 Hudson and Fife ( 1 9 40 ) were the first to report on the soils of the terraces . This work ( on mole drainage ) was in response to a ma jor l imitation of the soil for agricultural purposes . It has a perched water table which results in poor drainage in winter . They documented the grain size distribut ion down the profile and showed that the soil was dominated by their fine sand ( 0 . 2 - 0 . 0 02 mm) fraction . They a lso noted the "clay bulge" between 44 a d 60 cm depth and described iron concretions (see also Te Punga 1 9 5 4 ) which commonly occur in a zone above the " clay bulge" . Hudson and Fife were also the first to note "the presence of a narrow sandy layer an inch or two in thickness " , ( the Aokautere Ash o f Cowie 1 9 6 4 ) at approximately 2 . 2 m depth . They regarded the origin of the silt as "marine sediments now forming an e levated coastal plain" . Fife ( 1 945 ) in studying a "yellow-grey loam" ( sic) (Grange 1945 ; Pohlen et al . 1 9 4 7 ) in the Manawatu ( the Tokomaru s ilt loam) provided the first data on the chemistry of the soil . Using pH and base exchange chemistry he showed a marked change in the chemical properties within the B horizon and between the B and C horizons . His data ,came from an untopdressed profile among forest remn ants and although the exact site is unknown, ( it is believed to be in the vicinity of grid reference T24 / 3 0 6 8 7 9 , J . A . Pollok pers . comm . 1 9 8 6 ) , it probably represents the best chemical data for a virgin forest soil of this terrace . Taylor ( 1 94 8 ) grouped the yellow-grey loams of the North Island (Grange 1 9 4 5 ) with the South Island Lowland Tussock Soils (Grange 1 9 4 6 ) and changed the name to yellow-grey earths to emphasis the zonal nature of the group . It was not until the 1 : 2 5344 0 North Island soil map ( Soil Survey Staff 1 9 5 4 ) was published however that the group was formally described and the Tokomaru silt loam identified as belonging to the group . The group is characterised by "greyish topsoils , yellowish subsoils with a hard, massive pan" below the subsoil . Greyish bands of gleyed soil immediately above the pan pass down into vertical cracks in the pan . Although they describe the parent material for the Tokomaru silt loam as alluvium, the parent material for the yellow-grey earth group is given as , amongst others "drift deposits including f ine volcanic ash and other loess like beds" . They also state " examination of the minerals of the sand fraction has shown 110 . . . . . . the parent material of the soil is st rat ified and that there has been some accumulation of airborne material during soil formation" ( Soil Survey Staff 1 9 5 4 ) . A comprehens ive summary of the phys ical and chemical properties of the yellow-grey earths was given in a symposium on this soil group in 1 95 8 (New Zealand Soil News 6 : 2 0 6-230 ) . In a detailed study of the sediments on the marine bench south of Palmerston North , Oliver ( 1 9 4 8 ) described a sandstone (Otaki Sandstone ) equivalent at least in part to the Drift Formation of Park ( 1 9 1 0 ) . He included the overlying silts in the Otaki Formation . According t o Oliver most of the Otaki Formation was deposited in a shallow marine to beach environment with much of the sand being derived from reworked Tertiary sediments to the north . Te Punga ( 1 95 3 ) in a study o f the Rangitikei Valley correlated the alluvium (greywacke derived conglomerates plus sands ) overlying the Cast lecliffian sediments ( i . e . the Drift formation) with the Hawera Series of Thomson ( 1 9 1 6 ) . Rich ( 1 9 5 9 ) in a study of the Cenozoic geology of the lower Manawatu Valley included the gravels and over lying silts in the Tiritea Formation . He described approximately 40 metres of rarely fossiliferous interlaminated gravels , sands and silts, which often have ripple marks , capped by 6 met res of yellow-grey silt . He suggested that this capping of "thin, yellow, and in places sandy, silt layers may represent alluvial or aeolian deposition . A sheet of yellow-gray silt forms the top member of the Tiritea Formation in most places . · · · · · · a distinct vertical parting invites comparison with loess . An aeolian origin is suggested by a lack of stratificat ion and by a persistent 3 to 6" band of gray-white pumice ash 3 to 5 feet below the top · · · · · · . Thickness decreases away from Anzac Park but the silt with the ash band persists southwards to the vicinity of Linton . " In the north he traced the ash to an a rea northeast of Colyton and suggested that the "pumice material was probably air-borne to site of deposition" and "pumiceous material came originally from the Taupo volcanic zone" . On the greywacke along the inner (east ) edge of the Tiritea Formation, Rich also describes outcrops of sands with " steeper cross bedding, 17-30° · · · · · · suggesting some o f the sand is wind blovnw . He f inally concludes that "The widespread silt forming the 1 1 1 topmost member of the formation suggests that the final phase o f the Tiritea deposition may have been the aeolian distribut ion of loess­ like silt " . Earlier, Birrell ( 1 9 5 6 ) had also referred to the youngest unit on the Tokomaru marine bench as "loess-like silt s " . Cowie ( 1 963 , 1 9 64a ) realised that the thin sand of Hudson and Fife ( 1 9 4 0 ) and the ash of Rich ( 1 9 5 9 ) were parts of a much more extensive unit that formed a thin veneer mant ling the landscape . He named it the Aokautere Ash . At its type section ( 1 . 5 km east of the Tokomaru s ilt loam site of this study) the ash consists of 1 . 5 cm of fine pinkish pumiceous silt overlain (with a sharp boundary) by 1 1 cm of a normally graded coarse purniceous sand which grades into the overlying silt . The base of the lower pumiceous silt is sharp and undulating . The ash is relatively continuous in the road cutting at its type section but elsewhere in the Manawatu is discontinuous . Isopachs show that the Aokautere Ash increases in thickness towards the central North Island . Vucetich and Howarth ( 1 97 6 ) have proposed that the Aokautere Ash, Scinde Island Ash and Oruanui Breccia are members of the Kawakawa Formation, a c . 2 0 , 0 0 0 year o ld rhyolitic eruptive from Lake Taupo . Recent work ( Self 1 9 8 3 ; Self and Healy 1 9 8 7 ) would group t he above members with the Wairakei Breccia (Grindley 1 9 6 5 ) and proposed the name Wairakei Formation . The problem of correlation and nomenclature has not been satisfactorily resolved so for the purposes of this work the term Aokautere Ash sensu stricto (Cowie 1 9 6 4a ) is used . Cowie ( 1 964b) demonstrated that the Aokautere Ash and therefore the enclosing silts must have been deposited subaerial ly so that the silts were of a loessial origin . He showed that the loess was thin or absent on the Ohakean Terrace (Te Punga 1 953b) and that the post­ Aokautere Ash loess thinned and became finer towards the southeast away from each ma j or river, so drawing the conclusion that the loess was derived from material blown off the terraces built during the Ohakean aggradation . This terrace formed during the aggradation phase of the last stadial (Milne 1 973a , 1 9 7 3b) . It is now recognised that in the southwestern North Island the silty material overlying the terrace gravels (all part of the drift regime of earlier workers ) is composed of multiple loess units each separated by a palaeosol (Cowie and Milne 1 1 2 1 97 3 ; Leamy e t al . 1 9 7 3 ; Milne 1 97 3a , 1 9 7 3b) . During colder stadial periods aggradation occurs in the river valleys as a consequence of devegetation and accelerated erosion (Vella 1 9 6 3 ; Leamy et al . 1 9 73 ) and with the relat ively colder, windier and drier condit ions silt size material can be removed from the aggradat ion surfaces and deposited as loess on older and higher terraces . During interglacials or interstadials soils develop as the climat ic condit ions improve, only to be buried by loess deposited during a subsequent cooling . On the Tokomaru marine bench between two and four periods of loess accumulation a re preserved (Cowie 1 9 7 3 ; Mcintyre 1 9 7 5 ; Milne and Smalley 1 9 7 9 ; Anthony 1 9 8 4 ) with the Tokomaru silt loam developed in the youngest of these . Since Cowie ( 1 9 6 4b ) there has been a series of detailed studies undertaken on various aspects of the pedological properties of the Tokomaru silt loam . The distribut ion of Fe , Mn, V, Ni , Cr , Co and Ti between the c oncretions and soil (Brooks 1 9 6 5 ) showed that there was a marked concentrat ion of all these elements except Ti in the concretions . Comparison between the parent soil and the gleyed cracks showed a loss of all these elements (Co was beyond detection limit ) in the gleyed material . Symes and Wells ( 1 973 ) in an X-ray study of the topsoil mineralogy from Mount Egmont to Palmerston North reported only trace amount s of ash in the Tokomaru silt loam . Their method however was unsuitable for identifying minor amounts of volcanic components but they did show a systematic increase in quartz content away from Mount Egmont . Kirkman ( 1 973a , 1 97 3b) showed that the occurrence of amorphous Si , Al and Fe reached a maximum in the B horizon . Soil water and related soil physical parameters in the Tokomaru s ilt loam were investigated by Gradwell ( 1 9 7 4 ) and Scatter et al . ( 1 97 9 ) . Thei r work confirmed inferences from the morphological description of the Tokomaru silt loam in that quantitative measurements were obtained to show the gradual change in bulk density and water properties down to the pan which is relatively dense and impervious . Below the pan the data indicate little further change until the z one of influence of the Aokautere Ash . 1 1 3 I n 1 975 Pollok published the first result s of a n ongoing invest igation of the pedology of the Tokomaru silt loam . He (see Pollok, 1 9 8 4 ) designated a pseudogley horizon in the B horizon and the dense pan a fragipan in the C horizon . Using extractable chemistry, clay mineralogy and micromorphology he demonst rated ( l ike Fife 1 9 45 ) that there was a marked difference between the B and C horizons . The Tokomaru silt loam has a measure of variable charge and Pollok ( 1 9 8 4 ) suggested that this was due t o ferrolysis . Pollok concluded that the soil is the product of polygenesis with the early formation of the f ragipan in the loess followed by subsequent pseudogleying which is the prominent current process . During a survey of Kairanga County, Cowie ( 1 97 8 ) studied a site adj acent to the one presently being invest igated and presented data similar to that of F i fe ( 1 945 ) and Pollok ( 1 97 5 ) . In studying the relat ionship between the yellow-grey earths and adjacent yellow-brown earth/yellow-brown loam intergrades he concluded that the difference between the groups was not due to different parent materials . Rather they were the result of variations in climatic factors , with seasonal wett ing and drying p roducing the compact fragipan of the yellow-grey earth . Initial results of this investigation (Wallace and Neall 1 9 8 2 , 1 9 8 4 ) presented the sand mineralogy o f the Tokomaru s ilt loam and identified significant rhyolitic and andesitic tephra components ( other than the Aokautere Ash) . These results showed a marked stratigraphic break at approximately 0 . 5 m which is thought to be related to an hiatus in loess accumulation marking the end of the Otiran Glacial stage . A threefold division for the post -Aokautere Ash loess was proposed : ( 1 ) an upper mixed tephra/l oess unit , ( 2 ) a middle quart zofeldspathic l oe s s , ( 3 ) a lower tephric loess down to the ash . In a study of the relationship between the yellow-grey earths and the yellow-brown earth/yellow-brown loam intergrades Parfitt et al . ( 1 98 4 ) presented limited mineralogical data on the Tokomaru silt loam . Like Cowie ( 1 9 7 8 ) they suggested that the differences between the yellow­ grey earths and intergrades were due to climat ic factors . High summer water def icits in the yel low-grey earths exert hydraulic suction that produces the increase in bulk density . This impedes drainage leading to separate weathering paths and different soils . 114 The Tokomaru silt loam, an Aeric Fragiaqualf in U . S . Soil Taxonomy, is a member of the central zone of yellow-grey earth soils ( se e Bruce 1 9 8 4 ; Cowie 1 9 8 4 ) . It has developed in last stadial Ohakean loe s s which probably started accumulat ing approximately 2 3 , 0 0 0 years ago ( at least prior to the 2 0 , 0 00 year old Aokautere Ash) and may have continued until approximately 9 7 6 0 years B . P . (based on a radiocarbon dat e in the Rangit ikei River, Milne and Smalley 1979 ) . THE PRESENT STUDY The purpose of the current investigat ion was to study the accumulation of aeolian materials from various sources ( including l oe ssic, aerosolic and tephric) in the development of the Tokomaru s ilt loam . The sample site ( informally known as Pollok' s Pit ) is located on one of the Massey Univers ity farms adjacent to Clifton Terrace at T2 4 / 32 98 8 1 . Clearance of the original broadleaf /podocarp forest began in the 1 8 8 0s and after the initial grass was sown "the area where the profile pit is located was kept as a museum piece" ( Pollok 1 9 75 ) . It has not been actively topdressed or cultivated and a wel l-defined charcoal layer at approximately 5 cm (the burnt remains of the original bush clearing phase ) , the preservation of granules in planes parallel to the surface , and mineralogically discrete layers indicate that the soil has only been minimally disturbed . Samples were fractionated into grain sizes and whereas the sands and coarse silt were subjected to detailed optical investigations , dis solution techniques were employed to determine mineralogical trends in the finer fractions . The first stage of the dissolution which involved repeated heating in HCl removed micas and mafic minerals (Brindley 1 957 ; Henderson et al . 1 9 7 2 ) . After this the samples were t re ated repeatedly with H2SiF6 so removing the feldspar ( Chapman et al. 1 9 6 9 ) and leaving a residue of quartz (plus minor cristobalite in s ome cases ) . Optical investigation showed that there were numerous tephra additions to the soil and that these were concentrated in the sand fraction . This fraction was therefore analysed for maj o r and trace e lements in an attempt to support the mineralogical evidence of 1 1 5 volcanic addit ions to the loess . Chemical analyses were also carried out on the whole soil in an attempt to locate chemical trans locat ions due to pedogenic processes . Phosphorus is relatively immobile in the soil , it being readily f ixed by amorphous Al-Fe compounds . As it is a ma jor plant nutrient phosphorus is removed f rom the subsoil during plant growth and accumulates in the A horizon, therefore if a surface is stable there is a gradual accumulat ion of P . This P is normally retained i f the soil is buried (e . g . by tephra , loess, colluvium etc . ) and the subsequent palaeosol may have a relatively high P content . This property has been used (Walker 1 9 6 5 ; Leamy and Burke 1 9 7 3 ; Tonkin et al . 1 97 4 ; Runge et al . 1 97 4 ; Mcintyre 1 9 7 5 ) to identify palaeosols . Phosphorus dist ribution was therefore determined in a search for palaeosols in the upper zones of the soil . Trace element chemistry of minerals in tephras has been used (Rankin 1 9 7 3 ; Kohn 1 9 7 0 ; Kohn and Neall 1 9 7 3 ) to characterise individual tephras . Apart from the Aokautere Ash, the tephric material s in the Tokomaru silt loam occur as dustings diluted by loess , so that bulk sampling methods are inappropriate . An a lternative is to analyse individual minerals on an electron microprobe (Westgate et al . 1 9 7 0 ; Westgate and Gorton 1 98 1 ; Froggatt 1 983) . Such an invest igation of the volcanogenic components in the Tokomaru silt loam was undertaken for correlation with potent ial sources . Although pollens are not preserved in the loess due to the oxidis ing environment , the occurrence of different forms of phytoliths (plant opa l ) hinted at a potential for discerning the vegetative history . Phytoliths are composed of biogenic silica that forms replicas of plant cells or c rystals within plant cells . These are released when the cell decays . It is unclear whether silica is an essential element for plant growth or even advantageous to the plant but Japanese workers believe that silica deposited within rice plant cells makes the plant more resistant to fungal and insect attack (Yoshida et al . 1 9 62a, 1 9 62b) . Phytoliths are formed when s ilica in solution moves through the plant system until water loss due to transpiration allows the silica to precipitate, most commonly in the leaves . Struve ( 1835 ) was one of the earliest workers to investigate 1 1 6 silica in plants and Ehrenberg ( 18 4 7 ) used the term phytolitharia for some dust constituents he described . It was Ruprecht ( 1 8 6 6 ) who first used the term phytolith for "minute stoney parts of plants" . Subsequent work (e . g . Jones and Handreck 1 9 67 ; Twiss et al . 1 9 6 9 ) has shown that phytolith shape may be identified with particular plants and that they are commonly preserved in soils ( Baker 1 95 8 ; Beavers and Stephen 1 958 ; Wilding and Drees 1 97 1 ; Bartoli and Guillet 1 9 7 7 ) . Ecological reconstructions based on phytoliths have also been attempted (Baker 1 9 5 9 ; Rovner 1 9 7 1 ) . In New Zealand Raeside ( 1 9 6 4 a ) des cribed plant opal (phytoliths ) from loesses and later attempted to relate these to those he extracted from various tussocks and sedges (Raeside 1 9 7 0 ) . Potentially, phytoliths may be used like pollens and as the loess parent material to the Tokornaru s ilt loam accumulated on a grass/ shrub dominated surface compared with the pre-European bush cove r , phytoliths were extracted from samples T17 to T2 4 seeking this change in vegetation . In an attempt to identify the soil phytoliths , wood and leaves from elements of the present bush on the Tokomaru terrace, kahikatea (Podocarpus dacrydioides) , rimu (Dacrydium cupressinum) , totara (Podocarpus totara) , black beech (Nothofagus solandri ) and tawa ( Beilschmiedia tawa) were processed . Two peats representative of forest communities were also studied . Pollen data indicated one peat ( from Maruia , South Island) to be beech dominated while the other ( from Mt . Egrnont ) is from a mixed podocarp associat ion ( C . M . Lees pers . comm. 1 9 8 6 ) . \ I I RESULTS GRAIN SIZE' DATA The relative proportions of the various size fract ions are presented in Appendix 4 . The textures of all 1 17 samples are silt loams except for T1 and T17 which are silts and T2 0 which is a silty clay loam . Even the Aokautere Ash is of silt loam texture . This is due to s ignif icant amounts of non-volcanic material in the silt size fractions in the ash . The grain size data are very similar to those of Hudson and Fife ( 1 940 ) and Pollok ( 1 97 5 ) . Like Hudson and Fife cont inuous sampling was used ( in contrast to the horizon sampling of Pollok) , which gives much improved definition to the patterns of changes down the profile . (i) CLAYS : The main feature of the clay distribution down the profile is the "clay bulge" described by Hudson and Fife ( 1 9 4 0 ) and Pollok ( 1 97 5 ) . It is here reflected in the high clay content of sample T20 (Fig . 4 . 2 ) which is located towards the top of the Bgt2 horizon . Above this there is a variable c lay content with a minor increase just below the surface . In the Cxg horizon the clay content is relatively constant and it should be noted that this uniformity continues above the cap of the fragipan into the middle of the Btg2 horizon . Below the Cxg horizon there is a rise in c lay content at sample T8 followed by a general fall in clay content to the Aokautere Ash . This trend T2S T24 T23 T22 T21 T20 T1t T11 T17 T11 T15 T14 T13 T12 T11 T10 Tt Tt T7 Tt TS T4 T3 T2 T1 J---=-10.3 .5 c., 1.55 Cwg1 2.34 c211m 13-20 " m 20 40 Weight % of Totel Semple so 5-2 "m 0 5 20-5 !1m 10 20 12�3 " m l 250-125!1m 5 Weight % of Totel Semple Figure 4 . 2 : Var i a t i on in gra in s i z e d i s t r i bu t i on for the Tokoma ru s i l t loam . � � ()) 1 1 9 parallels the rising glass content in this region of the profile ( see mineralogy section) . Below the ash the clay content rises to levels similar to those of the Cxg horizon . (ii) SILTS : Silt distribut ion is broadly antipathetic to the clay dist ribut ion (Fig . 4 . 2 ) . The 5-2 � fraction, taken to represent global aerosolic dust (Mokma et al . 1 9 72 ) , has a relatively uniform distribution throughout although there are perturbations at the Aokautere Ash . In the 20-5 � fraction there is a marked decrease between samples T19 and T2 0 , a slight increase from samples T15 to T19 and higher values in the Aokautere Ash . The Aokautere Ash has a bimodal grain size distribution (modes at 250 � and 2 0 -5 �) so that the increase in the 2 0 -5 � fraction for the Ash, compared with the loess is attributed to increased medium silt sized glass shards . The higher H2SiF 6 soluble material in this fraction of the ash (compared with adjacent samples ) supports this conclusion . The mode of the loess is in the 63-20 � fraction . At the level of the Aokautere Ash in this fraction there is a lower coarse silt content compared with the adj acent Cwg horizons . The top seven samples , particularly the ABg (T2 4 ) and top of the Btg2 (T2 0 ) , have a lower coarse silt content than in the C horizon . Samples T16-T18 (the cap of the fragipan) have coarse silt levels s lightly below those of the underlying C horizons . (iii) SANDS : The sand fraction forms up to 6% of the loess (excluding the influence of the Aokautere Ash ) and although samples T9 and T12-T13 appear to be above background the only sign ificant shift in trend is between samples 19 and 2 0 where there is a general lowering of the total sand content (Fig . 4 . 2 ) . Individually the various divisions of the sands present quite different t rends . In the very fine sands ( 12 5- 63 �) there is a maximum at the Aokautere Ash . The top six samples ( T20-T2 5 ) t rend at slightly lower levels compared with the Cxg-Cwg horizons . The trends for the fine sand ( 2 50-125 �) show a maximum at the level of the Ash and the top four samples (T22- T25 ) have fine sand contents above those of the Cxg-1Cwg1 horizons . There are also slight increases at the levels of samples T9 and T13 . The medium sand ( 5 0 0 -250 �) content is at a maximum at the Ash and there is an increase in this fraction above sample T2 1 . Although the 1 2 0 coarser sand fractions are only a minor component they are cons idered significant because they reflect important trends in the mineralogy . Further , Hudson and Fife ( 1 94 0 ) also demonst rated a change in the coarse sand fract ion at approximately 45 cm depth . OPTICAL MINERALOGY The mafic content of the samples i s low, so to improve the quality of the data the various sand fractions were split into magnetic and non-magnet ic fractions . The mineral proportions were determined on both grain mounts and thin sections prepared from these f ract ions , but grain mounts of only whole samples were studied for the coarse silt ( 63 - 2 0 �) . The mineral proportions are recorded in appendix 5 . Minerals or mineral groupings showing repeatable and/or systematic t rends are plotted against depth ( sample number) . Although variations in trends within a particular f raction seem significant they can be biased by variations in the proportions of that fraction in the total sample (e . g . hornblende dominating a magnet ic fraction is insignificant , where the magnetic fract ion is a very minor amount of the whole sample) . To obviate this , data are usually presented as proport ions of the total sample but some data are presented as a propo rtion of the particular fraction . When plotted as a percentage of the total sample variations may seem small , but they are highly s ignificant because they are based on a much wider data base than is apparent . Absolute proportions (percent of total sample ) of minerals or mineral associations of demonstrably volcanic . origin are used to identify possible tephric additions to the loess, while variations in the loess are investigated using the relative proportions (percent of fraction) of non-volcanogenic minerals . Although the sand content of the samples is low it is important as much of the volcanic material is in this fraction . 12 1 FINE SAND FRACTION Non-Magnet ic Fraction : In this fraction the volcanic plagioclase is above background levels in samples T9-Tl0 and T13 while there are significant peaks at samples T5 and T22 -T2 5 (Fig . 4 . 3 ) . Volcanic lithics (monomineralic aggregates of plagioclase ) increase at the level of the Aokautere Ash (sample T3 ) and again in samples T l O , Tl3 and i n the top SO cm with maxima at samples T22 and T25 (Fig . 4 . 3 ) . The glassy material has been subdivided into shards and pumice in figure 4 . 3 . The Aokautere Ash (with approximately 9 % of the whole sample being glass in this fract ion) dominates and the influence of the ash continues for at least 4 0 cm (up to sample TB) and perhaps 90 cm (up to sample Tl2 ) above the visible top of the ash . The sample immediately underlying the ash ( sample T2 ) is a lso influenced . Above the Aokautere Ash there are significant increases in total glass content at sample 14 and in the top 50 cm, particularly samples T22 and T2 5 . There is also a marked change in the morphology of the glasses at S O cm. Below this level shards dominate, although in the Aokautere Ash shards and pumice are approximately equal , while in the top o f the profile pumice dominates . Excluding the influence of the Aokautere Ash, minerals of a sedimentary origin range from 7 5% in the Cxg to 55% in the top 50 cm . There is a significant and systematic increase in the proportion of sedimentary lithics (quart z-feldspar greywacke and illite greywacke ) with depth (Fig . 4 . 4 ) . Also, although there is a problem with obtaining representative data for the micas , the data in appendix 5 indicate a reduction in mica content in tne top 40-50 cm . Magnetic Fraction : The magnetic fraction of the fine sand varies between 4% and 39% (Fig . 4 . 6 ) . Generally a high magnetic content reflects a higher proportion of grains f rom volcanic sources . The pyroxene and hornblende content increase at the Aokautere Ash and at T25 T24 T23 T22 T21 T20 T11 T11 T17 T11 T15 T14 T13 T12 T1 1 T10 Tl Tl T7 Tl T5 T4 T3 T2 T1 .3 .s .75 Cxg 1 .55 Cwg1 2.21 2.34 A 0 0 . 1 0 . 2 0 0 . 1 0 . 2 0 . 3 0 20 40 60 80 t total sample t total samp le t of the non-magnetic f ine sand Figure 4 . 3 : Tokomaru soil - Abundance of volcanic p lagioclase ( A ) , p lagioclase volcanic lithic ( B ) , end glass ( C ) in the non-magnetic fract ion of the fine sands . I n C the tota l glass ( • ) has been subdivided into pumiceoua ( o ) and non-pumiceoua ( c ) trac t i ona . ...... "" "" T25 T24 T23 T22 T21 T20 T19 T18 T17 T1 6 T15 T14 T13 T12 T1 1 T10 T9 T8 T7 T6 T5 T4 T3 T2 T1 m Ah 0 . 1 ABg BAg 0 .3 Btg1 [A [-.5 Btg2 0 .75 Cxg 1 . 55 Cwg1 2.21 2C 2 .34 Cwg2 0 2 0 \ \ \ I \ \ \ I I \ f 4 0 60 I I I 80 % of sedimentary f raction Figure 4 . 4 : Distribution of the i l lite greywacke l i thic ( o ) and quartz + sedimentary plagioclase ( o ) as a proportion of the s edimentary fraction in the non-magnetic fraction of the fine sand in the Tokomaru soi l . 1 2 3 T25 T24 T23 T22 T21 T1t T18 T16 T15 T14 T13 T12 T1 1 T10 Tt TB 17 T6 T5 T4 T3 T2 T1 m Ah ABg 0.1 BAg la .3 Btg1 la .5 Btg2 la 1- .75 Cxg 1 .55 CWg1 2.21 2C Cwg2 4 6 8 10 % Total s ample Figure 4 . 5 : Variation in the tota l vo lcanic component of the non-magnetic very f {ne sand ( • ) and f ine sand ( 0 ) fractions of the Tokomaru soi l . 1 2 4 T25 I ... I T24 T23 T22 T21 T20 T1t T1t T17 T11 T1S T14 I C•t T13 T11 T11 T10 W1.SS Tt Tl T7 ICWV1 Tl TS T4 n T2 T1 I 0 10 20 3 0 • l of f ine sand A r 0 . 02 "" . 04 . 06 . 08 l of total sample . 10 . 12 . . c 0 . 0 1 . 02 l of total sample Figure 4 . 6 : Distr ibut ion of minera l phases in the m�gnetic fraction of the fine sand of the Tokomaru soi l . A - magnetic f rac t i on , B - hornb lende ( 0 ) , orthopyroxene ( · ) , cl inopyroxene ( o ) , and C - volcanic p lagioclase . .... N c..n 1 2 6 T25 A 8 T24 A8g T23 aAo .3 T22 .... , T21 .5 T20 T1t 8lg2 T11 .75 T17 T11 T15 T14 C.g T13 T12 T1 1 T10 1 .55 Tt Tl T7 Cwg1 Tl TS T4 T3 T2 2.34 T1 0 0 . 02 0 . 04 0 0 . 04 0 . 08 0 . 12 ' total sample ' total sample Figure 4 . 7 : Tokomaru soi l - Further abundance of vo lcanic components in the magnetic fraction of the f ine sand . A - opaques ( o ) , p lagioclase volcanic l i thic ( o ) : 8 - obsidian ( o ) and p lagioclase-opaque volcanic lithic ( o ) . 1 2 6a samples T S , T l3-T1 4 and T2 1-T25 (Fig . 4 . 6 ) . The relative proportions of the minerals also changes . At the Aokautere Ash orthopyroxene dominates with less clinopyroxene and hornblende lowest . In contrast clinopyroxene dominates samples TS and T2 1 -T2 5 and orthopyroxene is lowest . At sample Tl3 the clinopyroxene dominates but at sample Tl4 both hornblende and clinopyroxene diminish while orthopyroxene increases s lightly . The distribut ion of opaques (mainly t itanomagnetite and ilmenite ) is highly variable with peaks at samples T3 and TS , a high opaque content in T2 2-T25 and a broad zone of higher opaque content for samples T12 to Tl4 . Volcanic plagioclase (drawn into the magnetic fraction because of magnetic inclusions ) shows a marked increase at the top of the profile and at samples T3 , TS and T9 and a slight increase at sample Tl3 . The distribution of obsidian (Fig . 4 . 7 ) increases at samples T 3 , T l 4 and T21-T25 (particularly T25 ) . Data for two varieties of volcanic lithic fragments (monomineralic plagioclase and plagioclase + opaque varieties ) are documented in figure 4 . 7 . The plagioclase volcanic lithics contribute to samples T3 and TS and there are minor additions to broad zones encompassing samples T10-T14 and T2 0 -T2 5 . The plagioclase + opaque volcanic l ithic is highlighted in samples T3-T5 , Tl3 and T23-T25 . Figure 4 . 8 indicates that other than the Aokautere Ash the magnetic fine sand fraction contributes approximately 0 . 2 5 % volcanic material to a total sample . Trends within the sedimentary fraction are difficult to identify because at the level of the Aokautere Ash and in the top 50 cm the sedimentary data set is too small . There is a general trend of decreasing micas, epidote greywacke l ithics and chlorite greywacke lithics towards the top of the profile ( see appendix 5 ) . T25 T24 T23 T22 T21 T20 T19 T18 T1 7 T1 6 T15 T14 T13 T12 T1 1 T10 T9 T8 T7 T6 T5 T4 T3 T2 T1 m Ah 0.1 ABg BAg 0 .3 Btg1 ,-.5 Btg2 0.75 Cxg 1. 55 Cwg1 2.21 2C 2. 34 Cwg2 0 . 2 0 . 4 % of total sample Figure 4 . 8 : Abundances of the total volcanogenic component in the magnetic fractions of the f ine ( o ) and very f ine ( 0 ) sands in the Tokomaru soi l . 1 2 7 1 2 8 VERY FINE SAND FRACTION Both grain mounts of the whole fraction and thin sect ions of the magnet ic and non-magnetic fractions were used to invest igate t rends in the very fine sands . Non-magnet ic fraction : Except for the influence of the Aokautere Ash , minerals with a volcanic association are minor ( c . 5 % of the f raction rising to c . 1 8 % in the top 40 cm) and consist of glass and volcanic plagioclase . At the level of the Aokautere Ash glass dominates this fraction and constitutes 9 % of the total sample (Fig . 4 . 9 ) but for the remainder of the profile glass represents c . 0 . 4 % of the t otal sample and the sum of the volcanogenic material is c . 0 . 5% of the sample . The volcanic plagioclase , although only a t race constituent , indicates volcanic additions to samples T3 , TS and T22- T25 ( Fig . 4 . 9 ) . In the materials of a sedimentary origin there is a gradual increase in the proportion of illite greywacke lithics and a decline in the proportion of quartz with depth (Fig . 4 . 9 ) . Magnetic Fraction : Unlike the fine sand the magnet ic fraction of the very fine sand is a relatively constant component at approximately 3 % , rising to 1 0 % for samp les T21 to T25 . The distributions of the pyroxenes and hornblende (Fig . 4 . 10 ) a re similar to those in the fine s and with significant increases in samples T3 , TS , and T2 1 to T25 . A change at samples T13-T14 is also evident but additionally there is a s ignificant increase in hornblende content in samples T 9 and TlO . Orthopyroxene dominates the Aokautere Ash but its contribution to the very fine sand has been halved compared with the fine sand and while hornblende contributes s imilar amounts to both size fractions the clinopyroxene content of the very fine sand is greatly reduced. At saq:>le TS hornblende now dominates ( although reduced) and the m I .t.h I T24 T23 T22 T21 T20 T11 T11 T17 T11 T11 T14 I C•a T13 T12 T11 T10 W , . ss Tl Tl T7 ICWG1 Tl TS T4 n T2 T1 1 1 A I � a I • ' c 0 2 4 6 8 10 0 0 . 1 0 . 2 0 . 3 0 20 40 60 t total sample l total sample t of sedimentary components Figure 4 . 9 : Tokomaru soil - Mineral distribution in the non-magnetic fraction of the very fine sand . A - glass ; B - volcanic p lagioclase ; C - proportion of i l li te-greywacke lithic ( o ) and quartz + sedimen tary p lagioclase ( C ) in the s edimentary component . ...... N \D T25 T24 T23 �.3 m T21 �.S T20 T1t T11 U.1s T17 T11 T1S T14 I CID T13 T12 T11 T10 W us Tt Tt T7 1 Cwg1 Tl TS T4 T3 T2 T1 0 0 . 05 \ total sample A 0 0 . 02 0 . 04 ' total sample B 0 0 . 1 ' total sample Figure 4 . 1 0 : Abundances of minera ls in the magnetic fract ion of the very f ine sand in the Tokomaru s i l t loam . A - hornb lende ( 0 ) , orthopyroxene ( · ) , c l inopyroxene ( o ) , B - p lag ioc lase-opaque vo l can lc l i th i c ( o ) , opaques ( 0 ) ; C - glass ( o ) , obs idian ( D ) . c ...... w 0 1 3 1 pyroxenes are great ly reduced . Hornblende dominates sample T13 but , as in the fine sand, orthopyroxene dominates sample T14 . In the top 50 cm the amount of orthopyroxene has increased and the clinopyroxene decreased compared with the fine sand and they are eo-dominant in the very f ine sand . The hornblende content of both fractions is similar . The opaques trend (Fig . 4 . 1 0 ) indicates increases at samples T3 , T5 , T9 , T14 and T22-T2 5 which excepting for T9 is similar to the fine sand . The glass and obsidian contents (both a re microlitic varieties) have increased values for samples T3 and T22-T25 ( Fig . 4 . 10 ) . The ma jor volcanic lithic present is a plagioclase + opaque variety and although it shows a similar distribution to that in the fine sand, with peaks at T3, T5 (a shoulder on T3 ) , T 13 and T22-T2 5 (Fig . 4 . 1 0 ) it contributes only half that of the fine sand . The total volcanic component (Fig . 4 . 5 ) for the magnetic fract ion of both the fine sand and very fine sand fractions are similar . The distribution of the sedimentary components is complex . One striking feature is a drop in the biotite+chlorite , and chlorite greywacke lithic content in the top four samples (T22-T2 5 ) , see appendix 5 . Very Fine Sand Grain Mounts : The glass content of this fract ion reaches c . 9 % of the whole sample at the Aokautere Ash and then declines gradually reaching an average value of 0 . 1 - 0 . 2 % for most of the profile (Fig . 4 . 1 1 ) . There is significant glass mixed with loess for at least 4 0 cm (to sample T8 ) and perhaps 9 0 cm ( sample T12 ) above the visible top of the ash, if the broad rise in glass content at samples T 9-Tl 0 is related to the Aokautere Ash . As in the fine sand fraction there is a consistent pattern in the morphology of the glass with shards being greater than, or eo-dominant with pumice at the base of the section while pumice dominates in the top 4 0 cm (Appendix 5 ) . The amounts of other volcanic minerals a re too low to warrant individual plotting, however it is noticeable ( see appendix 5 ) that the sum of hornblende + pyroxenes and the volcanic plagioclase are both higher in the top 50 cm of the profile . ( i ) ( ii ) A r B . -T25 T24 T23 T22 T21 1----to.s T20 T11 T11 L-.-1.75 T17 T11 T15 T14 I C•g T13 T12 T11 T10 w ,.,, T9 Tl T7 ICWD' Tl TS T4 �:�r-21 T3 2 .34 T2 T1 .....___.. 0 2 4 6 8 0 20 40 60 I total sample I of the sedimentary co.ponenta ..... w IV Figure 4 . 1 1 : Tokomaru soil - Mineralogical variations within the very fine sand as determined on grain counts . A - ( i ) g lass , ( ii ) sum of the vo lcan ic componen ts : B - greywacke ( 0 ) , quartz + feldspar ( 0 ) . 1 3 3 Figure 4 . 1 1 charts the variation o f the sum of the volcanic component s and demonstrates that this fraction normally cont ributes between 0 . 5 and 1% to the total sample . At the level of the Aokautere Ash this contribut ion reaches over 9 % . Grains with a demonstrably sedimentary origin form between 7 0 and 9 0 % of this fraction ( reducing t o 1 5 % at the Aokautere Ash) and there are systematic trends within this sedimentary grouping . The proportion of epidote greywacke and mica greywacke lithics (plotted as greywacke lithics ) , increase with depth and there is a corresponding dec rease in the proportion of quart z + sedimentary feldspar (Fig . 4 . 1 1 ) . Also, muscovite and biotite /chlorite are reduced in the top 4 0 cm . COARSE SILT The coarse silt is the modal interval for the Tokomaru silt loam so mineral trends in this fraction have significant influence . Figure 4 . 12 plots the proportion of minerals which are from volcanic and sedimentary provenances together with various plagioclase types whose sources are equivocal . The fraction is dominated by sedimentary material and even at the Aokautere Ash c . 45% of the coarse silts (c . 1 5 % of the total sample ) are from a sedimentary source . Such material must have been t ranslocated since the ash was deposited . The glassy material of the Aokautere Ash provides c . 18 % of the total sample ( Fig . 4 . 12 ) and glass content gradually decreases to sample T8 . The glass content is constant between samples T10 and T2 1 with slightly higher values (up to 1 . 4% of whole sample) between samples T22 - T2 5 . The total volcanic component (glasses + hornblende + pyroxenes + volcanic plagioclase + high R . I . plagioclase + opaques + obsidians + volcanic lithics ) shown in the same diagram increases gradually from approximately sample T 1 6 and contributes 7 - 1 0 % towards the top of the profile . Although the amounts of individual components are low there is : ( 1 ) a s light increase in hornblende + pyroxenes in the top T25 T24 T23 T22 T21 T20 T111 T11 T17 T11 T15 T14 T13 T12 T1 1 T10 Tt Tl T7 Tl T5 T4 n T2 T1 .3 .5 .75 Cxg 1.55 Cwg1 2.34 A 20 40 60 80 100 Re lative abundance in the coarse s il t ( i ) ( i i ) 8 0 1 0 20 l total sample 20 40 60 80 Relat ive abundance 2 4 6 0 l of coarse s i l t Figure 4 . 12 : Variation in the mineralogy of the coarse s i lt of the Tokomaru soi l . A - Relative amounts of glass ( area a ) , sum of volcanogenic component ( area b ) and sum of the sedimen tary components ( area c ) ; B - Absolute abundance of glass ( i ) and tota l vo lcanic component ( i i ) ; C - Relative abundance of lithics ( 0 ) and quartz + plagioc lase ( o ) in the sedimentary component , D - Distribution of micas within the coarse s i l t . ...... w "" 50 cm, ( 2 ) an increase in the volcanic plagioclase at samples T5-T6 and T 1 9 -T2 5 , and ( 3 ) an increase in the high R . I . plagioclase in the top half of the profile ( appendix 5 ) . 1 3 5 Trends in the sedimentary components are similar to those identified in the coarser fractions . There is a reduction in the sedimentary lithic component and increase in the quart z + sedimentary plagioclase towards the top (Fig . 4 . 12 ) . The mineral data in indicate a significant reduction in mica in the top 50 cm . MINERAL CHEMI:STRY During the optical investigation in the present study several mineralogical components were identified that were consistent with derivation from a volcanogenic source ( such as glass selvedges and inclusions , euhedral c rystal outlines ) . If the source of this material can be identified then t ime planes are provided which enable the dat ing of soil parent materials and calculation of soil accumulation rates . The potential sources for these volcanic components are e ruptions from Mt . Egmont volcano or f rom the Taupo Volcanic Zone . In the latter source this would include rhyolitic tephras from the Taupo and Okataina cent res and andesitic tephras from the Tongariro centre (Fig . 4 . 1 ) . Although these centres have different mineralogies (Table 4 . 1 ) it is not possible to identify unequivocally these different s ources on mineralogy alone . The chemistries of the sources vary from basalt to rhyolite and t hey are situated iri different tectonic environments so the mineral chemistry from each centre might be expected to be different . Mineral chemistries have been used by, among others , Howarth and Rankin ( 1 97 5 ) , Westgate and Fulton ( 1 97 5 ) , Kohn ( 1 97 0 ) and Froggatt ( 1 98 3 ) to identify igneous sources . Initial techniques e . g . Kohn and Neall ( 1 973 ) involved the concentration of a phase from bulk samples Tab l e 4 . 1 : Summary of the mi neral ogy of tephra from some North I s l and vo l c an i c centres . TAUPO CENTRE C l ear g l ass + sod i c p l ag i oc l ase + orthopyroxene + opaques ( m* ) + c l i nopyroxene (m ) OKATAI NA CENTRE - - - C l ear g l ass + sod i c p l ag i o c l ase + orthopyroxene + horn b l ende � cumm i ngton i te � b i ot i te + c l i n o pyroxene (m ) + opaque s ( m ) TONGAR IRO CENTRE - - - Orthopyroxene + c l i nopyroxene + ca l c i c p l ag i oc l ase + opaques � o l i v i ne � hornb l ende ( tr* ) EGMONT CENTRE C l i nopyroxene + hornb l ende + c a l c i c p l ag i oc l ase + opaques � orthopyroxene (m ) + b i ot i te * m M i nor ; tr = Trace 1 36 1 3 7 for which both ma jor and trace elements were analysed . Where there is pos s ible contamination e . g . dilution of tephras in soils , mixing of tephras from various sources , or phases intimately intergrown or exsolved, then the concent ration process is crit ical and bulk sampling techniques are unsuitable . The use of the e lect ron microprobe obviates this problem because individual phases can be analysed . This is an advance in that small quant ities of sample will suffice . However, complicating factors include : ( 1 ) only ma j o r elements can practicably be analysed and ( 2 ) variat ions due to chemical zoning in individual grains can be determined, so enlarging the compositional range to which any unknown is referred . In the present study chemistries of phases from various sources were determined by electron microprobe in o rder to identify chemical discriminating factors (Appendix 7 ) . Aokautere Ash ( c . 20 ka B . P . ) , which is a readily identifiable marker horizon throughout the North Island occurs in the C horizon within the Tokomaru silt loam at 2 . 2 m depth, so potential reference tephras above the ash were sampled . Minerals were separated from pumice and lithic fragments because this reduced the potential for contamination and also because these fragments could readily be unambiguously correlated with known tephras . The chemistries of the pyroxenes , amphiboles, plagioclases , t itanomagnetites and glasses were then determined with the electron microprobe and plots of e lement pairs (one element plotted against another ) were constructed . In a study of Eltham County, Franks ( 1 9 8 4 ) showed that the post­ Aokautere Ash sequence of tephras from Mt . Egmont was thickest to the southeast ( i . e . towards Palmerston North) . Minerals from twelve of the larger erupt ions in this sector were thus sampled to attempt corre lation with the tephric components in the Tokornaru silt loam . This data set was extended by the whole rock data of Neall et al . ( 1 98 6 ) . Reference elect ron microprobe mineral data from the Taupo Volcanic Zone was obtained from Howorth ( 1 97 6 ) and Froggatt ( 1 98 2 ) and augmented with whole rock data for basaltic to dacitic compositions from Cole ( 1 9 7 9 ) , Reid and Cole ( 1 9 83 ) and Froude and Cole ( 1 98 5 ) . In an attempt to exclude possible differences in operator techniques with the mic roprobe analyses , minerals from the Waimihia Lapilli ( Taupo 1 3 8 cent re ) and Rotoma and Whakatane eruptives (Okataina cent re) were analysed as reference material to best represent these centres . Ma jor element mineral chemistry of tephras from the Tongariro centre is not available so the chemist ries of the lava minerals (Hackett 1 9 85 ) are used . When it had been established that it was possible to discriminate between potential sources us ing mineral chemistry, minerals from the soil were analysed for comparison with these sources . The minerals and glasses in the fine sand fraction from samples that have a demonst rable volcanogenic component (samples T l , T3 , T S , T 6 , T 9 , T l O , T13-T 1 6 and T2 1-T2 5 ) were investigated with the electron microprobe (Appendix 12 ) . PLAGIOCLASE : Plagioclase chemistry is usually sensitive to the compos ition of the magma from which it crystallises , (calcic plagioclases form in more basic magma types and sodic plagioclases form in more acidic magmas ) s o plagioclase composition should help differentiate sources . However it is of limit ed use in the present study because chemical zoning produces a very wide range in composition (An3 1 to Ango with typical ranges of 2 5% anorthite within a grain) . Further , zones of corrosion parallel to crystal outlines occur within plagioclases in the soil environments as the more calcic zones are preferentially removed . Notwithstanding these problems plagioclases associated with samples Tl and T3 (average plagioclase compos it ion An4 4 and An4 0 respectively) have lower anorthite content than shallower samples . Average composition for sample T6 is An55 , sample Tl3 is An55 , sample T24 is An4 9 and sample T25 is An52 . AMPHIBOLES : The amphiboles are pargasite to pargasitic hornblende in Mt . Egmont tephras and magnes io-hornblende, edenitic hornblende or edenite in the rhyolitic tephras f rom the central North Island . Amphiboles are absent or very rare in material from the Tongariro centre . Most major elements in the amphiboles produce a good discrimination between magma types . Potassium in particular, together with silicon, iron and titanium produce a distinction between andesites and rhyolites so Egmont sourced material can be readily identified (Figs . 4 . 13 ) . It is not possible to differentiate between the Okataina and Taupe centres . 139 When the amphiboles from the soils are compared with the reference material (Fig . 4 . 13 ) the dominant source of amphiboles in samples above the Aokautere Ash is shown to be Mt . Egmont . There is however a significant proportion of the amphiboles in the top of the profile ( e . g . T2 1 and T25) that have a Taupo Volcanic Zone signature . As expected the chemistry of the amphiboles in the Aokautere Ash is consistent with a Taupo Volcanic Zone source . ORTHOPYROXENE : In eruptives from Mt . Egmont orthopyroxenes are relatively rare (Tonkin 1 9 7 0 ; Kohn and Neall 1973 ; Franks 1 9 8 4 ; Neall et al . 1 9 8 6 ; Lowe 1 98 7 ) and only 12 orthopyroxenes were identified in the c , 1 0 0 0 pyroxenes invest igated within the fine sand fraction of the Egmont reference data in this study . If the references cited above and the data presented here are representative of the mineralogy of the Egmont volcano then orthopyroxene is only a trace const ituent in tephras from this source . It is therefore probably very rare in distal tephras . In contrast to the Egmont s ource orthopyroxenes are the dominant maf ic mineral in rhyolites and are common in andesites from the Taupe Volcanic Zone . A detailed comparison of the orthopyroxene chemical data from the Taupe Volcanic Zone and Egmont centre (Froggatt 1 9 82 ; Hackett 1 9 8 5 ; Lowe 1 9 87 ; this study) indicates that there is a limited discriminat ion between these two source areas . This comparison has however identified significant t rends with respect to the relationship between MnO, FeO and MgO within the eruptives from the Taupe and Tongariro centres . Most orthopyroxenes from the Taupe centre have MnO contents that t rend from c . 1 . 9% to 1 . 3% as MgO increases (Fig . 4 . 1 4 ) . This group is here referred to as high Mn orthopyroxenes . In figure 4 . 14 there is however another trend parallel to the high Mn orthopyroxene trend, with MnO between 0 . 4% and 1 . 3 % . These are here referred to as the low Mn orthopyroxenes . The high Mn orthopyroxenes also have relatively higher FeO (En40-En5 5 > and lower cao, Al2o3 , MgO and Tio2 0 . 8 Cl) ""' + 0 . 6 01 � ....... 01 � 0 . 4 0 Egmont centre • • • • Taupo Volcanic Zone Figure 4 . 13 : Comparison of the chemistries of the amphiboles from the Tokomaru soi l with those from possible volcanic s ources . Symbols - sample T3 ( 0 ) : samples T l , TS , T6 , T 9 , T 1 3 , T 14 ( o ) , and T2 1-T2 5 ( · ) . 1 4 0 2 . 0 2 . 0 1 . 5 0 c:: :E liP +I .t:: 01 •.-I G) 1 . 0 � 0 . 5 0 • 0 • • • 0 0 0 0 0 . � 0 OoO o Jglo8 o o ,oro Taupo \ 0 00 0 o ooR 1/o :'& ooo 0 cll.ool \8 \ :� · �· · ·; 0 0 • 0 0 oo 0 •• •• 48• 0 0 0 0 0 •�o ( 0 00 0 oo 0 Tongariro 0 centre • D 0 0 ••• Egmont cent re D D D 0 ������ OD 11 D • • • • • • • • 14 1 4 0 6 0 8 0 % Enstatite content Figure 4 . 14 : Bi-variant plot of MnO and enstat i te content for orthopyroxenes from the Taupo centre ( o ) , Tongar iro centre ( 0 ) and Egrnon t cen tre ( • ) . 142 compared with the low Mn orthopyroxenes . This dichotomy of MnO data is also reflected in data f rom the Aokautere Ash and its correlative, the Kawakawa Tephra Formation of Howorth ( 1 9 7 6 ) . Froggatt and Solloway ( 1 9 8 6 ) attributed the bimodal nature of the chemistry of the orthopyroxenes in some Taupe centre e rupt ives to andesitic contaminat ion but the orthopyroxenes in the reference material from the present study were separated from rhyolitic pumiceous lapilli that were collected from the middle of multiple shower units . These factors combined with an association with glasses more acidic than those known from Tongariro centre andes ites (Appendix 7 ) preclude an andesitic origin . The o rthopyroxenes with low MnO have relatively high enstatite content (En5 0-En75 ) and in those that have glass inclusions the glasses are commonly dacitic (Appendix 7 ) . This chemical data suggests that the low Mn orthopyroxenes formed in equilibrium with a magma of more basic composition than that with which they were erupted . The low Mn orthopyroxenes are presently known to occur in deposits from four formations (Taupe , Hinemaiaia , and Waimihia tephra formations and the Aokautere Ash ; Froggatt 1 982 ; this study) . Of the eleven major rhyolitic erupt ions from the Taupe cent re in the last 20 ka these four are t he largest (Latter 1 98 5 ; Lowe 198 6 ) . It is here suggested that whereas the smaller e rupt ions tap only the more evolved upper area of the magma chamber, the larger eruptions ( i . e . those with the more enstatitic orthopyroxenes ) are derived from deeper levels in the system . The chemistry of the orthopyroxenes and their associated glasses suggests that the magma chambers associated with the rhyolitic erupt ions from the Taupe centre may be zoned . The o rthopyroxene data from the soils indicates that within the framework of the potential sources considered here the orthopyroxenes originate mainly from either the Taupe or Tongariro centres . The absence of evidence for orthopyroxenes from the Okataina cent re supports results obta ined from the glass chemistry which showed that glasses from Okataina are rare . The rarity of orthopyroxenes with chemical characteristics s imilar to those of Mt . Egmont may be a reflection of the grain size used in this investigation ( fine sand) as 1 4 3 Kohn and Neall ( 1 973 ) record orthopyroxene from Mt . Egrnont smaller than this . However Tonkin ( 1 9 7 0 ) , Kohn and Neal l ( 1 973 ) , Franks ( 1 9 7 4 ) and Neall e t al . ( 1 9 8 6 ) support the findings of this study, i . e . pyroxenes from Egrnont are dominated by augite . Most of the orthopyroxenes from the soil plot within the fields of the high Mn and low Mn orthopyroxene identified in figure 4 . 1 5 . The soil orthopyroxenes which correspond to the high Mn orthopyroxenes probably originated from the Taupe centre , but the low Mn orthopyroxene field overlaps with that of the Tongariro field so in these cases it is not possib le to differentiate between the two sources . In the reference data from the Taupe cent re the low Mn orthopyroxene group forms a relatively small proport ion of " the total orthopyroxenes , whereas in the soil this group is a much greater proportion of the orthopyroxene population analysed . It is here suggested that this enrichment is due to the addition of orthopyroxenes from the Tongariro centre andesites . CLINOPYROXENE : Clinopyroxenes are common in Egrnont eruptives . Within the Taupe Volcanic Zone they are rare in the rhyolites and common in the andesites . As in Lowe ( 1 9 8 7 ) it is only possible to confidently discriminate between Egrnont and Tongariro centre sourced material using CaO . Minor amounts of Cr are however common in Taupe Volcanic Zone c linopyroxenes and rare in those from Egrnont so Cr in clinopyroxenes probably indicates a Taupe Volcanic Zone source . Lowe ( 1 9 87 ) showed that Tongariro sourced clinopyroxenes averaged wo42 while Egrnont sourced material had wo45 . In samples T1 , T5 , T2 4 and T25 the chemistry indicates that the clinopyroxenes are derived from both .Mt . Egrnent and Taupe Vo�banic Zone (Fig . 4 . 1 6 ) . It is not possible .to distinguish between the Tongariro and Taupe centres using clinopy�oxe� chemistry, however clinopyroxenes are rare in rhyolitic tephras cand :Ehere = ar��too many with Taupe Volcanic Zone signatures in sample�' -T2 4 :and . T2 5 for them all to be derived from the Taupe centre . It is therefore likely that some must be from Tongariro centre, possible derived from the Ngauruhoe volcano which began its present cone building phase c . 2 . 5 ka B . P . ( Latter 1 9 8 5 ) . 2 . 0 1 . 5 0 . 5 o a a . Taupo centre a Ill D 0 Do D 00 • 0 • Egmont centre 4 0 6 0 80 % Enstatite content Figure 4 . 1 5 : Distribution of orthopyroxene from the Tokomaru soi l on an MnO - enstatite p lo t . Symbols T2 1-T2 5 ( D ) , and T l , T 3 , T S ( o ) . 1 4 4 2 5 Egmont Centre <;6 2 0 u � 0 1 5 0 . 5 0 . 6 Mg/Mg + Fe 0 . 7 Figure 4 . 1 6 : Comparison between the chemistry of the c linopyroxenes from the soi l and those from possible source regions . Symbols - samp le T3 ( 0 ) ; samples T l , T 5 , T 6 , T9 , T 13 , T 1 4 ( o ) , and T2 1-T2 5 ( • ) . 1 4 5 1 4 6 GLASSES : The Mt . Egmont volcano and the members of the Taupo Volcanic Zone occur in two different tectonic settings (Cole 1 9 8 6 ) and have evolved along separate chemical lineages (Neall et al . 1 9 8 6 ; Cole 1 9 7 9 ; Reid and Cole 1 9 8 3 ; Froude and Cole 1 9 8 5 ) . While XRF analyses can characterise the chemistry of whole rock samples these represent only the less to moderately evolved members of a series as the most evolved members are represented by interstit ial glasses . These glasses require the microprobe for analys is . Microprobe analyses of glasses in rocks are consistent with the XRF data of whole samples from the same suite and . clearly extend the trends to more highly evolved end points (Fig . 4 . 17 ) . Utilising chemical data from the two environments , it can be shown that while the Taupo Volcanic Zone eruptives follow the basalt-andesite-dacite-rhyolite lineage , those from Mt . Egmont are higher in a lkalis and follow a basalt-trachyandesite-trachyte-rhyolite trend (Wallace et al . 1 9 8 6 ) . The two trends plot in distinct fields (Fig . 4 . 17 ) so mic roprobe analyses o f glasses should distinguish between these two sources . Recent data on the chemistry of glasses from tephras in lake sediments in Waikato ( Lowe 1 9 8 7 ) a re cons istent with these distinct fields . Within the Taupe Volcanic Zone there are several eruptive cent res and Froggatt ( 1 9 8 3 ) has demonst rated that among the rhyolites , purniceous glasses e rupted from the Okataina centre are chemically distinct from those erupted from the Taupo centre ( see also Lowe 1 9 8 7 ) . Additionally, while the <1 0 ka eruptives from Taupo (the Holocene Taupe erupt ives ) are indistinguishable from each other they are chemically different to glasses of the Kawakawa Formation ( i . e . Aokautere Ash) (P . W . Froggatt pers . comm. 1 9 8 4 ) . Within the given t ime frame (<2 0 ka ) it is possible to use the chemical variations in FeO, CaO and K2o to distinguish between rhyolitic glasses from the Okataina centre, the Holocene tephras from the Taupo centre, and the Aokautere Ash (Fig . 4 . 18 ) . The clear glas s fragments in the soil have chemistries consistent with a Taupo Volcanic Zone source . In the lower third of the profile the glas s composition is consistent with that of the Aokautere Ash and t here is a signif icant Aokautere Ash component up to 6 4 • Taupe Volcanic Zone 1iiii Egmont lavas lmiTmD Egmont glas s e s M gO 12 10 Na20 + 8 K20 6 4 2 5 5 15 7 5 T 55 15 75 Figure 4 . 17 : Harker diagrams demonstrating the discrete nature of the chemical trends between Egmont centre and . the Taupe Volcanic Zone . B - basalt , TA - trachyandesite , T - trachyte, R - rhyolite , D - dacite , A - andesite . 1 4 7 2 . � 2 . "" 5 �· The lowering of the mica content may be due to weathering but several factors are inconsistent with this : ( 1 ) The top 50 cm is a zone richer in relatively weatherable pyroxenes which are comparat ively unetched and euhedral compared with the highly etched pyroxenes in the Cxg and Cwg horizons where micas are common . It is difficult to envisage a situation where , given similar parent materials and pHs ( 4 . 9 - 5 . 3 in the t opsoils, compared with 5 . 0 - 5 . 2 in the Cxg; Pollok 1 9 7 5 ) micas would be weathered in preference to the readily weathered pyroxenes at one level and not at another . ( 2 ) Micas are still identifiable in the highly weathered tephras in the Hamilton bas in (chapter 3 ) whereas the pyroxenes and glass are aLmost completely weathered. (3 ) Compared with levels below 50 cm, mica content in the top 50 cm is lowered almost uniformly across the range of grain sizes >5 �· ( 4 ) The level of maximum weathering (Pollok 1 9 8 4 ) and hence the zone o f maximum degradation of minerals is between 51 - 6 4 cm depth i . e . below the zone of lowered mica content . It is therefore thought that the change in mica content does not reflect pedogenic processes but rather a change in parent material . Parf itt et al . ( 19 8 4 ) document a reduction in epidote and chlorite in 1 8 8 the top of the Tokornaru soil . There i s a lso a reduct ion in mica and epidote content at the boundary between tephric loess (with micas ) and an overlying tephric unit in yellow-brown learns from south Taranaki ( Stewart 1 9 8 2 ) . The greywackes and the Plio-Pleistocene sediments are the two possible ma j or sources for the micas in the loess , although Australia cannot be totally excluded as Marshall and Kidson ( 1 92 8 ) describes " flakey" sic minerals (probably micas ) in historic dust­ storm debris . In the greywackes, however, the micas are either fine­ grained ( < c . 2 0 �) or , when coarser , are deformed and relatively rare , while in the P lio-Pleistocene sediments micas are more common and coarser (up to sand-sized grains ) . This is good evidence for the micas t o have been eroded from the Plio-P leistocene sediments and deposited on the Ohakean aggradation surfaces , from where they were removed by aeolian processes . The sudden reduction in mica content of the loess may be due to the loess source being inundated by the sea and/o r expansion of t he forest at the end of the stadial . At the end of the last stadial De Angelis et al . ( 1 9 8 7 ) document a similar decrease in aluminosilicates (mainly illite ; Windom 1 97 5 ) in aerosols trapped in an Antarct ic ice core . The reduced mica content may also be reflected in the chemical data of Childs and Searle ( 1 975 ) . They show a pattern of reduced K2o content in A and B horizons compared with C horizons in yellow-grey earths and yel low-brown learns and att ribute the lowered K20 levels to loss o f potassium during weathering . An alternative explanat ion to weathering is that it represents a different parent material . Under acid c onditions in soils chlorite is more readily weathered than micas yet it is still present in significant quantities in yellow-brown loam/yellow-brown earth intergrades (e . g . Parfitt et al . 1 9 8 4 ) so the potassium dec rease which also occurs in the upper horizons of these soil s (unpublished data, C . W . Childs pers . comm. ) may not be due to mica weathering . Even where mica degradation does occur the potassium fixing properties of the clays will tend to minimise K leaching . In the Table Flat silt loam the K2o content is very low towards the base where the parent material is demonstrably different , i . e . t he "Tonga riro" tephra (Leamy et al . 1 97 3 ; Childs and Searle 1 9 7 5 ) mixed with 1oess . It is suggested that the decrease in potassium reflects a 1 8 9 reduction in potass ium-bea ring minerals (mica s ) . In some of the Holocene portions of deep-sea sediment s and ice cores (De Angelis et al . 1 9 8 6 ; Griggs et al . 1 9 8 3 ; Nelson et al . 1 9 85 ) there is a decrease in the mica content which is inferred to reflect a decreased aeolian content in the atmosphere as a consequence of climatic amelioration . The cyclical reduction in potassium in loess ial sequences (e . g . Childs and Searle 1 9 75 ) may be a reflection of the provenance of loessial materials that accumulated between stadial periods . Chemical trends which are due to tephra in the loess have been discussed above but some trends evident may not be related to tephra additions but rather to variat ions in the detrital mineralogy . Z ircon is a particularly stable mineral and has commonly been used a s an index of relative change in provenance and pedological studies ( Khangarat et al . 1 97 1 ; Rut ledge et al . 1975 ) . Changes in Zr content in a sedimentary sequence may be taken as reflecting changes due t o e ither weathering or changes in parent materials . In the Tokomaru soil the Zr content of the Ohakean loess is relatively uniform, except in the Aokautere Ash , but there is a marked increase for samples T22-T2 4 . This increase could be due to either an additional parent material or the removal of a fraction that does not include zircon ( i . e . weathering) . The fresh but weatherable minerals in T22 -T 2 4 suggest that minimal material has been translocated so the increase in Zr in these samples is thought to be due to a change in parent material . The increase in Zr cannot be due to the more volcanic nature of the top 50 cm, for although the sands which are dominated by volcanics do have an increased Zr content in the top 50 cm the increase is insufficient to account for the increased levels in the soil . I t is concluded that the increased Z r content of T22 -T24 is theref o re a reflection of increased zircon content of the loess at this level . Based on the significantly different quart z , lithics , mica and Zr conte nt in the top of the profile it is here suggested that the top 50 cm represent loess with a dif ferent provenance to that below 5 0 cm . It has been argued above that the top unit accumulated during the last 1 0-11 ka so it is here referred to as post-glacial loess . 1 9 0 POST-GLACIAL LOESS SOURCE In the South Island post-glacial loess is relatively common east of the main divide , but of local extent , (Bruce et al . 1 9 73 ) and at the present time storms frequently blow dust ( loes s ) from braided river systems onto adjacent terraces (Cox et al . 1 97 3 ; Ives and Stevenson 1 9 7 3 ) . In the North Island post-glacial loess is less extensive (Cowie and Milne 1 97 3 ; McCraw 1 9 7 5 ) although in the cent ral North Island this apparent absence may be an identification problem due t o the difficulty of different iating thin, shower bedded tephras f rom tephric loess (Pullar and Pollok 1 97 3 ; Lowe 1 9 8 0 ) . Holocene loess has been reported at Lake Ferry in the Wairarapa (Palmer 1 9 8 2 ) and Pullar ( 1 9 8 0 ) described tephric loess derived from pumice of the Taupe Tephra Format ion in the Rangitaiki River valley . In the Manawatu dust can be observed blowing from the Manawatu River flood plain during storms . The sand mineralogy of the present day Manawatu River sediments has a quartz : feldspar : lithics ratio simi lar to the post-glacial loess so the flood plain is a possible loess source . Micas are common in the present overbank deposits f rom the river however , and river sediment clays are currently dominated by micas (J . G . Churchman pers . comm. ) . A source with a relatively high mica content would be expected to produce loess with a high mica content , particularly if one considers the ease with which a platy mineral like mica can be lifted (Souster et al . 1 9 85 ) and the fore st present at this t ime would have provided an excellent loess t rap . The scarcity of micas in the post-glacial loess at the Tokomaru site may be due to either : ( 1 ) Weathering - micas may have been removed by weathering . It has been argued above however, that this is not the cause of the dearth of micas in the Ah to Btg1 horizons and data of Parfitt et al . ( 1 9 8 4 ) indicate that micas are even absent in the Ap horizon . ( 2 ) Non-deposition - Souster et al . ( 1 9 8 5 ) show that for grain sizes >20 � the relative proportion of micas in loes s increases with distance f rom. source because micas tend to 1 9 1 be transported further than other mineral grains . Notwithstanding the trapping ability of the forest, micas may have blown beyond the "Pollok ' s P it " site which is quite close to source . ( 3 ) Proximity of any accumulation site down wind from extens ive , sparsely vegetated flood plain areas . ( 4 ) Scarcity of micas in the loess source . Rhyolitic glass with chemistry similar to that of the Aokautere Ash reappears in the post-glacial loess . There a re no known tephras with similar chemist ry to the Aokautere Ash after 2 0 ka . B . P . so this glass must . represent recycled material . Glass is fragile and would not survive abras ion in the river and Lithgow ( 1 9 8 6 ) did not record glass in the sand fract ion of the Manawatu River sediments . The source of the glass in the post-glacial loess must therefore have been relatively localised . Based on these factors it is suggested that the major sources of the post-glacial loess a re ( 1 ) the thinly vegetated cliffs that were exposed in the valley as the river was downcutt ing, and ( 2 ) the river flood plain . Such cliffs are common in the Manawatu River valley and its tributaries (e . g . the Tiritea valley) today . In the Rangitikei River valley Milne ( 1 9 7 3 ) also considered the exposed valley sides might be local sources for loess . The slightly coarser nature of the post-glacial loess , even with reduced wind intensities can be reconciled if the following points are considered : ( 1 ) much of the energy used in transporting dust is expended in lifting grains from a surface ( Bagnold 1 97 3 ; Thorson and Bender 1 98 5 ) so where this energy is not required e . g . when grains fall naturally from a cliff, weaker winds may transport larger grains ; ( 2 ) the orographic effects of the cliffs might increase wind speeds locally . A . S . Palmer (pers . comm. ) reports observing quartz granules being blown from cliffs onto terraces in the southern Wairarapa . If valley-side cliffs are considered the dominant source of the post-glacial loess in the Manawatu then the loess should be slightly more mature than the Ohakean loess . Increases in quart z content are 1 9 2 thought to reflect increasing maturity in sediments (Folk 1 9 7 4 ) so the slight increase in quartz content and decrease in lithic content in the post-glacial loess are compat ible with increasing maturity . Similarly the s light increase in the Zr content in the post-glacial loess could be interpreted as represent ing a more mature parent material for this unit . THE PALAEOSOL r.N THE OHAKEA LQESS The Tokomaru marine bench and coverbeds form an extensive terrace out of which numerous valleys and gul lies have been eroded (Hesp and Shepherd 1 97 8 ) . Towards the head of one of these gullies (GR T2 4 / 3 4 4 8 8 6 ) there is a disconformable relat ionship between the upper c . 6 0 cm and the under lying loesses which contain the Aokautere Ash (Fig . 4 . 27 ) . This upper unit is inclined at a shallow angle on the gully side and shows an apparent constancy and continuity of pedological horizons f rom the terrace tread into the gul ly . Charcoal is restricted to the top 10 cm of the upper unit , and this , together with an absence of o rganic debris throughout the top 6 0 cm in the gully, indicates that the mass movement events described in the area by Jane ( 1 9 8 0 ) probably have not affected this profile . This unit was not emplaced by mass wast ing processes but rather is a unit mantling the contours of the landscape . It is thought to be of aeolian origin and is correlated with the post-glacial loess ident ified in the present study . If this correlation is correct then there was a significant hiatus between the Ohakean and post-glacial loesses during which t ime there was erosion of the Ohakean and older loesses . In the previous sections it has been demonstrated that the loess sequence being studied consists of a post-glacial loess overlying Ohakean loess in a disconforrnable relationship . In the Tokomaru soil at Pollok ' s Pit there is a transition zone between c . 50 cm depth and the cap of the fragipan at c . 8 0 cm (the Btg2 horizon) where the mineralogical and chemical trends change from those of the Cxg and Cwg horizons , which have reasonably constant properties , to those typical of the post-glacial loess . . The samples immediately below the post- Figur e 4 . 2 7 : A thin layer of post-g lacial loes s ( above arrow h eads ) unconformab ly overlying o lder loes s un i ts . The Aokautere Ash is v i s ible at the level of the hori z on t a l l ine to the left . 1 9 3 1 9 4 glacial loess have the h ighest clay content o f the soil ( note also the increased aluminium, t it anium and vanadium levels which a re related to the c lays ) . They happen to correspond to the two samples in the sequence prepa red for the phytolith studies where there were s ignificant nondescript f ragments of biogenic material . These fragments may represent highly corroded biogenic silica . I n other a reas of New Zealand a disconformity is commonly pre s erved in deposits that were laid down during the t ransit ion from s tadia l to post-glacial conditions . In the vicinity of Mt . Egmont a s o i l i s developed below a disconformity o f s imilar age t o that des cribed above ( Franks 1 9 8 4 ) . In Canterbury at Barrhill , Ives ( 1 9 7 3 ) des c ribed a post-glacial loess (probably a correlative of that des c ribed here ) that overl ies an indistinct palaeosol developed in a deflated late Pleistocene loes s . In wetter a reas of Southland, Bruce ( 1 97 3 ) recognised a poorly defined palaeosol below the modern soil and he reports that in drier a reas this palaeosol is represented by a textural change . I n central North Island there is evidence for a period of erosion and soil development at the end of the last stadial . There i s therefore evidence from other a reas of New Zealand for a per i od of soil development towards the close o f the last stadial and it i s here suggested that the zone of increased clay content below the post-glacial loess ( i . e . t he Btg2 horizon) is a relic of a soil that formed in the Manawatu at this t ime . This conclusion is supported by the c lay mineralogy of P ollok ( 1 9 7 4 ) which shows a marked increase in interstratified clays and heat collapsible 1 4 A clays at 51 - 6 4 cm depth . The tephric nature of the post-glacial loess and proximity o f the buried s oil to the present topsoil masks many of the chemical properties that have t raditionally been used to identify buried soils ( Runge et al . 1 97 3 ; Tonkin et al . 1 97 4 ; Childs and Searle 1 9 7 5 ) but the trends of Fe , Ba and Y a re informative . Down the profile the i ron content of the soil increases towards the base of the post-glacial l oe s s but dec reases at sample T2 0 (top o f Btg2 ) before increasing t owards the base of the Btg2 horizon . These t wo i ron maxima a re interpreted a s being related to two periods o f i ron mobility and pre c ipitation . Childs and Searle { 1 975 ) demonstrated that there was an 1 9 5 increase i n the Ba content i n the B hori zons of palaeosols due to the presence of barite . The h igher Ba content of the sands in sample T l 7 may be related to this phenomenon . Y levels a re low in the A and B horizons and rise to a maximum in the Cxg ( data f rom A . S . Palmer , pers . comm. , in the Wairarapa commonly show h igher Y values i n the top of C horizons ) . The increase in Y might reflect a relatively Y-rich parent material but the uniformity of soil Zr and sand Y dist ributions at this level tends to counter this possibility and there are no mineralogical or chemical t rends s imilar to that of Y . Most commonly Y substitutes for Ca in phosphates ( Taylor 1 9 6 9 ; Lambert and Holland 1 97 4 ) s o the low Y values in the A and B horizons may be due to weathering of apatite and the leaching of Y . The high Y levels in the Cxg may represent Y released f rom the upper horizons during weathering . I f the levels of Y in samples T5-T l l reflect the levels in unweathered loess, and the Y distribution was approximately uniform prior t o weathering as indicated by the distribution of Y in the sands above t he Aokautere Ash , then the amount of Y added to samples T 1 3-T17 ( area A in Fig . 4 . 2 1 ) approximately equals that removed from samples T 1 8 -T 2 0 ( area B in Fig . 4 . 2 1 ) . It is proposed that Y added to samples T 1 3-T 1 7 represents Y released by weathering of phosphates in the very top o f the Ohakean loess . FRAGIPAN GENESIS DEFINING PROPERTIES OF FRAGIPANS : Fragipans a re sufficiently important soil features that they a re used for classification in the US S o il T axonomy at the great group level in Alfisols , Inceptisols , Spodosols and Ultisols yet there i s still debate about what criteria should be used to define a fragipan (Grossman and Carlisle 1 9 6 9 ; Sma lley and Davin 1 982 ; Veneman and Lidbo 1 98 6 ) . This problem has led to a diverse range of suggested mechanisms for f ragipan formation ( e . g . s ee Smalley and Davin 1 9 8 2 ) . In pedology the concept of a pan involves an horizon that restricts root penetration . The term "fragipan" was introduced by G . D . Smith (Grossman and Carlisle 1 9 6 9 ) to distinguish uncemented compact 1 9 6 loam t o s ilt loam soilpans from hardpans ( cemented) , clay pans { clay dominated) and duripans ( s ilica cemented) . Later Smith et al . ( 1 97 5 ) introduced the term " densipan" to describe a dense albic horizon . The important factor differentiating a fragipan f rom the other soil hardpans is that it is hard but uncemented i . e . the apparent induration disappears on wetting a s the material s lakes or disperses . The range of properties of fragipans was extended to encompass indurated "drift " depos its by Fit zpatrick ( 1 9 5 6 , see also Fitzpat rick 1 9 7 6 and De Kimp 1 97 0 , 1 9 7 6 ) but more recently Mathews ( 1 9 7 6 } , Romans ( 1 97 6 ) and Avery ( 1 9 8 0 ) concluded that at least some of the "fragipans" o f Fit zpatrick ( 1 95 6 ) failed to s lake and were mainly cemented . Fit zpatrick { 1 9 7 6 ) acknowledged that "there a re probably at least two different horizons that have been called fragipans hence the lack of agreement and confusion that exists" . Recently Veneman and Lidbo ( 1 9 8 6 ) stated that "there exists a clear need to better define the term f ragipan" . Soil Survey Staff ( 1 97 5 ) describe fragipans a s compact loamy s ubsurface horizons of high bulk density which a re hard to extremely hard when dry, and firm to very firm when wet . They a re brittle when dry o r wet . This definition is u sed here . In New Zealand fragipans or related mas sive horizons a re integral parts of the yellow-grey earth soil group ( Cowie 1 9 8 4 ) . Their physical properties are typified by : ( 1 ) a low porosity ( S cotter et al . 1 97 9 ) , ( 2 ) a high bulk density, between 1 . 5 and 1 . 8 Mg/m3 ( Gradwell 1 9 7 4 ; Scotter et al . 1 9 7 9 , ( 3 ) a relatively well-sorted particle s i ze distribution with a s ilt mode, ( 4 ) columns that a re polygonal in cross-section with grey veins (gammations ) between the columns (Bruce 1 9 72 ) , and ( 5 ) skeletal grains which a re closely packed . MECHANISMS OF FRAGIPAN FORMATION : The primary characteristics of f ragipans a re ( 1 ) high bulk densit ie s , and ( 2 ) low porosities, both o f which influence the drainage properties of any overlying horiz ons . The most plausible theories on f ragipan formation involve e ither chemical 1 9 7 pathways o r soil desiccation processes t o produce a high bulk density ( see Grossman and Carlisle 1 9 6 9 ; and Smalley and Davin 1 9 82 for a deta iled discussion of these theories ) . Nikiforoff ( 1 9 5 5 ) and Fit zpat rick ( 1 9 5 6 ) invoked desiccation and f reeze-thaw processes respectively to explain the increase in density . More recently Fit zpat rick ( 1 97 6 ) and Langohr ( 1 9 8 7 ) have developed the f reeze-thaw principle further and suggest that in a permafrost environment , near-surface f ro zen ground draws water from deeper levels s o c ompressing the layers at those levels and producing a high bulk dens ity . Parfitt and Milne ( 1 9 8 4 ) a nd Parfitt et a� . ( 1 9 8 4 ) working in New Zealand suggested that under a high soil-water deficit , plant root suction would desiccate the subsoil placing it under high compressive stresses and so produce compaction . I nvestigators using dissolution techniques t o study possible chemical pathways for reducing porosity in fragipans concluded that there were bridges of S i , Al and Fe between skeletal grains ( Harlan et a� . 1 97 7 ; Hallmark and Smeck 1 9 7 9 ; Veneman and Lidbo 1 9 8 6 ; Bull and Bridges 1 9 7 8 ) . They also noted that there was a reduction in the number of voids in a fragipan compared with the underlying loess . Using the scanning electron microscope Norton et a l . ( 1 98 3 ) ident ified thin S i , Al and Fe coatings that they thought were probably acting as cement ing agents although they a cknowledged that c lays had been rearranged and could be the binding agent . Grossman and Carlisle ( 1 9 6 9 ) also favoured clays as the bonding agents but they did not exclude thin chemical films as possible bonding agents . FRAGIPANS IN NEW ZEALAND: Fragipans in New Zealand have not been studied in sufficient detail to be able to determine if amorphous coatings are common but data o f Kirkman ( 1 97 3 ) and Parfitt et al . ( 1 9 8 4 ) show that if amorphous S i , Al and Fe a re p resent they a re only minor . Barratt ( 1 9 8 1 ) describes ultra thin pale coat ings that "could act a s cement" and the iron distribution ( plus Ba and Y) in the Tokomaru soil indicates that there a re inc reased levels of these e lements in the t op of the fragipan compared with lower horizons . The ease with which the fragipan s lakes however indicates that the strength o f any chemical coatings is easily overcome , s o it seems 1 9 8 improbable that they a re ma jor factors i n fragipan strength . Any chemical coatings a lmost certainly post-date fragipan formation because where they have been identified they form thin coatings that cover grains that a re already in a very dense configurat ion and so do not cause the densification . Barratt ( 1 9 8 4 ) after studying the micromorphology of s ome New Zealand fragipans concluded that they resulted mainly from physical processes and it i s here concluded that fragipans in New Zealand formed by some form of densificat ion due to des iccation . Although a systemat ic study of fragipans has not been undertaken in the present investigation , properties observed in the Tokomaru soil that may be pertinent to the origin of the fragipan include : ( 1 ) A grain s i ze distribution dominated by silts (mean grain size of 1 4 � for the whole s ample or 2 8 � on a clay-free basi s ) but with s ignificant c lay content ( 1 5 - 1 7 % ) . ( 2 ) Joints divide the loess into polygonal columns and commonly extend for the full thickness of the Ohakean loess i . e . they a re continuous from the cap of the fragipan through the Cwg1 , Aokautere Ash and Cwg2 ( Fig . 4 . 2 8 ) . ( 3 ) The t op of individual columns ( i . e . the top of the fragipan ) often have a rounded cap ( c . 1 0 cm thick) which is noticeably stronger than lower portions of the column . During t he present study the initial disaggregation of samples taken from loess columns involved c rushing with a hydraulic press , and although only qualitative it was noted that the s ample from the cap of the f ragipan withstood s ignificantly higher pressures before yielding . ( 4 ) Remnants of the fragipan are discernible in the overlying Btg2 horizon . ( 5 ) Loes s from the fragipan slakes readily in water . This happens when small exfoliation bursts occur f rom ped surface s . There i s often no accompanying release of gas . ( 6 ) Chemically the f ragipan is relatively homogenous for the majo r elements except for an increase in Fe in the cap of the pan . There is more variation in the trace elements 1 9 9 Figur e 4 . 2 8 : We l l deve loped co lumnar s tructure formed in loes s near the Tokomaru s i te . The Aokau ter e Ash i s at the l eve l of the ar rowheads . with V increasing towards the cap while there a re higher values for Y in the centre o f the fragipan . The sand fraction Ba content increases in the cap . 2 0 0 To establish how the fragipan forms it is important t o e stablish a time f rame within which the process occurred . The Tokomaru soil profile i s capped by a post-glacial loess which is underlain by a Btg2 horizon , here interpreted as a buried soil that formed c . 12 ka B . P . The Btg2 incorporates fragments o f the f ragipan and is continuous with gammations that fill j oints in the fragipan , s o the ma jor features of the f ragipan were probably established by this t ime , ( although it is acknowledged that expansion and contraction within the gammations cont inues today ) . Raeside ( 1 9 5 6 , 1 9 6 4 a , 1 9 6 4 c ) and others ( see Bruce 1 9 8 4 ) a l so inferred t hat the fragipan was an inherited feature . The opening of j oints that are polygonal in plan section is a common natural phenomenon in geological materials , e . g . mudcracks (Dunbar and Rodgers 1 9 5 8 ) , s andstones ( Splet tstoesser and Jirsa 1 9 8 5 ; Kocurek and Hunter 1 9 8 6 ) , surface sediments o f a rid regions ( Hunt et al . 1 9 6 6 ; Neal et al . 1 9 7 9 ; Alaily 1 98 6 ) , columnar jointing in igneous rocks ( P ress and S iever 1 9 7 4 ; Healy 1 9 8 2 ; Tarbuck and Lutgens 1 9 8 4 ) and fragipans . I n igneous rocks these joints are thought to b e the result o f shrinkage due to cooling and where they occur in sediments they a re interpreted a s the result o f shrinkage and dens ification due to des iccation . Langohr ( 1 9 8 7 ) has a rgued that the joints in fragipans are the result o f permafrost and ice wedges . In New Zealand, however , this is an unlikely pathway because it is improbable that there was permafrost at this altitude in New Zealand during the Ohakean . McGlone ( 1 9 8 5 ) and Soons ( 1 97 6 ) have estimated that there was a temperature depression of between 6°C and 4°C during the last stadial . Furthermore , j oints and gammations in New Zealand loesses a re never a s wide a s s imilar types of features formed from ice wedges . Fitzpatrick ( 1 9 7 6 ) agreed that New Zealand f ragipans lack s ome of the ancillary features associated with permafrost and concluded that the polygons in many European pseudogleys and New Zealand yellow-grey earths were the result o f shrinkage . 2 0 1 I t i s improbable that plants caused des iccation and development of the f ragipan as the loess accumulated, ( Parfitt and Milne 1 9 8 4 ; Parfitt et a l . 1 9 8 4 ) because : ( 1 ) The contraction j oints are continuous across the Aokautere Ash so the Ohakean 1oess has probably acted as a whole unit during the des iccation and compaction process and the deeper levels would be beyond t he reach of the plant roots . ( 2 ) The Aokautere Ash does not appear to have fallen down the j o ints as might be expected if the f ragipan formed when the ash was only thinly covered by loess . ( 3 ) A report by Mc intyre ( 1 97 5 ) on the P distribution in a yellow-grey earth 1 5 km south o f "Pollok ' s Pit" showed a s imilar P distribution to that in f igure 4 . 2 0 . The P in the stadial loess had not been t ranslocated by vegetation as has happened in the Btg horizons and the P in the C horizons is dominated by inorganic P i . e . it is relatively unweathered . The unweathered nature of the phosphorus at this level is a l so demonstrated by Blakemore { 1 98 4 ) and suggests that there had been minimal weathering during loess accumulation . It has been argued above that there was probably minimal biological activity while the loess accumulated . Micromorphological data of Barratt ( 1 98 1 , 1 9 8 4 ) also indicate that the f ragipan formed when weathering and biological activity were at a minimum, so the vegetation was probably sparse . ( 4 ) I f this des iccation theory applied t oday to loess deposit s , a f ragipan should perhaps be developing under t he Barrhill f ine sandy loam. Thi s does not appear t o be o ccurring . A MODEL FOR FRAGIPAN FORMATION : The des iccation and densi f i cation exemplified by mudcracks is here used as a model for f ragipan formation . The model invokes natural drying to impose the s tress that results in densification . 2 02 In well-sorted material like loess , densificat ion and low porosity c annot occur unless there i s finer grained material or some form o f chemical "cement " to seal off the pores . The grain size distr ibution in the Tokomaru f ragipan is dominated by silts but there i s s ignif icant clay content . Many investigations ( e . g . Syers et al . 1 9 6 9 ; Smith e t al . 1 97 0 ; Windom 1 97 5 ; Duce et al . 1 9 8 0 ; De Angelis et al . 1 9 8 7 ) have shown that aerosolic dust conta ins clays , and the upper horizons of the presently accumulating Barrhill fine sandy loam contain c . 1 3 % clay . Whalley ( 1 9 7 9 ) and Derbyshire ( 1 9 8 3 ) have identi fied s ilt -sized aggregates of clay-si zed minerals in loess and the 15-17% c lay in the fragipan of the Tokomaru soil is thus interpreted a s being aeolian in origin . The fragipan parent materials were thought to comprise silt-si zed mineral grains (with or without clay coat ings ) and silt-si zed clay aggregates . This material a ccumulated under relatively dry condit ions with very low biologica l activity, but the actual nature of the environment i s little understood . I t is difficult t o envisage how loess or ash is stabilised in the landscape during windy conditions and with l imited vegetation . It may be t hat the limited vegetat ion was o f a form that produced a canopy that provided shelter f rom the wind but without significant surface activity . At s ome stage the loess becomes wetted . This may have been a repeated process during accumulat ion and therefore explains why the loess was t rapped . There could not have been many cycles of s ignificant wetting then drying however, as this would probably have produced repeated dispersion cycles and under such conditions the voids in t he Aokautere Ash might be expected to fill with t ranslocated clays and s ilts when the ash was thinly covered with loess . For example , at t he present t ime t ile drains in the Btg horizon may f i ll with s i lt and clay . The pumice lapilli in the Aokautere Ash only contain minor illuviated c lays and s ilts . During the wetting the s i lt­ sized c lay aggregates collapse and are redistributed a s clay coatings or bridges between the coarser grains . Dispersion may have been assisted by the presence of cyclic salts which were more common constituents of aerosols during stadial periods than during the Holocene (De Angelis et al . 1 9 8 7 ) and would have been deposited with 2 0 3 the loess . Consequently the density is increased and in the process many of the airways are blocked to produce closed voids . This gives a wet homogenous unit and natural drying results in a columnar polygonal shrinkage pattern and increased density si:rnilar to those formed by mudcracks ( see Fig . 2 in Bishop et al . 1 9 8 4 ) . As a consequence of the lack of bioturbation because of the low biological activity , high densities may be maintained at comparatively shallow depths . The drying phase further increases the density due to the forces induced by the low matric potential (Croney and Coleman 1 953 ; Croney and Jacobs 1 9 6 7 ) . This process may also pressurise the closed voids and explain the bursts which release material from the loess surface on rewett ing . It is difficult to determine the conditions and t ime required for fragipan formation . Columnar s tructures have been recorded such as f igure 4 . 2 9 developing under present climatic conditions in a matter of months rather than yea rs ( J . A . Pollok pers . comm. ) and in a s imilar t ime frame polygonal structures a re produced from the dewatering of loess slurries f rom German coal mines ( J . A . Pollok pers . comm. ) . It has been shown above that there was a period of e rosion and pedogenesis when the c l imate improved at the end of the deposition of last stadial loess . This probably happened before colonisation by the forest . It is here suggested that it was during this t ime that the final properties of the fragipan developed due to natural drying . The f ragipan i s now being destroyed during the current pha se of pedogenesis . YELLOW-GREY EARTH AND YELLOW-BROWN EARTH/YELLOW-BROWN LOAM INTERGRADE RELATIONSHIPS In New Zealand, soils derived f rom loess embrace a wide range of morphological , physical and chemical characteristics ranging from brown-grey earths (more arid environments ) through yel low-grey earths to yellow-brown earths (more humid environments ) . In the Manawatu Figure 4 . 2 9 : Thes e co lumnar s tructures developed in a few mon ths in a spo i l heap left after bui lding foundat ions were excava ted . Photographer Dr . J . A . Poll ok , 2 0 4 2 0 5 dist rict a t ransit ion occurs between the yellow-grey earths and intergrades between yellow-brown earths and yellow-brown loams ( soils formed mainly from volcanic ash parent materials) . The two soil groupings can be found on the same terrace , have similar textures ( dominated by silt ) , s imilar age and apparently formed from similar parent materials , yet have dramatically contrasting properties ( see Neall 1 9 82 , and Bruce 1 9 8 4 ) . The yellow-grey earths of the Manawatu typically have a fragipan with high dry bulk densities ( 1 . 5 - 1 . 8 5 Mg/m3 ) and very low permeability (Gradwell 1 9 7 4 , 1 97 8 ; Scotter et al . 197 9 ) . Thus they become waterlogged in winter to produce reduced, pale , grey B horizons ( often with large iron concretions) . They have "yellow" C horizons with orange mottles . The soils that are classified as being intergrades between yellow-brown earths and yellow-brown loams ( hereafter referred to as YBE-YBL) have moderate dry bulk densities ( 1 . 2 - 1 . 5 Mg/m3 ) , a re permeable , do not have a fragipan and have brown B and C hori zons , i . e . have a more uniform profile form . YBE-YBL a re free draining with significantly more ferrihydrite and allophane distributed uniformly throughout the profile , creating greater macroporosity which maintains free drainage . Further, they are commonly found in areas with slightly more rainfall and at slightly higher elevations than the yellow-grey earths . The fundamental difference between the yellow-grey earths and the YBE-YBL is the impeded drainage of the former caused by a comparatively impermeable fragipan . PAST EXPLANATIONS : Milne ( 1 97 3 ) suggested that the difference between the two soil groupings was caused by summer drying which produced a dense subsoil in yellow-grey earths . Later he completed a detailed map of the t ransition between yellow-grey earths and YBE-YBL (Milne 1 9 8 1 ) and showed that the soils were juxtaposed in an irregular, interdigitating pattern . He proposed that local s ite f actors had an influence in developing this pattern and that these factors acted early in pedogenesis to force the system along either a YBE-YBL or yellow-grey earth weathering path . Vegetation was a possible factor and Milne ( 1 98 1 ) suggested that the area �hich is at 2 0 6 an e levat ion o f c . 2 0 0 m st raddled the Pleistocene tree line and that the yellow-grey earths developed under shrubs and trees and the YBE­ YBL under tussock . Vegetation may have been a factor but , judging from the palynological evidence in Taranaki and south of Levin, the last stadial vegetation on the low terraces in the region was probably dominated by grasses with minor scrub (e . g . Dacrydium bidwillii, Dracophyllum, Leptospermum and Hebe) and rare forest trees (Nothofagus menziesii ) (McGlone and Neall pers . comm . ; Mcintyre 1 9 7 0 ) . According to Fleming ( 1 97 9 ) the Manawatu was beyond the forest vegetat ion zone during the last stadial . The uniform and relatively low phosphorus content of the YBE-YBL subsoils yet high proportion of organic P (Anon . 1 9 8 1 ) , the more disrupted nature of the Aokautere Ash , and the less contrasting nature of YBE-YBL soil horizons in successive loessial units indicate a significant degree of mixing or biological activity during accumulation . Such mixing is more compat ible with a scrub or bush environment . At least one member of the soil fauna , worms , are more numerous under forest vegetat ion and almost absent in dry t ussock vegetation, especially during stadial conditions ( Lee 1 9 5 9 ) . If the presence or absence of forest was a determining factor then it is more probable that the YBE-YBL formed under bush . Parfitt and Milne ( 1 9 8 4 ) and Parfitt et al . ( 1 9 8 4 ) att ributed the differences between the soils to increasing impermeability towards the yellow-grey earth end member . They proposed that desiccation and densi fication was induced by hydraulic suct ion from plant roots during periods of high soil-water deficit . As discussed above , this part icular mechanism does not adequately explain some features of fragipan formation and it cannot easily account for the complexity of the boundary relationship to the YBE-YBL soils . The theory also requires that the subtle variations in soil-water deficit observed at the present t ime operated during the last stadial . This is unlikely given the different wind regime probably operating during that period and the changed environmental conditions consequent upon a lowered sea level . A MODEL TO BXPLAm THE YELLOW-GREY KAR.'l'B, YELLOW-BROWN EAR.TB/YBLLOW-BROWN LOAM ::IN'l'ERGRADE RELAT:IONSHIP : Where a terrace is covered by multiple l oess units the repetitive occurrence of either 2 0 7 yellow-grey earth o r YBE-YBL soil profiles suggests that once a particular soil format ion pathway is established it is maintained . Only one exception has been observed; 4 km south of Massey University a yel l ow-grey earth profile has developed after a possible YBE-YBL profile precursor . Many parameters (e . g . morphology, chemistry, mineralogy and physical properties ) indicate that yellow-grey earth format ion results in an efficient differentiat ion into horizons and that this pattern is repeated for each new cycle (e . g . Dashing Rocks, Timaru) , whereas in the YBE-YBL there is much less differentiation into horizons within loess cycles and even between cycles . The distribution of phosphorus in YBE-YBL profiles emphasises this . In the Dannevirke and Kiwitea silt loams (Anon . 1 9 8 1 ) and Shannon silt loam (Mcintyre 1 9 7 5 ) much of the phosphorus in the profile is in the upper hori zons with subsoils and palaeosols having low and uniform phosphorus levels . This is in contrast with the yellow-grey earths where phosphorus distribution is more variable . Here P is relatively high in topsails and palaeosols , decreases markedly in B hori zons , but increases to a constant level in C horizons (Fig . 4 . 2 0 ; see also Childs and Searle , 1 9 75 ; Mcintyre 1 9 75 ) . I f the soils originally had similar levels of phosphorus , and phospho rus in topsails represents P translocated to the surface by biological activity while the loess was accumulating, then YBE-YBL have probably undergone more active pedogenesis throughout all stages of accumulation than yellow-grey earths . This conclusion is supported by the form of the phosphorus because in the C horizons of the yellow­ grey e a rths the P is dominantly inorganic P while at deeper levels in the YBE-YBL organic P is a higher proportion of total P . This continual pedogenesis may also explain why the Aokautere Ash t ends to be more diffuse in YBE-YBL profiles compared with in the yellow-grey earths . In contrast the yellow-grey earths have experienced more stop-start cyclical pedogenesis . Therefore although the c onditions that produced the yellow-grey earths (fragipan formation) a re repeated at the end of each stadia!, the factors that lead t o the YBE-YBL path were established at the first appearance of YBE-YBL in a sequence of loesses and were maintained to the present . To invest igate the factors that lead to the formation of the YBE-YBL it i s necessary to search for the first level where similar aged loesses develop along YBE-YBL or yellow-grey earth weathering paths . 2 0 8 In the Manawatu the cycle of YBE-YBL soil formation begins with a tephric palaeosol on comparat ively well-drained sands or gravelly alluvium and the allophane and ferrihydrite present produced a free­ draining soil . The volcanic centres of Egmont , Tongariro and Taupo have e rupted intermittent ly at least since the Tokomaru marine bench was cut ( Latter 1 985 ) so have probably regularly supplied tephra dust ings to the region . It is proposed that the re was slightly increased weathering and biological activity in the YBE-YBL, even during stadial periods so even though the accumulating loess was probably mainly quartzofeldspathic the weathering of the occasional tephra provided sufficient allophane and ferrihydrite to maintain good drainage . Both allophane and ferrihydrite are highly reactive and have large surface areas so small amounts have a disproportionate effect on the soil . Parfitt et al . ( 1 9 8 4 ) report 1-5% allophane in YBE-YBL in the Manawatu (excluding the influence of the Aokautere Ash ) and based on Fe0x it has been estimated that there is 1-3 % ferrihydrite (C . W . Childs pers . comm. ) In contrast the formations underlying the basal yellow-grey earth in a sequence of yellow-grey earths is often relatively impermeable or poorly drained . In the Rangitikei River valley the yellow-grey earth sequences are frequently underlain by thin layers of aggradational gravels that rest on impervious mudstones . Judging by the s eepage from along the contact between these gravels and the mudstone s , the gravels have a shallow water table and are poorly draine d . Although many yellow-grey earth sequences are underlain by the highly permeable Otaki Sandstone in the Manawatu, the loesses are often separated from the sandstone by silts or are underlain by silty alluvium so that they are initially poorly drained . Once a yellow-grey earth weathering path has developed, tephras falling on this surface during an interstadial will be sub jected to redox reactions . I ron is t ranslocated to form concretions while the aluminium and silicon form halloysite (Milne 1 9 8 1 ; Parfitt et al . 1 9 8 4 ) . Allophane is absent from the Tokomaru soil (except i.n "the Aokautere Ash ) and there is less than 2 0 9 0 . 5% ferrihydrite in the B and C horizons . During stadial periods the tephras are " sealed" in the loess at the position where they fall and there is little weathering or t ranslocat ion . At the site where there is a switch in the sequence of soil format ion the change is from a YBE-YBL type to a yellow-grey earth . Although this section has not been studied in detail the change occurs at a level whe re there is a part icularly reduced and clay-rich layer . This may have reduced the drainage and initiated a yellow-grey earth sequence . The theory suggested here to explain the origins of the differing weathering paths maintains that the YBE-YBL path has been followed at least since soon after the Tokomaru bench was cut , whereas the yellow-grey earth path has been re-established at the end of each stadial cycle . Like Milne ( 1 97 3 ) it is suggested that flora may have influenced the soil patterns . It is proposed that the YBE-YBL parent materials which were darker (warmer ) , freer draining (promoting longer growing cycles ) and with higher phosphorus were more favourable for some specific f lora-fauna association compared with yellow-grey earths . These slight site advantages would be maximised during the stadial periods . It is not poss ible to ascertain if the inte rdigitat ing relationship of the soils in the boundary area is solely a function of the present pedogenesis or a relic feature , but under the scenario developed above it is proposed that the complexity of the boundary relationship is an inter-relationship between the flora-fauna association and drainage . SEDIMENTATION HISTORY OF THE TOKOMARO SOIL The history of sedimentation revealed in a deep sea core from 12 0 km east of Cape Turnagain ( Stewart 1 9 8 2 ) may be relevant to the history of the Tokomaru soil � Close examination of the mineralogical 2 1 0 components at the level of the stadial/Holocene trans ition in this core shows that there were two stages in the change at the bounda ry . Initially there was a marked reduction in accumulation rate at c . 14 . 2 ka ( a fter the Rerewhakaaitu Ash ) . A decrease in quart z content in the coarse and fine s ilts at c . 12 ka . (after the Waiohau Ash ) is here interpreted as reflecting a reduction in the aerosolic component of the sediments . After c . 12 ka the sedimentation rates were relat ively low and uniform . These data indicate that changes in environmentally sensitive factors may not have been synchronised . Absence of synchronisation of changes in sediment s at the stadial /post-glacial trans it ion is substantiated by recent data from separate marine cores east of the North Island (R . B . Stewart pers . comm. ) which show a change in Globigerina bulloides and Neogloboquadrina pachyderma c . 4 0 cm above the ma jor colour change in these cores . Furthermore , data from Antarctic ice cores (Petit et al . 1 98 7 ; Raisbeck et al . 19 8 7 ) , Tierra del Fuego (Heusser and Rabassa 1 98 7 ) and the North Atlantic (Ruddiman and Mcintyre 198 1 ) indicate that there was an inflection in the general trend of climatic amelioration at the end of the last stadial . The marked change in sedimentation rates at 1 4 . 2 ka has been interpreted as reflecting the southward migration of the westerly wind system ( Stewart and Neall 1 9 8 4 ) marking the beginning of a climatic amelioration while the change at c . 12 ka is here interpreted as reflecting the termination of the loess source due to the rising sea level or spreading forest . In the Tokomaru soil there is a reduction in mic rofossils and sponge spicules and increase in forest phytoliths at 5 0 cm and this has been interpreted as reflecting a change in sea level and/or afforestation . Furthe rmore , as well as the change in biogenic silica at 50 cm depth there is a reduction in mica content and s light increase in sand content . Griggs et al . ( 1 9 8 3 ) record a similar reduction in micas and increase in sands in the Holocene sections of marine cores east of the South Island . The age of the level where this change occurs is c . 12 ka , after adjusting for the effects of sediment bioturbation ( Stewart 1982 ) . In the Manawatu a combination of ameliorating climate and a reduced accumulation rate led to t he development of a soil at the close of the Ohakean sub stage . If the correlation between the loess 2 1 1 and cores is sound t hen loess was still accumulating at this lat itude at c . 12 ka . This is inconsistent with an absence of loess above the Rotoaira Lapilli ( 1 3 . 8 ka B . P . ) from an area southeast of Lake Taupe (Topping 197 3 ; Froggatt and Solloway 1 9 8 6 ) or above the Rerewhakaaitu Ash ( 1 4 . 7 ka B . P . ) north of Taupe (Kennedy 1 9 8 2 ) . Thus loess ceased accumulating in the central North Island earlier than in the southern North I sland . ACCUMULATION AND SEDIMENTATION RATES As a result of the Deep Sea Drilling Projects there have been numerous investigations studying the palaeontology and sedimentology of marine cores to ident ify trends in palaeoceanography and palaeoclimatology (Burn et al . 1 97 3 ; Kennett et al . 1 9 7 5 , 1 98 5 ; Stewart and Neall 1 98 4 ; Nelson et al . 1 9 8 5 ) . Variations i n the biogenic components of marine sediments ( silica and carbonate content ) are interpreted in terms of changes in productivity due to variations in the nutrient status of water masses , while variations in the aerosolic dust accumulation and sedimentation rates have been interpreted either in terms of changes in source areas (ma rine t ransgressions inundating or afforestation stablising s ource areas ) or changes in transport mechanisms ( shifts in wind patterns ) . After correlating features in the Tokomaru soil profi le with events for which there is temporal control it is possible t o determine sedimentation rates ( thickness of sediment /time , cm/ka . ) and accumulation rates (weight of mineral flux, gm/cm2 /ka . ) for the loess parent materials . The t emporal controls used include : ( 1 ) the Aokautere Ash ( 2 0 ka at 2 . 2 1 m depth) , ( 2 ) the changes in mineralogy (micas ) , grain size ( sands ) , and inversion of the dominance of marine microfossils over phytoliths ( 12 ka at 5 0 cm depth ) , ( 3 ) the tentative correlation of the tephra dusting at 1 . 15 m with the Rerewhakaaitu Ash ( 1 4 . 7 ka ) , and 2 1 2 ( 4 ) the increase in volcanogenic materials toward the top of the profile ( 1 0 . 5 ka at 4 0 -50 cm depth) . It is unrealistic to expect changes in sedimentat ion rates (and resultant accumulation rates ) to be isochronous with tephras , and the ma j or changes at tephras may be relics of these temporal controls , so the distribution pattern should be smoothed across these z ones . Changes that occur across boundaries that have environmental significance (e . g . changes in biogenic component , changes in the dist ribution of the detrital components ) , or general trends within a zone of uniform sedimentation rate are more representat ive of real changes or trends in accumulat ion rates . The sedimentation rates for the Tokomaru soil range from 4 . 55 cm ka - 1 for the post-glacial loess to 50 cm ka - 1 for Ohakean loess . Sedimentation rates in loess are very dependent on proximity to source , so rates from different areas are not directly comparable , but the ranges of rates from the Tokomaru soil are similar t o those from other areas of New Zealand (calculated trom Bruce 197 3 ; Kennedy 1982 ) , United States (Ruhe et al . 1 97 1 ; Kleiss 1 9 7 3 ) ( and marine cores east of New Zealand ( Stewart 1 9 8 2 ; Griggs et al . 1 9 8 3 ; Nelson et al . 19 85 ) . Historic sedimentation rates on the Canterbury Plains ( Cox et al . 1 97 3 ; Ives and Stevenson 1 9 7 3 ) are 2-7 cm ka-1 . Quartz accumulation rates in the Tokomaru soil (Fig . 4 . 3 0 ) are higher than those from a marine core east of Cape Turnagain ( Stewart and Neall 1 9 8 4 ) . The much higher rates for the Tokomaru soil 63-20 � fract ion which represents the loessial component of aeo l i an materials (Bagnold 1941 ; Ruhe 1 9 6 9 ; Jackson et al . 1 9 7 1 ) are a reflection of proximity to source . This conclusion is supported by the grain size data which shows that the modal interval for the soil profi le is 28 � while that of the core is finer ( c . 8 �) . The rates for the 5�2 � fraction from both s ources are similar, reflecting the more global nature of this •aerosolic component (Rex and Goldberg 1 9 62 ; Walker and Costin 1 9 7 0 ; Jackson et al . 1 97 1 , 1 97 3 ) . The distributions of quartz in the 63-20 � and 5-2 � fractions are taken to represent the loessial and aerosolic dust components respective ly . These demonstrate that there is an increasing T25 T24 T23 T22 T1 6 T1 5 T1 4 T1 3 T1 2 T1 1 T1 0 T9 T8 T7 T6 T5 T4 T3 T2 T1 Ah ABg BAg Btg1 Btg2 Cxg Cwg1 2C Cwg2 m a b 0 .1 0 .3 ,_ , .. .5 0 .75 1 . 55 2.21 2 . 34 0 2 4 6 8 1 0 Figure 4 . 3 0 : Quartz accumulation rates in the fine s i lt ( a ) and coarse silt ( b ) in the Tokomaru soi l . 2 1 3 12 2 1 4 accumulation rate towards the end of the Ohakean stadial before a dramatic drop to Holocene accumulat ion rates (Fig . 4 . 3 0 ) . These results are consistent with the documented increasing rates of aeolian sedimentation towards the end of the last stadial in North America (Ruhe et al . 1 9 7 1 ; Kleiss 1 97 3 ) , in tephric loess in Taranaki (B . V . Alloway pers . comm. ) and in marine sediments t o the east of the North Is land ( Stewart and Neall 1 9 8 4 ) . In the Tokomaru soil the highest rates occur between 1 4 . 2 ka and c . 12 ka . Data in Stewart ( 1 9 82 ) also show that sedimentation of the terrestrial components in a marine core east of Cape Turnagain cont inued at a relatively high rate unt il approximately 12 ka when a Holocene rate began . Ma jor factors that may contribute to the increases towards the end of the stadial include : ( 1 ) increased source area , ( 2 ) increased severity of the transport mechanism, and ( 3 ) increased sediment supply . In the South Island the glacial maximum occurred at c . 1 8 ka . ( Suggate and Moar 1 97 0 ; McGlone 1 9 85 ) and sea level began to rise after this time so an increased source area is improbable . Stewart and Neall ( 1 9 8 4 ) have suggested a contraction in the circum-polar wind system as part o f the amelioration at approximately this time , so an increas ingly severe wind system is a doubtful cause of the continuing high accumulation rate . It is concluded that the increasing rates reflect increasing sediment supply . East of the Ruahine Range Hubbard and Neall ( 1 98 0 ) and Marden et al . ( 1 9 8 6a , 1 9 8 6b) concluded that large volumes of gravels were moved during a period towards the culmination of the Ohakean . Richmond ( 1 9 62 ) , Wellman ( 1 972 ) , Ives ( 1 97 3 ) and Tonkin et al . ( 1 97 4 ) t heorised that the maximum loess accumulation should be associated with the recessional stage of a glacier and the data p resented here supports this thesis . During the last stadial, mass movement and solifluction p rocesses were common in the southern North Island and valleys probably infilled with debris because of a declining load : discharge ratio of the rivers brought about by the lowered rainfall . The climat ic amelioration increased rainfall before the expanding forest stabilised the land surface and the debris was flushed down the valleys to form broad unstable aggradation surfaces which were the source of the loess . Eventually a rising sea level, expanding bush cover and a diminution of source material curtailed the high loess accumulation rate at c . 12 ka B . P . 2 1 5 CHAPTER FIVE SUMMARY AND CONCLUSIONS CRISTOBALITE GENESIS 1 . Cristobalite origin : This study has shown by means of oxygen isotope analysis , degree of mineral c rystallinity, and grain morphology that cristobalite has not formed in situ in the soils investigated here . These data indicate that the cristobalite c rystallised at a relatively high temperature , consistent with magmatic origins . 2 . Tridymite : XRD spectra from silt fractions of the soils indicate that cristobalite is usually accompanied by t ridymite . Although some of the tridyrnite may occur as a discrete phase , SEM studies suggest that it more often occurs intimately intergrown with cristobalite . 2 1 6 3 . Cristobalite sources : Investigation o f selected possible high temperature sources (tephras from the Taupe Volcanic Zone, lavas from the Egmont Volcanic Centre and hydrothermal deposit s ) indicate that cristobalite and or tridymite is common in hydrothermal . deposits but only in some tephras and some lavas . Cristobalite and t ridymite in the soils of the Hamilton basin are derived from the Taupe Volcanic Zone and have been transported to the region by aerial tephra deposition . 4 . Cristobalite distribution : The variable distribut ion of cristobalite in topsoils is related to the dispersal pattern and depth of burial of cristobalite-bearing tephras . 2 1 7 5 . Cristobalite as a tephra tracer : Cristobalite is deduced to be a stable phase in the pedosphere and this , together with the narrow grain size limits within which it occurs and the ease of beneficiat ion indicates that it may have a use as a tracer for t ephras . 6 . rnorganic opal-A : Inorganic opal-A ( amorphous silica) has been identified from the Hamilton Ash Group zone of the Hamilton and Naike soils . Grain morphology indicates that this was formed in the soil and oxygen isotope data are consistent with this interpretation . S ilica released during weathering of tephras develops into silica gels and desiccation of these gels produces opal-A . 2 1 8 TOKOMARU SOIL 1 . Tephric additions : Based on chemistry, mineral proportions and mineral chemistry of the sand fraction in the Tokomaru soil, it is possible to identify pulses of tephric additions to the loess , and to identify their sources : 0 -50 cm 1 . 1-1 . 2 m 1 . 2-1 . 3 m c . 1 . 6 m c . 2 . 0 m 2 . 2 1-2 . 3 4 m 0 -11 ka - Mixed rhyolitic and andesitic tephras from the Egmont Volcanic Centre and the Taupo Volcanic Zone . 1 4 . 7 ka - Rhyolitic ash, possibly the Rerewhakaaitu Ash from the Okataina Volcanic Centre . e * 1 5 . 2 ka - Andesitic tephra from the Egmont Volcanic Centre . * e 17 ka - Andesitic tephra from the Egmont Volcanic Centre . e* 1 9 ka - Andesitic tephra from the Egmont Volcanic Centre . 2 0 ka - Aokautere Ash, a ma jor eruption from the Taupo Volcanic Centre . * estimated age assuming a constant accumulation rate between the Aokautere and Rerewhakaaitu ashes . 2 . Biogenic silica : In the Tokomaru soil there is a dramatic change in the form of biogenic silica down the profile with sponge spicules and microfossils prevalent below 50 cm and phytoliths dominant above this level . The change is interpreted to represent post­ glacial afforestation and is inferred to have occurred at 11-12 ka . B . P . The dramatic change in biogenic silica morphology with depth suggests a potential use of phytoliths to investigate both spatial and temporal variations in vegetation in "normal" parent materials . 3 . Soil Stratigraphy : Three strat igraphic units are recognised above the Aokautere Ash in the Tokomaru soil : 2 1 9 ( I ) Post-glacial Loess - The upper 0 . 5 m, while still dominant ly quartzofeldspathic , is characterised by increased rhyolitic glass , obsidian , volcanic lithics, volcanic minerals (which are mainly unetched) , Sio2 , CaO, Zr, and decreased micas , greywacke lithics , Tio2 , Al2o3 , K2o, Cr , V and Y compared with the underlying loess . The post-glacial loess has accumulated during the past c . 11- 12 ka . ( I I ) Quart zofeldspathic loess : Between 0 . 5 and 1 . 7 m there is more mica in the silt and sand fractions compared with the post-glacial loess and much less volcanogenic material compared with the adjacent units . Notwithstanding the general low volcanogenic cont ributions to this unit there are two distinct pulses of Egmont-derived tephra and a dusting of rhyolitic material with Okataina Volcanic Centre affinit ies . ( II I ) Tephric loess : The zone between 1 . 7 m and 2 . 2 1 m ( i . e . immediately overlying the Aokautere Ash) is one wherein there is a transition in mineralogical and chemical properties from those of the Aokautere Ash to those of the quart zofeldspathic loess, particularly in the coarser grain s i ze s . There is a pulse of Egmont-derived tephra at 2 . 0 -2 . 1 m . 4 . Initial soil development : While it is acknowledged that the Btg2 horizon is within the region where weathering is currently occurring, this horizon is interpreted as resulting ·from weathering that initially devel oped in the quartzofeldspathic loess at c . 12 ka B . P . It represents the soil that began to develop after the dramatic reduction in accumulation rates at about that time . There is a lso evidence for localised gullying in the quartzofeldspathic loess at that t ime . 2 2 0 5 . Fragipan formation : I t i s inferred that the fragipan formed by a p rocess that init ially involved the wetting of material composed of well sorted silt-sized quartz , feldspars and clay aggregates , and t he collapse of the clay aggregates to produce a close packed homogenous silt . Subsequent desiccation resulted in shrinkage c racks and columnar structures . The fragipan is inferred to have formed towards the end of the last stadial . 6 . Yellow-grey earth to Yellow-brown loam/Yellow-brown earth intergrade relationships : It is concluded that the complexity of the yellow-grey earth to yellow-brown loam/yellow-brown earth relationship is a function of drainage and a soil flora+fauna a ssociation . These two soils have developed along fundamentally different weathering paths : ( I ) Yellow-brown loam/yellow-brown earth intergrades are well drained l ow bulk density soils , where the formation of allophane and ferrihydrite has occurred essentially in situ as primary minerals weather so that they are evenly distributed throughout the profile . ( I I ) Yellow-grey earths are poorly drained and waterlogging is common so as the ferrornagnesian minerals weather, Fe is translocated and precipitated at specific sites as mottles and/or concretions . Once these two soil patterns are established they tend to be maintained through different climatic cycles . To understand the paramount factors that govern which weathering path will dominate it is necessary to investigate the cover beds where the two paths were established, i . e . in most cases in the Manawatu, the Tokomaru marine bench . It i s concluded that the initial drainage status is important in determining the weathering path and that once established a combination of drainage and a specific flora+fauna association maintains the separate paths . The complexity of the present boundary perhaps reflects competition between the two mechanisms . 2 2 1 7 . Variations in accumulation rates : The quartz accumulat ion rates in t he silt fract ions demonstrate that there are increasing rates from t he level of the Aokautere Ash up to the top of the quartzofeldspathic loess , with markedly higher rates between 1 4 . 7 ka and 12 ka . At the base of the post-glacial loess there is a dramatic reduction in accumulation rates . The loess that a ccumulated between 1 4 . 7 ka and 12 ka may not be related to cold climate conditions but rather to the increased supply of suitable s ource material . 8 . Chronology: The following chronology is therefore suggested for the Tokomaru soil : 2 0-14 . 7 ka Continued accumulation of loess from a quart zofeldspathic source with diminishing input from Aokautere Ash-derived glass and occasional dustings from eruptions at Egmont Volcanic Centre and the Okataina Volcanic Centre . All these aeolian materials fell on a surface where there was comparatively l ittle biological activity . Towards the end of this period there was s low climatic amelioration . 1 4 . 7-12 ka Increased climatic ameliorat ion although the vegetation is still dominated by grass and scrub . There is large scale aggradation, possibly towards the end of this period . Within this zone there is an increase in quart z accumulation rates , either for the full period or towards the top of the 12-11 ka 11 - 0 ka zone . Dramatic reduction in quart z accumulation rates due to a reduction in source area . Erosion occurs near the edge of the Tokomaru terrace and there is increased biological activity and increased weathering . Forest expands over the area . Post-glacial loess accumulated from more restricted and localised sources . There are signif icant dustings f rom both the Egmont Volcanic Centre and Taupe Volcanic Zone . 2 2 2 Append i x 1 : Gra i n s i ze data for the Wai arek a , Hami l ton , Na i ke and Te Kowhai so i l s ( gm ) . Wai arek a c l ay Samp l e W 1 W2 W3 W4 W5 W6 W7 I n i t i a l * 1 39 .00 109 . 80 1 26 . 1 0 95 . 10 1 1 4 . 20 86 . 10 145 . 70 +1 11111 6 . 4 28 .25 42 . 63 1 000-500 lJm 1 . 27 2 .05 4 . 00 4 . 43 1 7 . 62 6 . 73 3 1 . 42 500-250 lJm 0 . 55 0 . 9 1 2 . 25 5 . 66 1 1 . 78 4 . 59 27 . 40 2 50- 1 25 \Jm 1 . 65 1 . 68 2 . 95 4 . 90 8 . 75 4 . 75 1 6 . 64 1 25-63 lJm 2 . 56 2 . 96 3 . 4 7 2 . 95 4 . 14 3 . 76 9 . 1 2 63-20 lJm 9 . 54 9 .83 7 . 1 6 5 . 90 6 . 96 3 . 62 2 . 91 20-5 lJm 1 4 . 06 1 1 . 52 1 0 . 60 5 .80 4 . 94 2 .87 2 . 42 5 -2 \Jm 3 . 06 2 . 69 2 . 33 1 .06 0 . 68 0 . 54 0 .43 < 2 \Jm 44 . 70 36 . 20 42 . 60 2 2 . 20 1 8 . 70 4 . 30 2 . 20 Sum 7 7 . 39 67 . 84 75 . 36 5 9 . 30 73 . 57 59 . 4 1 1 3 5 . 1 7 Te Kowhai s i l t l oam Samp l e TK 1 TK2 TK3 TK4 TK5 TK6 TK7 TK8 TK9 TK 10 I n i t i a l * 7 1 .00 7 2 . 40 7 9 . 70 68 .60 69 .80 85 .80 76 . 20 7 1 . 50 96 .00 1 05 . 80 +1 11111 0 . 1 1 0 .08 tr tr 0 . 4 1 0 .05 tr 0 . 04 1 000-500\J m 0 . 30 0 . 26 0 .04 0 .01 0 . 10 0 . 16 0 .0 1 0 . 03 0 . 05 tr 500-250 lJm 0 . 58 0 . 58 0 . 1 7 0 . 20 1 . 26 1 . 86 0 . 20 0 . 2 1 0 . 5 1 o . 1 0 2 50- 125 lJm 2 . 05 1 . 98 1 . 1 9 2 . 1 5 7 . 50 6 .82 2 . 07 2 . 65 6 . 31 3 . 64 1 25-63 11m 4 .02 4 . 79 4 . 23 6 . 57 9 . 75 9 . 89 9 . 98 1 1 . 10 1 7 .02 20 . 03 63-20 lJm 8 . 50 8 . 30 1 3 . 50 1 0 . 60 1 1 . 90 1 2 . 26 1 4 . 70 1 6 . 43 1 7 . 20 24 . 30 20-5 11m 1 6 . 60 1 8 . 00 21 . 50 1 7 . 30 1 0 . 34 1 6 . 20 1 3 . 90 1 3 . 00 1 4 . 70 1 4 .00 5-2 11m 3 . 70 5 . 60 4 . 90 2 . 60 1 . 66 2 . 30 1 . 70 1 . 60 2 . 00 1 . 70 ( 2 \Jm 1 3 . 70 1 4 . 30 1 5 . 20 1 2 . 60 9 . 60 1 1 . 90 9 . 50 4 . 50 7 . 40 1 0 . 80 Sum 49 . 56 5 3 . 89 60 . 73 5 2 .03 52 . 1 1 61 .80 52 . 1 1 49 . 52 65 . 23 74 . 57 Hami l ton c l ay l oam Samp l e R 1 R2 R3 R4 R5 R6 R7 RB R9 R 1 0 I n i t i al * 9 1 . 38 89 . 36 9 1 . 92 7 1 . 8 7 74 . 20 72 . 84 73 . 70 81 . 20 83 . 40 7 1 . 50 1 000-50011 m 1 . 25 0 . 35 0 . 23 0 . 25 0 . 1 0 0 .07 0 . 04 0 .05 0 . 08 0 . 1 1 500-250 lJm 1 . 30 1 . 27 1 . 1 8 0 . 50 0 . 5 1 0 . 20 0 . 20 0 . 20 0 . 26 0 . 4 2 2 50- 125 IJI1l 2 .87 2 . 98 2 . 69 1 . 30 0 . 9 1 0 . 38 0 . 31 0 . 30 0 . 3 1 0 . 5 5 1 25-63 IJil1 4 . 18 5 .08 4 . 60 2 . 1 7 1 . 44 0 . 64 0 .44 0 . 38 0 . 26 0 . 58 63-20 IJ1l 9 . 5 7 9 . 63 8 . 59 5 . 1 0 3 . 67 2 . 00 1 . 40 1 . 1 0 0 . 23 0 . 93 20-5 IJI1l 1 5 . 94 1 7 . 55 1 5 . 39 9 . 50 7 . 28 3 . 80 2 . 59 2 . 00 1 . 76 2 . 24 5-2 IJ1l 3 . 59 3 . 39 3 . 63 2 . 90 2 . 10 1 . 10 0 . 93 0 .80 0 . 80 1 . 1 8 ( 2 IJ1l 1 8 . 93 22 . 56 25 .87 24 . 90 29 .45 34 . 10 32 .83 3 7 . 50 42 . 1 7 4 7 . 86 Sum 57 .63 62 .8 1 62 . 1 8 46 .62 4 5 . 46 42 .29 38 . 74 42 . 33 45 .87 5 3 . 8 7 Na ike c l ay S amp l e N 1 N 2 N 3 N4 N5 N6 N7 NB N9 N 10 I n i t i a l * 1 10 . 00 94 . 20 86 .40 70 . 90 70 .60 80 . 10 91 . 60 78 . 90 83 . 20 7 3 . 90 + 1 11111 0 . 1 8 0 . 08 tr tr tr tr tr tr 0 . 07 0 . 28 1 000-50011 m 0 . 22 0 . 22 0 .05 0 .02 0 . 02 0 .0 1 0 .02 0 .07 0 . 24 0 . 62 500-250 IJI1l 0 . 57 0 . 52 0 . 2 1 0 .09 0 .05 0 . 09 0 . 08 0 . 14 0 . 44 1 . 10 250- 1 2511 m 2 .83 2 . 20 1 . 26 0 . 4 1 0 . 34 0 . 30 0 . 30 0 . 37 0 . 77 1 . 77 1 25 -63 IJ1l 3 . 03 2 . 31 1 . 33 0 . 51 0 .48 0 . 56 0 . 65 0 . 67 1 . 22 2 . 09 63-20 IJI1l 7 . 46 6 .02 3 . 42 1 . 42 1 . 33 1 . 52 1 . 95 1 . 97 2 . 73 2 .92 20-5 IJI1l 1 6 . 06 1 2 .85 7 . 48 3 . 99 3 . 7 1 4 . 58 5 . 1 2 4 . 80 5 . 39 6 . 58 5-2 IJI1l 3 . 29 2 . 18 2 . 59 1 . 72 2 . 1 6 2 . 1 3 2 . 01 2 . 47 2 . 54 2 . 52 <2 IJ1l 38 . 80 3 5 . 80 42 . 60 36 . 10 36 .80 41 . 30 44 . 20 35 . 60 36 .00 2 7 . 80 Sum 72 . 44 62 . 18 58 . 94 44 .26 44 . 89 50.49 54 . 33 46 .09 49 . 40 4 5 . 68 * I n i t i a l wei ght . tr - trace . Appen d i x 2 : Wei ght percent (cri stoba l i te + tr i dym i te ) and quartz in the Hami l ton, Naike and Te Kowhai s i l t and c l ay fract ions . R 1 R2 R3 R4 R5 R6 R7 R8 R9 R10 N1 N2 N3 N4 N5 N6 N7 NB N9 N10 TK1 TK2 TK3 TK4 TK5 TK6 TK7 TK8 TK9 TK1 0 --- 63-20 J.1 m - - - - C+T 18 16 1 1 22 20 22 26 18 14 12 10 1 3 1 1 13 10 6 6 7 6 4 18 19 23 25 20 20 22 21 18 1 5 R 14 26 26 1 9 38 43 52 42 54 55 24 19 42 22 33 37 38 33 33 30 26 20 36 44 45 50 36 53 47 42 Q 28 35 40 42 43 4 1 30 24 22 25 46 41 45 38 2 7 30 34 4 1 4 0 32 1 0 8 8 6 4 4 4 5 4 5 - --- 20-5 11 m ----- C+T R Q 25 .0 73 34 . 6 29 . 5 7 1 33 . 3 30 . 2 79 32 . 7 3 5 . 6 63 3 1 . 6 3 7 . 9 70 3 1 . 0 34 . 3 62 25 . 8 3 1 .0 7 1 1 9 .8 28 . 8 77 1 3 . 6 20 . 3 35 1 2 . 5 4 . 3 28 8 .4 26 .0 72 42 . 5 34 . 8 68 23 . 2 2 3 . 8 67 32 . 9 1 7 . 3 35 1 1 . 5 1 0 . 7 38 6 . 3 1 0 . 8 63 7 . 8 9 . 4 63 1 3 . 0 1 1 . 7 1 0 9 . 7 1 2 . 1 50 1 3 . 2 6 . 9 20 7 . 4 1 9 . 5 67 7 .6 24 . 6 7 1 6 . 5 2 1 . 5 76 8 . 4 1 1 .0 70 2 . 4 9 . 5 74 3 . 0 9 . 0 76 2 . 7 1 2 . 0 70 3 1 3 . 7 76 5 . 9 1 4 . 4 75 2 . 9 1 0 . 4 7 1 3 . 3 ---- 5-2 1.1 m ---- C+T R Q 2 7 . 1 64 24 2 1 . 0 7 1 24 2 5 . 0 76 23 29 .0 58 26 1 6 . 1 65 22 7 . 6 58 1 5 1 6 . 0 66 1 1 3 . 3 69 1 2 7 . 0 48 1 0 4 . 0 64 5 1 5 . 4 83 33 1 8 . 5 75 28 1 6 . 6 72 18 5 . 9 5 2 5 . 9 4 . 5 58 3 . 1 3 . 7 58 3 . 0 2 . 3 56 3 . 4 1 . 8 57 5 . 2 4 .4 60 7 . 8 1 . 9 64 3 . 8 2 5 . 4 7 1 7 . 2 1 3 . 9 63 5 . 4 1 7 . 0 79 4 . 3 9 . 4 65 2 . 8 1 . 1 47 2 . 3 7 . 5 72 3 . 5 7 . 5 53 2 . 5 1 5 . 4 66 4 . 9 8 . 4 58 2 . 6 5 . 7 55 2 . 7 - - < 2 J.1 m - c Q 8 . 8 3 . 9 8 . 9 3 . 6 9 . 1 3 . 5 6 . 9 2 . 7 5 . 7 2 . 0 3 . 9 1 . 2 3 . 0 1 . 4 2 . 7 0 . 5 1 . 7 0 . 4 1 . 3 1 .0 5 . 9 4 . 1 5 . 9 3 . 9 2 . 7 1 . 4 1 . 8 0 . 8 1 . 2 0 . 3 1 . 3 0 . 3 1 . 8 0 . 2 1 . 5 0 . 7 1 . 6 0 . 8 1 . 8 1 . 2 7 . 9 1 . 1 I 7 . 6 1 . 1 4 . 4 0 . 5 3 . 0 0 . 7 2 . 7 0 . 2 2 . 2 0 . 4 2 . 1 0 . 3 3 . 7 0 . 6 2 . 9 1 . 5 2 . 8 0 . 6 Q = Quartz ; C = Cri stoba l i te ; C+T = Cri stobal i te p l u s Tri dymi te;f! =. C/(C+T) rat i o . 2 2 3 APPENDIX 3 : Descript ion of the minerals identified in the Tokomaru silt loam. 2 2 4 ( 1) QUARTZ : Quart z occurs as discrete grains broadly in two forms : ( 1 ) rounded frosted grains ( occasionally with dusty inclusions ) that can be up to 3 mm in diameter . This form is of a sedimentary origin ; ( 2 ) conchoidally fractured euhedral fragments or bipyramidal c rystals, both of which often have glass selvedges and/or inclusions . This form is of volcanic origin . Quart z is also common in lithic fragments ( see below) . (2) PLAGIOCLASE: Grains of plagioclase are divided into two broad categories : ( 1 ) S lightly rounded, usually untwinned grains that have a relatively low refractive index ( <1 . 54 ) and are commonly cloudy or dusty due to very fine-grained alteration products . This type has been albitised and is referred to as a sedimentary plagioclase ; ( 2 ) Clear , high relief , highly angular fragments or euhedral tabular crystals of a complexly zoned ( normal, reverse and oscillatory zoning) plagioclase that varies in compos ition up to An8 0 ( labradorite) . They commonly have anomalous brownish interference colours , glassy re­ entrants and selvedges of glass or volcanic lithic materia l . They frequently contain pyroxene , opaque and/ or glassy (both clear or brown glass ) inclusions . Occasionally the cores , which are usually more calcic , have preferentially weathered out in zones parallel to the optical zoning or grain outline . Within. the silt-size fractions where fragments are usually not sufficiently large t o be able to recognise zoning or inclusions two additional forms of plagioclase have been recognised . One is referred to as "low R . I . plagioclase" , being composed of clear, low refractive index ( approximately equal to that of the mounting medium) grains which often have grey 2 2 5 interference colours . These grains often have glass selvedges . The second form, referred to as "high R . I . plagioclase" is clear and has a relatively high refractive index compared with Canada balsam but without anomalous interference colours . This group also often has glass selvedges . Because o f their obvious volcanic origin all of these forms of plagioclase are referred to as volcanic plaqioclase . Plagioclase is also common in lithic fragments ( see below) . (3 ) MICROCLINE: Microcline occurs as clear to s lightly dusty, rounded to subrounded (often approximately square in outline) single grains or as the coarser grains in a silty mat rix of a greywacke lithic . No other potassium feldspar was identified on a routine basis . (4) LITHIC FRAGMENTS: Lithic fragments of various types are common in the loess . P revious investigat ions of the sand and silt mineralogy of soils have employed grain mounts to determine the mineral content and so have not been able to unambiguously identify t he various rock types . In this study thin sections were used enabling this difficulty to be overcome . Grains that have been described as lithic fragments have been divided into three groups . ( 1 ) The first group comprises sub-rounded silt to fine sand size quartz , quartz + feldspar or epidote in a clay to f ine silt matrix . This mat rix is composed of either colourless micas ( sericite or illite) which are aligned and often draped over the coarser grains , or is an o range-yellow material ( chlorite or vermiculite and iron oxide coatings ) . Occasionally the matrix is absent and the fragments are composed of interlocking quartz and/or feldspar and/or epidote grains . There are also rare chert and a rgillite fragments . This group is consistent with derivation from greywacke . (2 ) The second form of lithic f ragment is rare , occurring only in the top 10 erns of the profile . It is commonly oblate , up t o 5 x 3 mm in size and grey under natural light . In 2 2 6 thin sect ion it i s seen t o comprise mainly quart z and feldspar in a clayey matrix, cemented by an iron oxide in a very open spongey texture . It is different from concretions in the Btg horizons and is resistant to repeated deferration . But for the iron oxide cement the texture is very similar to that in the natural topsoil . Because of this factor and the association of this form of lithic with charcoal remaining from the original forest burning it is suggested that this form has resulted f rom soil fusion during this burning . ( 3 ) The third form of lithic fragment comprises euhedral to subhedral silt sized plagioclase with or without opaque grains . Occas ionally pyroxene o r amphibole grains are present . Usually these minerals form a holocrystalline interlocking mosaic but a thin zone of glass may be present between grains . The mineralogy is consistent with derivation from a volcanic source and these grains are therefore referred to as "volcanic lithics" . (5) MICAS : Muscovite, biotite and chlorite form rounded s lightly deformed flakes which, because they have strong elect rostatic force s , are difficult to sample representatively . This problem is compounded as the pre-treatment given the samples may exploit any weathering-induced weakness in the micas and split thick flakes into t hinner sheets . Muscovite appears to be the most stable mica and forms clear buckled flakes which are almost isotropic but with a birefringent rim due to deformation and expansion at the edge of the flake . Biotite c omprises pleochroic brown and green varieties which are often altered t o chlorite . Like muscovite, biotites have ·de formed rims . Occasionally biotite is euhedral, undeformed and with a hexagonal outline . As well a s occurring closely a ssociated with biotite , a green variety of chlorite also occurs as distinct monocrystalline grains . ( 6 ) EPrDOTE GROUP: For the purpose of the mineralogical analysis individual epidote group minerals were not differentiated from each other . "Epidote" occurs as rounded equidimensional 2 2 7 colourless t o pale lemon grains of high relie f . "Epidote" as individual grains is relat ively rare in the coarser grain sizes ; it is more common in the silts . It is common, however , as the larger grains in greywacke lithics in the coarser fractions . ( 7 ) CLINOPYROXENE: Clinopyroxenes form colourless to pale green grains that are often chemically and opt ically concent rically zoned and twinned . Grains often contain apatite , glass and opaque inclusions , and sometimes are partially enclosed by selvedges of glass or volcanic lithic material . In the upper portions of the profile ( above c . 50 cm) clinopyroxenes form euhedral stubby crystals whereas at deeper levels they have very irregular out lines due to weathering and show coxcomb terminations and etched prism faces . ( 8 ) ORTHOPYROXENE: Orthopyroxene is represented by pleochroic green to pink hypersthene that occasional ly has dark brown oxidised ( "burned" ) rims . Grains can contain glass and/or opaque inclusions and frequently have glassy selvedges . Like the clinopyroxenes the o rthopyroxenes are euhedral in the upper port ions of the profile ( although more prismatic in form than the clinopyroxenes ) and at depth are etched with coxcomb terminations . ( 9 ) AMPHIBOLES : Although they are only a relatively minor component of the soil there is a wide variety of amphibole types . P leochroic green-brown and green hornblendes a re the common forms but there a re minor red-brown oxy-hornblendes and rare blue-green varieties . Grains are occasionally twinned and are more commonly euhedral and less altered compared with the pyroxenes . They may contain glass and opaque inclusions and somet imes have glassy selvedges . Rarely the amphibole is a twinned, non-pleochroic pale brown var iety that has very thin (micron thick) t ransverse exsolution lamellae and a relatively low extinction angle . This amphibole may be cummingtonite, but none with a suitable o rientation for positive optical identification was found . 2 2 8 (10 ) OPAQUES : The opaque minerals are magnet ite , ilmenite and t itanornagnet ite or their oxidised equivalents . They are usually black but there are grains with thin orange oxidised rims . Their morphology can vary from rounded frosted grains through to perfect euhedral octahedra (titanomagnetite) o r hexagonal plates ( ilmenite ) . The euhedral varieties may contain glass inclusions or selvedges and, rarely, volcanic lithic selvedges . Some opaques are exsolved . (11) VOLCANIC GLASSES : The term glass has been used for irregular , colourless , isotropic material that has a low refract ive index . Where this material has a brown colour it is referred to as obs idian (glass and obsidian from the same sample are usually chemically equivalent ) . Grains form ( a ) keel or slight ly curved platelette shapes derived from the breakup of glass bubbles , (b) i rregular solid glass (or obs idian) forms with conchoidally fractured surfaces and ( c ) rounded pumice fragments where the vesicles are preserved . Where there is a h igh density of vesicles or the vesicles form long tubes the pumice grains have a translucent "white" colour . The coarser pumice fragments commonly have layers of clays deposited in the vesicles or silt grains t rapped at constrictions in elongate vesicles . At the level of the Aokautere Ash and in the uppermost 50 cm of the profile the pumice fragments are up to 5 mm in diameter . Where there are crystallites present in the glasses the adject ive microlitic is used . These crystals are very fine prismatic grains of pyroxenes and amphiboles or more equant plagioclase and opaques . As the crystal content increases the microlitic glasses grade t owards the volcanic lithic group . (12) TRACE CONSTITUENTS : Minerals that have been identified in t race amounts include titanite , garnets ( some with spiral trails of inclus ions ) , zircons , tourmaline , allanite and ( ? ) perovskite . Also cristobalite forms fine needle s in close association with fibrous feldspar in pale brown grains with a fibre-radiating spherulitic texture similar to those in devitrified ignimbrites and rhyolites . Rarely fossils (biogenic opal ) were noted . These include spherical , cylindrical and disc-like radiolaria, sponge sterrasters and spicules , diatoms and plant phytoliths . A more detailed description of the phytoliths is given in chapter 4 . 2 2 9 Append ix 4 : Tokomaru s i l t loam gra in s i z e distribution ( gm ) . Samp l e * T l T2 T3 T4 T5 T 6 T7 T8 T9 I n i t ia l 52 . 3 2 63 . 6 0 1 1 4 . 4 0 6 4 . 3 0 6 1 . 4 0 59 . 0 0 6 3 . 0 0 62 . 5 0 62 . 7 3 > 50 0�m 0 . 0 1 0 . 02 l . 5 0 0 . 04 0 . 0 1 0 . 0 1 5 0 0- 2 5 0�m 0 . 0 1 0 . 1 3 5 . 9 0 0 . 2 9 0 . 1 1 0 . 04 0 . 0 1 0 . 0 1 0 . 0 1 2 5 0- 1 2 5�m 0 . 08 0 . 3 4 1 0 . 7 6 l . 3 7 0 . 4 9 0 . 2 0 0 . 1 2 0 . 07 0 . 1 5 1 2 5 - 6 3 �m 2 . 2 1 2 . 3 1 1 2 . 2 9 4 . 6 1 3 . 0 5 2 . 5 9 2 . 7 4 2 . 7 2 2 . 9 9 6 3 - 2 0�m 3 0 . 7 0 3 1 . 2 0 4 0 . 4 0 3 1 . 8 0 3 1 . 3 0 3 1 . 3 0 3 4 . 1 0 3 3 . 0 0 3 4 . 7 0 2 0- 5 �m 8 . 7 0 9 . 0 0 2 5 . 3 0 1 0 . 9 0 8 . 4 0 8 . 5 0 8 . 3 0 9 . 5 0 9 . 0 0 5-2�m 1 . 7 0 1 . 8 0 2 . 9 0 l . 7 0 1 . 7 0 1 . 7 0 2 . 0 0 2 . 1 0 1 . 8 0 < 2� m 7 . 1 0 8 . 2 0 1 1 . 4 0 7 . 1 0 8 . 0 0 9 . 0 0 9 . 5 0 1 1 . 5 0 8 . 9 0 Sum 5 0 . 4 9 5 3 . 0 0 1 1 0 . 4 5 5 7 . 8 1 53 . 0 5 53 . 3 3 5 6 . 7 7 58 . 9 0 5 7 . 5 4 Samp l e * T l O T l l T 1 2 T 1 3 T 1 4 T 1 5 T l 6 T 1 7 I n i t i a l 67 . 7 0 6 6 . 0 0 5 6 . 0 0 5 9 . 1 0 1 1 5 . 3 0 62 . 7 0 6 7 . 3 0 62 . 1 0 > 5 0 0�m 0 . 0 1 0 . 0 1 5 0 0 - 2 5 0�m 0 . 0 1 0 . 0 1 0 . 0 1 0 . 0 1 0 . 0 1 0 . 0 1 0 . 0 1 0 . 0 1 2 5 0- 1 2 5�m 0 . 1 4 0 . 1 4 0 . 1 1 0 . 1 7 0 . 2 7 0 . 1 0 0 . 0 7 0 . 07 1 2 5 - 6 3�m 2 . 8 3 2 . 4 5 2 . 5 7 2 . 3 1 4 . 4 6 2 . 2 3 2 . 3 2 2 . 2 3 6 3 - 2 0�m 3 6 . 2 0 3 5 . 1 0 3 0 . 6 0 3 2 . 2 0 62 . 4 0 33 . 9 0 3 4 . 9 0 3 1 . 9 0 2 0- 5�m 9 . 4 0 1 0 . 0 0 8 . 0 0 8 . 4 0 1 7 . 1 0 9 . 4 0 1 1 . 0 0 1 0 . 3 0 5- 2�m 1 . 8 0 1 . 9 0 1 . 7 0 1 . 9 0 3 . 9 0 2 . 3 4 2 . 2 0 3 . 3 0 < 2�m 9 . 8 0 9 . 6 0 8 . 7 0 9 . 1 0 17 . 4 0 9 . 6 0 1 0 . 7 0 8 . 6 0 Sum 60 . 1 7 5 9 . 1 9 5 1 . 6 8 5 4 . 08 1 0 5 . 5 3 57 . 5 8 6 1 . 1 9 5 6 . 4 1 Samp l e * T 1 8 T 1 9 T2 0 T 2 1 T 2 2 T 2 3 T 2 4 T2 5 I n i t i a l 65 . 1 0 1 0 8 . 2 0 64 . 4 0 6 3 . 9 0 62 . 1 2 6 1 . 3 0 6 4 . 2 0 5 6 . 9 0 > 5 0 0�m 0 . 0 4 0 . 0 1 0 . 01 0 . 0 1 0 . 02 5 0 0- 2 5 0�m 0 . 0 1 0 . 0 1 0 . 02 0 . 0 1 0 . 04 0 . 0 6 0 . 05 0 . 0 6 2 5 0 - 1 2 5�m 0 . 07 0 . 09 0 . 0 9 0 . 1 3 0 . 3 4 0 . 4 1 0 . 4 1 0 . 4 4 1 2 5 - 6 3�m 2 . 1 8 4 . 5 2 1 . 5 4 l . 6 3 1 . 8 7 1 . 9 0 2 . 1 6 1 . 7 8 6 3 - 2 0�m 3 1 . 0 0 5 0 . 5 0 2 6 . 3 0 2 5 . 4 0 2 8 . 0 0 2 6 . 2 0 2 5 . 7 0 2 3 . 6 0 2 0- 5 �m 9 . 7 0 1 9 . 2 0 9 . 2 0 9 . 6 0 1 1 . 7 0 1 0 . 9 0 1 1 . 5 0 9 . 0 0 5-2�m 2 . 2 0 4 . 4 0 2 . 1 0 1 . 9 0 2 . 0 0 1 . 7 0 2 . 5 0 1 . 7 0 < 2�m 9 . 6 0 1 8 . 4 0 1 6 . 6 0 1 3 . 6 0 1 2 . 9 0 12 . 2 0 1 4 . 2 0 8 . 6 0 Sum 54 . 7 5 9 7 . 1 1 5 5 . 8 5 5 2 . 3 1 5 6 . 8 5 53 . 3 7 5 6 . 5 2 4 5 . 2 0 * I n i tial weight Append i x 5 : Moda l d a t a from the s an d and coarse s i l t frac t i ons of the Tokomaru s i l t l oam . Data are based on 700 count s un l ess otherw i se spec i f i ed and are expressed in the t ab l es as frequency percent . Abbre v i at i on s of the m i nera l c ategor i es i dent i f i ed : Cpx Opx Hb l de V l i t h i c PO l i th i c P l i t h i c 0 vol e S p l ag V p l ag HR ! p l ag LR I p l ag C gwk e E gwk e I gwk e M gwke QF gwk e 0 sed tr C l i nopyroxene Orthopyroxene Horn b l ende Vo l c an i c l i t h i c P l ag i oc l ase-opaque vo l c an i c l i th i c P l ag i oc l ase vo l c an i c l i th i c Ot her vo l c an i c types Sed imentary p l ag i oc l ase Vo l can i c p l ag i oc l ase H i gh refract i ve i ndex p l ag i oc l as e L ow refract i ve i ndex p l ag i oc l ase C h l or i te greywacke l i th i c E p i dote greywacke l i th i c I l l i te greywacke l i th i c M i c a greywacke l i th i c Quartzofe l dspath i c greywacke l i th i c Other gra i n s of sed imentary or i g i n Trace amounts 0 sed i nc l udes t i t an i te , g arnet , z i rcon , tourma l i ne , a l l an i te , foss i l s and phyto l i ths . 2 3 0 Appendix 5 . 1 - Magnet i c fract ion of the f i ne sand . Samp le Hbl de Cpx Opx V p l ag P l i th i c P O l i th i c Opaque Pum i ce G l as s Obs i d i an 0 vole C gwke E gwke Epi dote M icas 0 sed Counts % magnet i c Samp l e Hbl de Cpx Opx V p l ag P l i th i c PO l i th i c Opaque Pumi ce G l ass Obs i d i an 0 vo l e C gwke E gwke Epi dote Micas 0 sed Count s % magnetic Samp l e Hb l de Cpx Opx V p l ag P l i th i c P O l i th i c Opaque Pum i ce Gl ass Obs i d i an 0 vo l e C gwke E gwke Epidote M icas 0 sed Counts % magnet i c T 1 T2 3 . 1 5 .0 5 . 6 8 . 4 5 . 9 1 2 .8 2 . 7 2 . 4 5 . 0 1 . 6 1 3 .6 20 . 5 0 . 3 4 . 9 0 . 1 1 . 2 1 . 4 2 .0 3 . 0 8 . 6 2 . 2 1 3 . 5 46 . 8 1 2 . 3 9 . 3 4 . 3 0 . 7 0 .8 1 . 2 14 8 T10 Tl1 1 5 .8 1 7 .4 4 . 9 1 0 . 5 6 . 0 9 . 3 4 . 1 1 . 5 4 . 3 4 . 7 1 1 . 1 1 6 . 8 0 . 4 1 .0 1 . 0 0 . 3 2 . 5 1 . 9 1 . 8 1 . 7 2 . 0 1 . 4 37 . 7 2 3 . 7 7 . 1 8 . 2 1 . 1 1 . 3 0 . 1 1 4 10 T 19 T20* 7 . 0 1 2 . 3 1 2 .8 25 . 7 6 . 2 2 5 . 7 0 .8 2 . 3 4 . 1 7 . 5 1 3 . 7 0 . 6 1 . 4 0 . 6 3 . 5 1 . 4 6 . 6 3 . 0 4 . 0 6 . 8 36 . 2 6 . 4 0 . 9 4 . 6 6 . 0 530 273 6 1 4 * Determined on the tota l T3 T4 T5 T6 4 .0 3 . 0 25 . 5 32 . 3 5 . 1 6 . 4 32 . 3 30 .0 1 1 . 2 7 . 0 1 3 . 7 1 4 . 2 2 . 7 1 . 4 2 . 6 2 .6 4 . 8 1 . 7 1 . 4 0 . 6 1 5 . 3 1 4 . 2 7 . 5 6 . 3 4 . 4 1 . 5 5 . 1 4 . 3 3 . 6 9 . 3 6 . 9 6 . 7 1 . 4 0 . 2 1 3 . 7 1 8 . 4 1 . 9 1 . 5 1 0 . 8 7 . 9 3 . 1 0 . 7 1 4 . 4 1 7 . a 3 . 7 6 .0 1 . 8 1 . 7 1 . 2 0 . 8 0 . 1 0 . 3 2 . 6 0 . 4 0 . 5 0 . 8 0 . 2 8 5 24 24 T1 2 T 1 3 T 14 T 1 5 1 8 . 8 1 8 . 0 1 3 . 0 7 . 9 9 . 2 1 8 . 9 1 1 . 1 1 4 . 2 7 . 8 1 1 . 9 1 5 . 5 1 0 . 4 2 . 2 2 . 2 1 . 1 0 . 7 6 . 6 3 . 8 3 . 2 1 .8 20 . 3 20 . 6 14 . 5 1 4 . 4 2 . 7 1 . 3 2 . 4 1 . 3 0 . 4 0 . 2 0 . 2 2 . 6 0 . 6 3 . 5 1 . 5 2 . 8 0 . 7 5 . 2 2 . 5 1 . 5 4 . 3 3 . 0 6 .8 1 6 . 1 8 . 6 1 8 . 4 25 . 5 8 . 1 7 . 6 3 . 5 9 . 1 0 . 1 0 . 3 0 . 9 1 . 3 5 . 4 3 . 5 8 14 1 3 1 1 T21 T22 T23 T24 22 . 1 22 . 0 23 . 2 2 0 . 4 38 . 4 4 1 . 1 46 . 5 45 . 3 1 3 . 9 1 9 . 5 8 . 1 1 3 . 2 1 . 2 1 .0 0 . 7 0 . 7 1 . 7 0 . 7 0 . 9 1 . 1 5 . 5 1 . 3 3 . 6 2 . 7 0 . 4 o . g 0 . 6 0 . 8 3 . 2 2 . 2 1 . 7 0 . 4 3 . 3 3 . 0 4 . 8 5 . 6 2 . 2 3 . 1 5 . 4 7 . 9 2 . 5 1 . 5 3 . 1 1 . 3 4 . 3 2 . 2 0 . 6 0 . 4 0 .4 1 . 7 0 . 1 0 . 1 0 . 1 0 . 4 0 . 7 0 . 1 0 . 1 0 . 2 690 1 005 803 740 25 39 35 38 f ine sand fract i on . 2 3 1 T7 TB* T9 36 . 7 23.8 1 4 . 3 29 . 8 1 7 . 1 5 . 0 8 . 7 1 8 . 6 2 . 8 1 . 4 6 . 0 1 . 1 1 . 3 1 . 9 5 . 8 26 . 0 9 . 1 2 . 0 2 . 2 0 . 5 1 . 5 0 . 2 0 .4 8 . 0 0 . 9 6 . 1 0 . 7 2 . 0 1 . 9 1 . 9 6 . 2 38 . 4 4 . 7 8 . 0 0 .2 0 .4 0 . 5 1 . 9 2 . 2 0 . 2 0 . 2 270 16 9 1 5 T16 T17 T 18 8 . 5 2 . 2 5 .4 5 . 8 3 . 4 3 . 2 1 3 . 0 3 . 4 4 . 3 1 . 4 0 . 5 2 . 4 0 . 8 1 . 6 18 .4 5 .0 9 . 2 1 . 4 0 . 2 1 . 6 2 . 3 2 . 2 2 . 1 5 .8 1 .0 2 . 7 6 . 1 6 . 0 9 . 7 23 . 2 64 . 3 53 . 0 1 2 . 6 6 . 0 6 . 5 1 . 0 4 .0 0 . 5 0 . 3 0 . 5 285 289 499 7 4 6 T25 1 7 . 2 3 7 . 9 7 . 6 0 .4 0 .9 3 .6 0 .4 0 . 7 6 . 4 1 1 . 5 5 . 7 6 .6 0 . 5 0 . 2 0 .2 9 16 33 2 3 2 Append i x 5 . 2 - Non-magnet i c frac t i on of the f i ne sand . Samp l e T 1 T2 T3 T4 T5 T6 T7 TB* T9 E gwke 1 . 6 tr 0 . 3 0 . 5 0 . 6 1 . 2 0 . 7 I gwke 22 . 4 2 . 1 0 . 2 tr 5 . 7 1 6 . 9 1 5 . 2 1 8 . 7 1 8 . 0 Q F gwke 20 . 0 5 . 7 0 . 3 1 . 7 7 . 2 1 0 . 4 1 3 . 3 1 7 . 6 20 . 7 V p l ag 8 . 2 7 . 3 0 . 7 6 . 0 22 . 7 23 . 9 1 8 . 9 1 4 . 1 1 6 . 1 S p l ag 4 . 3 0 . 6 1 . 1 1 . 1 2 . 9 7 . 3 4 . 2 Quartz 30 . 9 5 . 0 0 . 2 2 . 6 3 . 8 9 . 9 1 7 . 6 28 . 5 29 . 6 P 1 i th i c 2 . 5 1 . 8 0 . 2 0 . 6 1 . 2 0 . 9 1 . 8 0 . 3 2 . 7 Pumi c e 1 . 6 35 . 0 44 . 8 38 . 0 1 8 . 2 7 . 4 6 . 1 2 . 5 1 . 2 G l as s 5 . 6 40 . 7 53 . 8 50 . 9 38 . 8 27 . 2 20 . 1 7 . 9 5 . 1 M i c as 2 . 2 tr tr 0 . 9 1 . 4 2 . 0 1 . 2 0 . 7 M i c roc l i ne 0 . 5 0 . 4 tr 0 . 3 0 . 7 0 . 8 0 . 9 0 s ed tr 0 . 2 0 . 5 0 . 1 0 vo l e 1 . 1 1 . 0 Samp l e T 10 T 1 1 T 1 2 T 1 3 T 1 4 T 1 5 T 1 6 T1 7 T 18 E gwke 0 . 9 1 . 5 1 . 3 1 . 9 1 . 1 1 . 5 1 . 1 1 . 6 0 . 4 I gwke 24 . 3 2 1 . 7 18 . 1 1 5 . 8 1 9 . 5 1 9 . 0 23 . 9 25 . 5 22 . 2 Q F gwke 1 3 . 9 1 9 . 4 22 . 5 1 9 . 6 1 7 . 3 20 . 5 1 5 . 6 1 6 . 4 1 9 . 4 V p l ag 1 9 . 4 9 . 1 6 . 9 9 . 5 8 . 3 4 . 2 3 . 7 4 . 6 4 . 5 S p l ag 3 . 3 5 . 9 6 . 6 6 . 4 7 . 4 7 . 3 7 . 4 7 . 7 5 . 7 Quartz 28 . 2 34 . 6 38 . 1 39 . 4 30 . 8 3 7 . 5 4 1 . 9 30 . 5 3 0 . 6 P 1 i th i c 4 . 2 2 . 8 2 . 1 4 . 5 2 . 6 3 . 1 0 . 8 1 . 1 0 . 9 Pum i ce 0 . 6 0 . 6 0 . 1 1 . 1 1 . 4 0 . 8 1 . 5 1 . 0 G l a s s 3 . 6 3 . 0 2 . 5 0 . 8 5 . 0 4 . 0 2 . 8 5 . 1 6 . 9 M i cas 1 . 2 1 . 3 0 . 4 1 . 1 6 . 1 1 . 2 1 . 3 5 . 6 7 . 9 M i c roc l i ne 0 . 2 0 . 7 0 . 9 0 . 7 0 . 8 0 . 1 0 . 6 0 . 3 0 . 3 0 s ed 0 . 2 0 . 1 0 . 1 0 . 1 0 . 4 Samp l e T 1 8 T 1 9 T20* T21 T22 T23 T24 T25 E gwke 1 . 0 0 . 7 1 . 7 o . 1 0 . 1 0 . 6 0 . 1 1 . 2 I gwke 24 . 3 20 . 4 1 8 . 6 9 . 1 5 . 7 8 . 0 7 . 8 1 1 . 2 QF gwke 1 8 . 9 1 6 . 4 1 7 . 2 1 2 . 8 1 0 . 1 1 0 . 4 9 . 4 1 0 . 8 V p l ag 5 . 0 4 . 2 9 . 5 1 9 . 5 35 . 5 26 . 5 28 . 3 2 1 . 7 S p l ag 5 . 8 5 . 3 7 . 8 7 . 2 3 . 8 5 . 1 3 . 0 2 . 8 Quartz 30 . 1 36 . 6 34 . 9 30 . 4 20 . 2 34 . 9 32 . 5 30 . 5 P 1 i th i c 0 . 4 1 . 0 1 . 4 4 . 0 4 . 1 1 . 5 3 . 1 5 . 2 P um i ce 0 . 9 1 . 9 3 . 7 1 0 . 9 1 5 . 8 1 1 . 4 1 2 . 9 1 0 . 7 G l ass 6 . 7 7 . 0 3 . 6 4 . 1 3 . 8 1 . 2 2 . 2 5 . 0 Mi cas 6 . 2 5 . 9 1 . 1 1 . 3 0 . 5 0 . 2 0 . 3 M i c roc l i ne 0 . 6 0 . 3 0 . 3 0 . 4 0 . 3 0 . 3 0 . 5 0 . 6 0 sed 0 . 2 0 . 3 0 . 1 0 . 2 0 . 1 * Determi ned on the total samp l e . Number o f gra i n s counted ; TB = 3 1 0 ; T20 = 360 . 2 3 3 Appen d i x 5 . 3 - Magnet i c frac t i on of the very f i ne sand . Samp l e T 1 T2 T3 T4 T5 T6 T7 TB T9 Hb l de 4 . 9 9 . 0 5 . 7 4 . 9 1 0 . 0 8 . 3 7 . 7 6 . 6 6 . 4 Cpx 1 . 8 2 . 2 1 . 8 0 . 8 2 . 2 2 . 3 2 . 2 1 . 6 1 . 3 Opx 1 . 1 4 . 4 7 . 4 5 . 8 3 . 9 2 . 6 2 . 0 1 . 2 2 . 0 G l as s 0 . 8 2 . 4 9 . 8 6 . 6 2 . 1 1 . 7 0 . 8 1 . 0 0 . 4 Obs i d i an 3 . 4 9 . 3 25 . 1 1 5 . 9 9 . 1 2 . 7 3 . 1 1 . 9 1 . 0 Opaque 2 . 5 3 . 6 7 . 0 2 . 1 6 . 1 7 . 4 3 . 8 3 . 6 4 . 1 V p l ag 1 . 6 1 . 6 1 . 4 1 . 3 2 . 2 1 . 5 0 . 5 1 . 0 0 . 6 P O l i th i c 4 . 0 7 . 8 1 0 . 6 3 . 9 3 . 7 1 . 4 1 . 1 1 . 5 0 . 4 P l i t h i c 0 . 4 1 . 2 0 . 4 0 . 3 0 . 2 0 . 6 0 . 6 0 . 3 0 . 1 V l i th i c 1 . 5 2 . 2 3 . 2 1 . 4 0 . 6 0 . 3 0 . 3 0 . 2 0 . 1 0 vo l e 0 . 5 0 . 8 4 . 9 7 . 8 4 . 4 2 . 4 3 . 4 3 . 1 1 . 8 C gwke 3 3 . 0 1 7 . 9 1 1 . 2 21 . 8 22 . 6 29 . 1 27 . 2 33 . 1 3 3 . 6 E gwke 1 6 . 5 14 . 2 2 . 5 1 0 . 6 1 2 . 1 1 5 . 9 1 7 . 4 1 6 . 6 1 5 . 9 E p i dote 9 . 0 5 . 4 0 . 8 2 . 3 4 . 1 8 . 7 1 0 . 5 1 0 . 7 7 . 6 M i c a s 1 6 . 5 1 6 . 2 5 . 7 1 3 . 5 1 6 . 6 1 2 . 7 1 6 . 6 1 4 . 8 20 . 3 0 sed 2 . 6 1 . 5 0 . 2 0 . 7 0 . 4 2 . 4 2 . 6 2 . 8 3 . 7 % magnet i c 2 . 9 2 . 8 5 . 0 2 . 7 3 . 4 2 . 3 1 . 8 1 . 9 2 . 5 Samp l e T 10 T1 1 T 1 2 T 1 3 T 1 4 T1 5 T 16 T 1 7 Hb l de 9 . 1 5 . 6 4 . 0 7 . 9 2 . 4 3 . 6 3 . 5 4 . 9 Cpx 2 . 2 1 . 4 0 . 6 2 . 9 1 . 4 1 . 3 0 . 5 0 . 8 Opx 3 . 2 2 . 6 2 . 3 4 . 8 5 . 2 4 . 1 3 . 5 3 . 1 G l as s 0 . 9 0 . 4 1 . 4 0 . 3 0 . 7 0 . 8 0 . 9 Obs i di an 2 . 7 1 . 0 1 . 0 1 . 4 1 . 5 2 . 8 2 . 0 1 . 1 Opaque 4 . 5 2 . 9 3 . 1 3 . 8 4 . 7 2 . 9 2 . 6 1 . 6 V p l ag 0 . 3 0 . 6 0 . 6 1 . 2 0 . 6 0 . 3 0 . 5 0 . 3 PO 1 i th i c 0 . 5 1 . 0 0 . 9 2 . 9 1 . 5 2 . 4 1 . 1 0 . 8 P l i th i c 0 . 3 0 . 5 0 . 8 0 . 5 0 . 3 V l i th i c 0 . 2 0 . 3 0 . 8 0 . 5 0 . 8 0 . 3 0 . 4 0 vo l e 3 . 7 3 . 5 2 . 2 3 . 0 3 . 8 3 . 2 2 . 8 1 . 8 C gwke 26 . 0 4 1 . 2 4 3 . 2 35 . 2 40 . 5 33 . 0 32 . 0 39 . 1 E gwke 1 4 . 0 1 7 . 4 1 5 . 7 1 5 . 0 1 3 . 2 1 0 . 2 1 3 . 6 1 3 . 1 E p i dote 5 . 6 5 . 5 6 . 0 5 . 7 5 . 6 5 . 7 8 . 7 8 . 8 M i c a s 24 . 0 1 2 . 5 1 6 . 3 1 2 . 1 1 5 . 4 27 . 4 24 . 2 1 9 . 9 0 sed 2 . 9 3 . 9 2 . 6 1 . 7 2 . 6 2 . 1 3 . 0 2 . 2 % magnet i c 2 . 2 3 . 5 2 . 8 3 . 1 3 . 5 2 . 2 2 . 0 2 .0 Samp l e T18 T19 T20 T21 T22 T23 T24 T25 H b l de 5 . 1 7 . 8 1 2 . 9 1 3 . 0 1 6 . 6 1 4 . 7 1 5 . 2 1 1 . 2 Cpx 1 . 2 0 . 8 8 . 5 1 5 . 3 25 . 2 26 . 4 20 . 1 2 1 . 3 Opx 1 . 8 3 . 3 8 . 5 1 9 . 6 25 . 2 22 . 2 22 . 0 2 1 . 7 G l ass 1 . 4 1 • 1 3 . 1 6 . 4 4 .0 7 . 8 6 . 4 6 . 2 Obs i d i an 1 . 3 2 . 3 2 . 3 3 . 2 6 . 6 1 4 . 3 22 . 3 28 . 8 Opaque 1 . 9 1 . 4 3 . 5 4 . 0 5 . 4 2 . 9 2 . 6 1 . 6 V p l ag 0 . 1 0 . 1 1 . 5 0 . 8 0 . 5 0 . 9 0 . 6 0 . 5 PO l i th i c 0 . 9 0 . 4 0 . 6 1 . 0 2 . 0 1 . 2 1 . 9 0 . 9 P l i th i c 0 . 1 0 . 2 V l i th i c 0 . 3 0 . 8 1 . 2 0 . 7 1 . 2 0 vo l e 1 . 7 2 . 4 3 . 6 1 . 8 2 . 0 1 . 7 2 . 1 1 . 8 C gwke 36 . 1 26 . 0 1 4 . 7 7 . 6 2 . 2 0 . 9 0 . 5 2 . 3 E gwke 1 0 . 5 14 . 2 8 . 5 5 . 1 1 . 5 1 . 4 1 . 4 0 . 7 E p i dote 7 . 3 1 1 . 0 1 1 . 3 8 . 1 4 . 1 2 . 1 2 . 4 0 . 9 M i c a s 28 . 7 25 . 1 1 7 . 3 1 0 . 3 1 . 4 0 . 5 0 . 2 0 . 2 0 sed 2 . 1 3 . 6 2 . 9 2 . 6 1 . 3 1 . 4 1 . 3 0 . 6 % magnet i c 2 . 0 1 . 6 1 . 7 3 . 0 6 . 7 8 . 0 9 . 7 1 0 . 6 2 3 4 Appendi x 5 . 4 - Non -magnet i c frac t i on of the very f i ne sand . Samp l e T1 T2 T3 T4 T5 T6 T7 TB T9 G l as s 5 . 0 37 . 3 89 . 7 73 . 1 32 . 2 22 . 7 1 0 . 5 1 2 . 9 7 . 2 Obs i d i an 0 . 1 V p l ag 0 . 6 1 . 0 1 . 3 1 . 0 2 . 2 1 . 0 1 . 2 0 . 8 0 . 7 LR I p l ag 0 . 3 2 . 0 1 . 5 0 . 7 0 . 7 1 . 0 1 . 0 0 . 5 V l i th i c 0 . 3 0 . 1 0 . 1 0 . 1 I gwke 24 . 1 1 2 . 4 1 . 3 5 . 9 2 1 . 6 21 .0 20 . 9 1 7 . 5 25 . 0 QF gwke 23 . 7 1 7 . 6 2 . 4 9 . 0 1 7 . 7 1 7 . 0 1 7 . 4 1 7 . 8 20 . 2 Quartz 26 .0 1 5 . 6 2 . 4 4 . 8 1 3 . 9 20 . 1 25 . 5 25 . 4 25 . 4 S p l ag 1 8 . 4 1 5 . 6 0 . 9 4 . 4 1 2 . 8 1 5 . 7 2 2 . 3 23 . 7 1 9 . 7 M i croc l i ne 0 . 4 0 . 1 0 . 2 0 . 2 M i cas 1 . 3 0 . 3 0 . 1 0 . 6 1 . 1 0 . 8 0 . 6 1 . 0 0 sed 0 . 1 0 . 1 0 . 1 0 . 4 0 . 3 0 . 3 0 . 2 Samp l e T10 T 1 1 T 1 2 T 1 3 T 1 4 T 1 5 T 16 T 17 G l as s 4 . 5 4 . 4 3 . 1 3 . 5 2 . 2 2 . 9 5 . 2 3 . 0 Obs i d i an V p l ag 0 . 2 0 . 9 1 . 0 1 . 2 0 . 6 2 . 2 1 . 6 0 . 7 L R I p l ag 0 . 2 0 . 9 0 . 6 0 . 5 0 . 6 0 . 9 0 . 8 V l i th i c 0 . 2 0 . 3 0 . 2 0 . 4 0 . 2 I gwke 24 . 1 2 1 .8 1 3 . 0 9 . 4 1 9 . 3 1 4 . 6 1 1 . 8 1 9 . 3 Q F gwke 25 . 4 2 1 . 6 3 3 . 3 2 1 . 6 1 8 . 7 1 5 . 3 27 . 4 2 1 . 3 Quartz 26 . 4 29 . 3 28 . 3 25 . 6 29 . 1 32 . 9 32 . 6 27 . 3 S p l ag 18 . 1 1 7 . 0 1 7 . 4 32 . 5 24 . 0 26 .0 1 6 . 5 2 3 . 7 M i croc l i ne 0 . 2 0 . 5 0 . 4 0 . 6 0 . 2 M i cas 0 . 4 0 . 4 0 . 4 0 . 7 0 . 5 1 . 0 0 . 7 0 sed 0 . 4 3 . 7 2 . 9 4 . 2 4 . 7 4 . 2 2 . 3 3 . 7 Samp l e T18 T 1 9 T20 T21 T22 T23 T24 T25 G l as s 5 . 6 8 . 3 3 . 4 3 . 0 5 . 8 1 2 . 6 6 . 8 1 0 . 3 Obs i di an 0 . 2 V p l ag 1 . 3 1 . 0 2 . 5 2 . 6 8 . 9 3 . 9 4 . 0 6 . 0 LR I p l ag 0 . 4 0 . 2 0 . 2 1 • 1 0 . 7 0 . 2 V l i th i c 0 . 2 I gwke 1 2 . 1 1 1 . 3 6 . 4 4 . 2 3 . 7 1 . 5 1 . 3 3 . 6 QF gwke 28 . 9 1 3 . 9 2 5 . 6 23 . 1 22 . 0 1 2 . 8 1 4 . 2 24 . 4 Quartz 29 . 5 37 . 0 33 . 2 3 1 . 4 25 . 5 32 . 8 4 3 . 4 3 1 . 3 S p l ag 21 . 1 25 . 7 2 5 . 6 29 . 6 2 5 . 9 29 . 6 25 . 0 20 . 6 M i croc l i ne 0 . 7 0 . 7 0 . 2 0 . 2 0 . 4 M i c a s 0 . 6 1 . 4 0 . 2 0 . 7 0 . 2 0 . 2 0 sed 0 . 8 1 . 0 1 . 9 4 . 4 8 . 0 5 . 2 4 . 2 3 . 0 Append i x 5 . 5 - Gra i n mounts of t h e very f i ne s and . Samp l e Quartz M gwke E gwke S p l ag Mi cas Mi croc l i ne Epi dote 0 sed LR I p l ag HR ! p l ag V p l ag Hb lde Cpx Opx Opaque Pumice G l ass Obs i d i an PO l i th i c V l i th i c P l i th i c Samp l e Quartz M gwke E gwke S p l ag Mi cas Mi croc l i ne Epi dote 0 sed LR I p l ag HRI p l ag V p l ag Hb l de Cpx Opx Opaque Pumice G l ass Obs i d i an PO l i t h i c V l i th i c P l i th i c Samp l e Quartz M gwke E gwke S p l ag M icas Mi croc l i ne Ep i dote 0 sed LR I p l ag HR I p l ag V pl ag Hb lde Cpx Opx Opaque Pumi ce G l as s Obs i d i an PO l i th i c V l i t h i c P l i th i c T1 T2 3 1 . 3 23 . 5 34 . 4 33 . 8 8 . 2 1 . 7 9 . 0 1 2 . 0 3 . 6 2 . 5 0 . 9 0 . 4 0 . 8 0 . 3 0 . 3 0 . 8 2 . 2 2 . 6 4 . 1 2 . 0 1 . 8 2 . 0 0 . 5 0 . 1 0 . 1 0 . 2 1 . 0 1 0 . 8 1 . 4 5 . 2 0 . 1 0 . 1 0 . 2 1 . 3 0 . 1 0 . 1 T 10 T1 1 2 3 . 5 20 . 7 24 . 2 28 . 1 7 . 6 6 . 7 23 . 9 28 . 0 4 . 9 1 . 8 0 . 7 1 . 3 0 . 5 0 . 2 0 . 4 4 . 9 4 . 3 0 . 5 1 . 3 1 . 4 2 . 0 0 . 1 0 . 1 0 . 1 0 . 2 0 . 4 1 . 9 1 . 1 4 . 2 3 . 1 0 . 4 0 . 1 0 . 6 0 . 2 T 1 9 T20 1 7 . 6 21 . 3 34 . 4 20 . 4 2 . 6 3 . 3 30 . 7 36 . 2 2 . 5 2 . 5 0 . 2 4 . 7 0 . 1 0 . 6 0 . 2 0 . 4 7 . 5 3 . 9 0 . 4 1 . 1 0 . 6 0 . 2 0 . 6 0 . 2 0 . 2 0 . 4 0 . 1 0 . 2 0 . 4 0 . 9 1 . 1 2 . 6 0 . 1 0 . 1 0 . 5 T3 T4 T5 T6 2 . 9 4 . 6 1 3 . 3 24 . 3 7 . 0 1 2 . 7 1 6 . 2 25 . 5 1 . 0 0 . 6 7 . 9 4 . 2 3 . 2 4 . 5 1 3 . 0 1 7 . 3 1 . 1 1 . 4 2 . 4 3 . 0 0 . 3 0 . 2 0 . 4 0 . 1 0 . 1 0 . 1 0 . 1 0 . 6 0 . 6 4 . 2 2 . 7 3 . 7 2 . 9 0 . 8 1 . 2 1 . 1 0 . 3 1 . 7 0 . 6 1 . 1 2 . 7 0 . 2 0 . 1 0 . 1 0 . 2 0 . 1 0 . 1 0 . 1 0 . 2 0 . 3 0 . 3 0 . 1 0 . 1 33 . 8 39 . 6 1 9 . 4 6 . 9 40 . 8 3 1 . 1 1 8 . 1 1 1 . 2 0 . 6 0 . 4 0 . 6 0 . 4 0 . 2 0 . 2 1 . 3 0 . 5 1 . 0 0 . 2 0 . 1 0 . 1 T 1 2 T 1 3 T 14 T 1 5 25 . 1 28 . 2 26 . 8 20 . 1 24 . 7 28 . 7 24 . 0 27 . 1 1 1 . 8 5 . 7 9 . 4 4 . 2 2 3 . 9 28 . 0 25 . 9 34 . 0 3 . 5 1 . 4 1 . 5 3 . 0 2 . 1 0 . 5 2 . 4 0 . 7 0 . 1 0 . 2 0 . 1 0 . 6 0 . 1 0 . 7 0 . 4 0 . 2 5 . 2 3 . 2 6 . 3 6 . 0 0 . 4 0 . 9 0 . 4 2 . 0 0 . 5 0 . 5 0 . 2 0 . 2 0 . 1 0 . 1 0 . 1 0 . 5 0 . 4 0 . 2 0 . 2 0 . 7 0 . 5 1 . 0 1 . 7 0 . 5 0 . 7 0 . 6 0 . 2 0 . 1 0 . 1 0 . 3 0 . 2 0 . 4 0 . 5 T21 T22 T23 T24 29 . 8 23 . 1 22 . 3 3 7 . 0 26 . 8 1 7 . 2 21 . 5 2 1 . 0 4 . 2 1 . 3 1 . 7 1 9 . 6 29 . 5 3 1 . 1 1 4 . 8 1 . 5 0 . 4 0 . 6 0 . 2 2 . 1 9 . 1 1 . 0 1 . 4 0 . 3 0 . 4 0 . 4 0 . 5 0 . 1 0 . 6 8 . 3 5 . 9 5 . 3 6 . 6 0 . 1 4 . 0 1 . 4 0 . 7 2 . 1 2 . 3 4 . 0 4 . 7 0 . 4 0 . 6 0 . 2 1 . 1 0 . 3 1 . 2 1 .8 0 . 3 1 . 3 2 . 6 1 .8 0 . 1 0 . 4 0 . 4 0 . 1 1 . 5 3 . 6 4 . 2 2 . 0 1 . 9 0 . 2 2 . 0 2 . 1 0 . 4 0 . 8 1 . 2 0 . 4 0 . 6 1 . 1 2 3 5 T7 TB T9 1 9 . 8 24 . 8 22 . 5 26 . 1 25 . 7 25 . 7 1 1 . 9 6 . 3 1 3 . 1 22 . 6 26 . 3 2 1 . 8 5 . 3 3 . 2 3 . 9 0 . 7 0 . 4 0 . 1 0 . 3 0 . 4 0 . 4 0 . 1 0 . 3 0 . 1 3 . 5 4 . 9 4 . 5 0 . 9 0 . 1 1 . 0 0 . 9 1 . 3 0 . 3 0 . 3 0 . 6 0 . 1 0 . 3 0 . 2 0 . 5 3 . 1 1 . 3 2 . 3 3 . 7 3 . 9 2 . 5 0 . 2 0 . 1 0 . 1 0 . 3 0 . 1 0 . 8 0 . 1 T 1 6 T 1 7 T 18 1 7 . 2 23 . 4 20 . 0 37 . 1 29 . 9 30 . 3 2 . 6 8 . 0 2 . 7 28 . 3 27 . 9 27 . 5 4 . 6 3 . 5 6 . 4 0 . 5 0 . 2 3 . 3 0 . 2 0 . 4 0 . 2 0 . 3 0 . 2 6 . 3 4 . 1 4 . 4 0 . 2 0 . 5 1 . 0 0 . 2 0 . 7 0 . 4 0 . 2 0 . 1 0 . 2 0 . 1 0 . 4 0 . 2 0 . 4 0 . 2 0 . 8 0 . 3 1 . 4 0 . 7 1 . 9 0 . 1 0 . 2 0 . 4 T25 1 5 . 8 1 6 . 9 0 . 6 33 . 6 0 . 4 2 . 1 0 . 2 1 . 5 1 0 . 9 0 . 6 3 . 4 0 . 9 0 . 9 1 . 1 0 . 4 3 . 6 2 .6 3 . 6 0 . 4 Append i x Samp l e Quartz M gwk e E gwke S p l ag E p i dote M i c a s 5 . 6 Mi croc l i ne 0 sed Hb l de Cpx Opx Opaque G l ass V p l a9 HR I p l ag LR I p l ag 0 vo l e Counts Samp l e Quartz M gwke E gwke S p l ag Ep i dote M i cas M i croc l i ne 0 sed Hb l de Cpx Opx Opaque G l ass V p l ag HR I p l ag LR I p l ag 0 vo l e Coun ts Samp l e Quartz M gwke E gwke S p l ag Ep i dote M i cas Mi croc l i ne 0 sed Hb l de Cpx Opx Opaque G l ass V p l ag HR I p l ag LRI p l ag 0 vo l e Count s - Gra i n mounts o f the coarse s i l t fract ion . T 1 T2 T3 T4 T5 T6 T7 6 . 8 8 . 2 3 . 9 6 . 0 7 . 9 9 . 3 6 . 4 26 . 8 34 . 5 1 3 . 6 23 . 6 25 . 7 2 1 . 1 20 . 2 1 . 6 1 . 9 1 . 6 2 . 2 3 . 4 2 . 9 2 . 0 3 6 . 4 28 . 1 1 6 . 4 1 7 . 3 28 . 0 4 1 . 6 4 3 . 1 6 . 3 6 . 9 2 . 9 4 . 2 7 . 2 5 . 7 8 . 0 2 . 4 4 . 4 1 . 7 1 . 8 5 . 1 4 . 9 4 . 7 6 . 8 2 . 6 1 . 2 0 . 7 1 . 9 1 . 3 2 . 1 1 . 9 0 . 3 2 . 4 0 . 4 1 . 5 0 . 5 1 . 4 0 . 4 0 . 4 0 . 2 0 . 1 0 . 2 0 . 1 0 . 1 0 . 1 0 . 2 0 . 2 0 . 1 0 . 2 0 . 1 0 . 1 0 . 3 0 . 3 0 . 1 0 . 2 0 . 3 0 . 5 4 . 0 47 . 4 35 . 0 7 . 4 4 . 2 1 . 3 0 . 9 0 . 6 0 . 5 0 . 2 . 1 . 3 1 . 0 0 . 5 0 . 4 0 . 9 1 . 1 0 . 5 0 . 2 0 . 4 8 . 1 7 . 3 4 . 4 6 . 3 9 . 8 6 . 1 9 . 5 0 . 3 0 . 4 1 . 9 0 . 5 0 . 2 0 . 9 0 . 1 790 680 800 8 14 623 590 750 T 10 T 1 1 T 1 2 T 13 T 14 T 15 T 16 7 . 6 5 . 1 6 . 9 9 . 6 7 . 1 20 . 6 9 . 5 3 1 . 1 2 1 . 9 24 . 2 21 . 8 3 1 . 4 29 . 2 34 . 6 1 . 6 1 . 7 3 . 2 2 . 0 0 . 8 2 . 0 1 . 9 39 . 3 5 0 . 2 43 . 7 46 . 5 34 . 2 24 . 5 28 . 9 4 . 9 4 . 8 3 . 0 4 . 3 5 . 2 5 . 7 4 . 6 5 . 1 2 . 5 3 . 0 4 . 2 3 . 4 2 . 8 4 . 4 2 . 5 3 . 7 3 . 8 1 . 1 4 . 0 1 . 0 5 . 2 1 . 0 1 . 4 1 . 7 0 . 9 1 . 5 1 . 4 0 . 7 0 . 2 0 . 3 0 . 3 0 . 4 0 . 2 0 . 2 0 . 1 0 . 2 0 . 1 0 . 4 0 . 3 0 . 5 0 . 3 0 . 9 0 . 3 0 . 2 0 . 1 0 . 3 0 . 6 0 . 5 0 . 7 0 . 2 0 . 3 0 . 4 0 . 6 0 . 1 0 . 7 0 . 4 0 . 8 1 . 6 1 . 1 6 . 0 2 . 2 5 . 3 7 . 7 8 . 4 5 . 8 9 . 7 4 . 2 6 . 6 0 . 6 0 . 1 0 . 1 0 . 1 5 1 4 700 600 800 6 18 680 5 90 T 18 T 1 9 T20 T2 1 T22 T23 T24 T25 1 1 . 6 1 4 . 1 1 4 . 1 24 . 8 9 . 3 9 . 3 1 0 . 0 8 . 0 38 . 1 3 3 . 6 2 1 . 5 26 . 3 1 2 . 0 20 . 3 1 2 . 9 1 0 . 6 2 . 9 1 . 3 2 . 5 1 . 3 1 . 0 0 . 4 0 . 5 0 . 7 23 . 4 2 3 . 4 33 . 0 20 . 2 43 . 6 38 . 8 4 1 . 5 48 . 1 3 . 9 4 . 9 3 . 6 4 . 2 5 . 8 4 . 9 5 . 6 6 . 4 3 . 8 4 . 9 3 . 0 0 . 7 0 . 7 0 . 6 0 . 7 0 . 4 1 . 3 1 .8 1 . 1 1 . 0 1 . 6 2 . 9 1 . 9 1 . 8 1 . 6 0 . 9 0 . 3 0 . 5 0 . 9 1 . 4 1 . 2 1 . 0 0 . 3 0 . 3 0 . 3 0 . 6 0 . 9 0 . 8 0 . 7 0 . 5 0 . 5 0 . 2 0 . 7 0 . 4 1 . 2 0 . 5 0 . 9 0 . 2 0 . 1 0 . 2 0 . 5 0 . 2 0 . 2 0 . 1 0 . 4 0 . 5 0 . 4 0 . 1 0 . 5 0 . 6 0 . 5 0 . 6 1 . 3 0 . 9 1 . 3 1 . 1 1 . 0 1 . 8 1 . 3 2 . 4 1 . 7 1 . 3 2 . 5 1 . 7 5 . 6 3 . 7 1 1 . 6 8 . 8 1 0 . 6 5 . 2 1 4 . 3 7 . 0 5 . 2 8 . 1 7 . 0 6 . 9 9 . 2 1 1 . 2 5 . 1 1 0 . 3 0 . 2 0 . 2 0 . 3 o . 1 0 . 7 0 . 8 6 1 2 6 1 6 6 1 0 570 770 750 824 823 2 3 6 TB T9 9 . 5 5 . 1 1 9 . 8 3 1 . 5 1 . 2 1 . 6 46 .8 4 1 . 8 6 . 7 4 . 3 4 . 6 3 . 1 2 . 5 1 . 4 1 . 1 0 . 9 0 . 3 0 . 4 0 . 3 0 . 3 0 . 4 0 . 8 1 . 3 0 . 3 0 . 3 0 . 3 0 . 1 5 . 1 7 . 2 0 . 1 640 830 T 1 7 1 4 . 4 34 . 4 2 . 4 24 . 0 6 . 1 3 . 2 2 . 9 1 . 3 0 . 5 0 . 1 0 . 3 0 . 5 0 . 4 2 . 0 6 . 7 0 . 3 735 2 3 8 Appendi x 6 : GEOCHEMICAL DATA FROM THE TOKOMARU S I LT LOAM. 6 . 1 : Major e l ement ana lyses of the who l e soi l . Samp le T1 T2 T3 T4 T5 T6 T7 TB T9 T10 T 1 1 T 12 T 13 S i02 70 . 28 70 . 38 69 . 66 70 . 1 4 69 . 70 70 . 2 1 70 . 1 2 70 . 74 7 1 . 1 5 70 .89 70 . 7 1 7 1 .20 70 .6 1 A l 2o3 1 3 . 1 1 1 3 . 37 1 3 . 85 1 3 . 7 2 1 3 .89 1 3 . 80 1 3 .46 1 3 . 38 1 3 . 34 1 3 . 2 1 1 3 . 35 1 3 . 1 5 1 3 . 38 T i02 O . .S5 0 . 54 0 . 33 0 .42 0 . 54 0 . 5 5 0 . 54 0 . 54 0 . 53 0 . 54 0 . 54 0 . 53 0 . 54 Fe2o3 3 . 65 3 . 38 2 .6 1 3 . 1 0 3 . 73 3 . 53 3 . 5 1 3 . 44 3 . 47 3 . 38 3 . 4 1 3 . 45 3 . 57 MnO 0 . 05 0 . 10 0 .05 0 .06 0 .05 0 . 05 0 . 04 0 . 04 0 .05 0 . 05 0 . 04 0 .04 0 .03 MgO 0 . 92 0 . 90 0 . 52 0 . 69 0 . 90 0 . 93 0 . 88 0 .88 0 .88 0 . 89 0 . 9 1 0 .89 0 . 90 CaO Na2o K20 P2o5 LOI 1 . 38 1 . 38 1 . 49 2 . 99 2 . 92 3 . 03 1 . 94 1 . 97 2 . 39 0 . 14 0 . 1 1 0 . 05 4 . 04 4 . 31 5 . 28 1 . 38 2 .9 1 2 . 1 9 0 .07 5 .09 1 . 46 2 . 96 1 . 93 0 .09 4 . 93 1 . 38 1 . 29 3 .09 2 . 96 1 . 88 1 .88 0 . 1 1 0 . 09 4 . 65 4 . 43 1 . 22 1 . 20 2 . 98 2 . 93 1 . 90 1 . 93 0 .09 0 .09 4 . 27 4 . 18 1 . 2 1 2 . 97 1 . 93 0 . 09 4 . 26 1 . 1 8 1 . 1 3 1 . 1 1 2 . 98 3 . 04 3 . 00 1 . 9 1 1 . 9 1 1 . 89 0 . 1 0 0 . 1 0 0 . 1 0 4 . 25 4 . 1 6 4 . 33 Tota l 99 . 05 99 . 36 99 . 26 99 . 7 7 1 00 . 18 100 . 1 8 99 . 20 99 . 48 99 . 75 99 . 42 99 . 38 99 . 60 99 . 46 Sample T 14 T 15 T 1 6 T 1 7 T18 T19 Si02 Al 2o3 T i02 Fe2o3 M nO M gO CaO Na2o K20 P2o5 LOI 70 . 86 70 . 43 69 . 89 69 .56 69. 37 68 . 9 7 1 3 . 57 1 3 . 49 1 3 . 63 1 3 . 73 1 3 . 80 14 . 10 0 . 55 0 . 56 0 . 57 0 . 5 7 0 . 58 0 . 61 3 . 59 3 . 59 3 .84 0 . 04 0 . 04 0 . 04 0 . 93 0 . 92 0 .92 1 . 10 1 .06 1 .03 2 . 97 2 . 93 2 . 92 1 . 88 1 .89 1 . 90 0 . 10 0 . 10 0 . 10 4 . 35 4 .44 4 . 56 4 . 1 4 4 . 28 4 . 14 0 .03 0 .03 0 .02 0 . 9 1 0 . 89 0 . 79 0 . 99 0 . 97 0 . 89 2 .9 5 2 .87 2 .84 1 .86 1 .83 1 . 7 7 0 . 1 0 0 . 09 0 . 06 4 . 83 4 .05 4 . 60 T20 T2 1 T22 T23 68 . 78 68 . 59 71 .08 71 . 3 1 1 4 . 4 1 1 4 .09 1 3 . 1 3 1 2 . 92 0 . 62 0 . 58 0 .49 0 .46 3 .86 4 . 57 3 .86 3 . 4 7 0 . 01 0 . 02 0 .02 0 . 02 0 . 64 0 . 59 0 . 52 0 . 5 1 0 . 75 0 . 76 0 .92 1 . 00 2 .67 2 .66 2 .84 2 .87 1 . 66 1 . 56 1 . 37 1 . 28 0 . 03 0 .03 0 .03 0 . 04 6 .66 6 .84 5 . 70 6 . 02 T24 T25 7 1 . 79 63 . 89 1 2 . 7 1 1 0 . 86 0 .45 0 . 37 3 . 1 5 1 . 93 0 . 03 0 . 04 0 . 5 1 0 . 46 1 . 07 1 .05 2 . 9 1 2 . 58 1 . 25 1 . 1 3 0 . 05 0 . 1 5 6 . 5 1 1 7 .8 1 Tota l 99 . 94 99 .45 9 9 . 40 99 . 6 7 98 . 76 98 . 79 100 . 09 100 . 29 99 .96 99 . 90 1 00 .43 100 . 27 Append i x 6 . 2 : Major e l ement ana l yses of the sand frac t i on ( we i ght precent ) . Samp l e T 1 T2 T3 T4 T5 . T6 T7 TB T9 T10 T 1 1 T 1 2 T 1 3 S i 02 80 . 33 78 .92 72 .28 7 5 . 03 7 7 .03 79 .43 80 . 62 81 . 64 81 . 04 80 . 91 8 1 . 66 82 . 56 82 . 06 A l 20J 1 0 . 04 1 0 . 63 1 2 .87 1 2 . 05 1 1 . 5 1 1 o . 8o 1 0 . 1 7 9 . 87 1 0 . 1 6 1 0 . 1 6 9 . ao 9 . 55 9 . 66 T i 02 0 . 26 0 . 25 0 .25 0 . 23 0 . 27 0 . 26 0 . 23 0 . 2 1 0 . 25 0 . 25 0 . 22 0 . 20 0 . 20 Fe2o3 1 . 3 7 1 . 34 1 . 92 1 . 6 1 1 . 65 1 . 37 1 . 1 9 1 . 07 1 . 33 1 . 27 1 . 1 7 1 . 04 1 . 1 2 MnO 0 . 02 0 .02 0 . 05 0 . 04 0 . 03 0 . 02 0 . 02 0 . 02 0 .02 0 .02 0 . 02 0 . 02 0 . 02 MgO 0 . 45 0 . 4 1 0 . 44 0 . 39 0 . 58 0 . 50 0 . 4 1 0 . 40 0 .44 0 . 44 0 . 4 1 0 . 3 7 0 . 4 3 C aO 1 . 04 1 . 20 1 . 74 1 . 35 1 . 6 1 1 . 31 1 . 07 0 . 98 0 . 99 0 . 99 0 . 93 0 . 86 0 . 92 Na2o 3 . 0 7 3 . 27 3 . 72 3 . 52 3 . 31 3 . 22 3 . 1 7 3 . 1 2 3 . 1 4 3 . 1 4 3 . 1 1 3 . 09 3 . 1 2 K20 1 . 72 1 . 87 2 . 53 2 . 40 1 . 89 1 . 76 1 . 66 1 . 66 1 . 72 1 . 7 1 1 . 65 1 . 63 1 . 63 P2o5 o . o4 o .o3 o . o4 o . o3 o . o3 o .o3 o . o3 o . o3 o . o3 o .o3 o . o3 o . o2 o . o3 LO I 1 . 1 8 1 . 67 3 . 90 3 . 25 1 . 93 1 . 47 1 . 2 1 1 . 1 1 1 . 2 1 1 . 1 9 1 . 07 1 . 0 1 1 . 0 1 Tota l 9 9 . 52 99 . 6 1 99 . 74 99 . 90 99 .84 100 . 1 7 99 . 78 1 00 . 1 1 1 00 . 33 100 . 1 1 1 00 .07 1 00 . 35 100 . 20 Samp l e T 14 T 1 5 T 16 T 1 7 T18 T19 T20 T21 T22 T23 T24 T25 S i02 81 . 75 81 . 99 81 . 55 8 1 . 38 81 . 70 8 1 . 72 83 .65 84 . 7 7 84 . 37 83 . 22 83 .39 82 . 92 A 1 2o3 9 . 7 1 9 . 70 9 . 77 9 . 8 7 9 . 76 9 . 38 8 . 70 8 . 1 7 7 . 72 7 . 73 7 . 64 7 . 94 T i 02 0 . 20 0 . 1 9 0 . 20 0 . 1 9 0 . 1 9 0 . 16 0 . 1 5 0 . 1 6 0 . 1 8 0 . 2 1 0 . 2 1 0 . 2 2 Fe2o3 1 . 1 5 1 . 1 2 1 . 20 1 . 26 1 . 29 1 . 06 0 . 78 0 . 88 1 . 2 1 1 . 58 1 . 5 1 1 . 52 HnO 0 . 02 0 .02 0 . 02 0 . 0 1 0 .0 1 0 .0 1 0 . 01 0 . 02 0 . 03 0 . 04 0 . 04 0 . 04 MgO 0 .43 0 . 43 0 . 43 0 . 4 3 0 . 44 0 . 36 0 . 29 0 . 46 0 . 87 1 . 20 1 . 1 7 1 . 1 3 CaO Na2o K20 P2o5 0 . 88 0 .85 0 .84 0 . 83 0 .81 3 .09 3 .08 3 . 04 3 . 06 3 . 00 1 . 64 1 . 67 1 . 68 1 . 67 1 . 64 0 . 03 0 . 02 0 . 02 0 . 02 0 .02 0 . 73 0 . 64 2 . 99 2 .87 1 . 59 1 . 48 0 . 02 0 . 0 1 0 . 85 2 . 70 1 . 36 0 . 01 1 . 36 1 . 79 2 . 5 1 2 . 45 1 . 1 9 1 . 1 4 0 .01 0 . 02 1 . 76 2 . 36 1 . 1 1 0 . 02 1 . 72 2 . 5 1 1 . 18 0 . 02 LO I 1 . 1 1 1 . 1 8 1 . 30 1 . 36 1 . 37 1 . 1 9 0 . 92 0 . 77 0 . 57 0 . 58 0 . 65 0 . 76 Tot a l 1 00 .01 1 00 . 2 5 100 . 05 1 00 . 08 100. 23 99 . 2 1 99 . 50 1 00 . 1 5 100 . 02 99 . 96 9 9 . 86 99 . 96 2 3 9 Append i x 6 . 3 : Trace e l ement data for the total soi l ( �g/g ) . Samp 1 e T 1 T2 T3 T 4 T5 T6 T7 TB T9 T 1 0 T 1 1 T 1 2 T 1 3 Cr 5 8 . 0 51 .0 2 7 . 0 33 .0 55 . 0 5 5 . 0 55 .0 53 . 0 56 . 0 53 .0 56 .0 51 . 0 5 4 . 0 V 78 .0 71 . 0 3 6 . 0 52 . 0 74 . 0 73 .0 74 .0 74 . 0 72 . 0 72 .0 74 .0 7 2 . 0 7 5 . 0 Ba 458 .0 482 .0 54 7 . 0 509 .0 479 . 0 472 . 0 472 .0 470 . 0 47 1 . 0 478 .0 482 .0 489 . 0 495 . 0 Se 9 .0 9 . 0 8 . 0 6 . 0 1 0 . 0 9 . 0 9 . 0 9 . 0 8 . 0 7 .0 8 .0 9 . 0 9 . 0 Mn 433 .0 860 .0 4 1 0 . 0 470 .0 460 . 0 373 .0 367 .0 352 .0 385 . 0 456 .0 352 .0 355 . 0 295 . 0 T i 326 1 . 0 31 7 1 . 0 1863 . 0 2395 . 0 3098 . 0 3235 .0 3275 .0 3243 . 0 3277 . 0 321 5 . 0 3244 . 0 3229 . 0 3264 . 0 Zn 5 1 . 4 53 .6 4 7 . 8 50 . 7 54 . 3 52 . 2 53 . 3 52 . 5 52 . 7 52 . 3 54 . 6 54 .0 5 5 . 3 C u 6 . 9 6 . 3 6 . 2 6 . 7 6 . 9 5 . 9 6 . 0 5 . 3 6 . 1 6 . 1 6 . 8 7 . 3 6 . 5 N i 1 6 . 0 14 . 6 1 1 . 9 14 . 5 1 8 . 4 1 7 . 7 1 5 . 4 1 3 . 5 1 7 . 8 1 5 . 5 1 5 . 4 1 6 . 3 1 3 . 5 Nb 7 . 1 7 . 0 5 . 9 6. 7 6 . 2 7 . 0 6. 6 5 . 8 7 . 1 6. 0 6. 5 6. 5 6 . 3 Z r 34 7 . 0 340 .0 1 9 7 . 0 265 . 0 3 1 1 . 0 333 .0 340 .0 336 . 0 340 . 0 336 .0 334 .0 34 1 .0 345 . 0 y 24 . 8 25 . 2 24 . 1 25 . 2 25 . 2 25 . 3 24 . 8 25 .0 23 . 8 24 .0 23 . 9 24 . 4 2 5 . 9 Sr 274 . 0 264 .0 1 6 2 . 0 208 . 2 257 .0 266 .0 267 . 0 267 .0 266 . 0 264 .0 265 . 0 263 .0 263 . 0 Rb 83 . 5 83 . 6 9 2 . 4 9 1 . 6 84 . 7 82 . 1 81 .0 81 . 6 82 . 2 82 .8 82 . 0 79 . 7 77 . 7 Pb Ga 1 1 . 8 1 2 . 2 1 2 . 5 1 5 . 1 Sample T14 T 15 1 4 . 7 1 4 . 0 1 3 . 5 1 3 . 7 1 3 .0 1 2 . 7 1 4 . 8 1 4 . 3 1 5 . 2 1 4 . 0 1 3 . 9 1 5 . 0 T 16 T 17 T 18 T 19 T20 T2 1 1 3 . 2 1 3 . 7 1 3 . 3 1 3 . 0 1 4 . 9 1 3 . 9 1 4 . 6 14 . 5 T22 T23 T24 T25 Cr 54 .0 5 7 . 0 5 7 . 0 57.0 59 . 0 56.0 56 .0 5 2 . 0 4 7 . 0 45.0 44 .0 38 .0 V 7 7 . 0 78 . 0 80 . 0 83 .0 86 .0 90 . 0 90 .0 92 . 0 78 . 0 73 .0 69.0 5 5 . 0 Ba 496 . 0 490 . 0 484 . 0 496 . 0 476 .0 432 .0 385 .0 369 . 0 359 . 0 343 .0 338 . 0 305 . 0 Se 9 . 0 9 . 0 9 . 0 10 .0 9 . 0 1 0 . 0 8 .0 8 . 0 6 .0 6 . 0 6 . 0 5 . 0 Mn 288 . 0 280 .0 3 1 6 . 0 284 .0 238 . 0 1 9 1 .0 124 . 0 1 1 5 .0 1 40 .0 1 80 .0 276 .0 348 .0 T i 3305 .0 3332 .0 3420 . 0 351 5 . 0 3544 .0 3778 .0 3906 . 0 3728 . 0 2968 . 0 2842 .0 2696 .0 2228 .0 Zn 53 . 2 53 . 4 5 3 . 8 54 .2 4 9 . 0 44 . 1 36 .8 34 . 4 33 . 6 3 5 . 3 36 . 1 7 3 . 3 Cu 7 . 0 7 . 7 7 .8 6 .6 5 . 1 6 .6 5 .3 4 . 6 4 . 1 2 .3 3 .2 6 . 5 N i 1 3 . 7 1 3 . 7 1 3 . 0 1 3 . 4 1 2 . 6 1 2 . 8 9 . 8 8 . 4 7 . 4 6 . 7 6 . 0 6 . 2 N b 6 . 2 6 . 7 6 . 9 8 . 1 7 . 7 7 . 8 8 . 5 7 . 2 7 . 0 5 . 9 5 . 9 4 . 7 Z r 345 . 0 338 . 0 334 .0 320 . 0 322 . 0 3 14 .0 306 . 0 314 . 0 342 . 0 353 . 0 349 . 0 300 .0 y 27 . 9 29 . 1 28 . 7 2 5 . 4 22 . 6 20 .0 1 5 . 2 1 3 . 0 1 2 . 2 1 2 . 5 1 1 . 4 1 1 . 0 Sr 263 .0 259 . 0 257 .0 254 . 0 2 5 1 .0 240 .0 218 .0 2 1 4 . 0 23 1 . 0 236 .0 236 . 0 2 1 7 .0 Rb Pb Ga 78 . 1 78 . 7 1 3 . 1 1 3 . 1 1 4 . 2 1 4 . 3 7 9 . 0 7 7 . 4 7 5 . 4 7 3 . 5 7 2 . 3 73 . 1 1 3 .8 1 3 . 2 1 4 . 0 1 3 . 3 1 3 . 2 1 2 . 6 1 7 . 0 1 5 . 0 1 7 .0 1 7 . 4 1 7 . 2 1 6 . 3 69 . 7 69 . 0 1 2 . 0 1 1 . 1 1 3 . 0 1 3 . 6 70 . 6 55 . 5 1 1 . 6 1 5 . 5 1 3 .0 1 1 .0 1 2 . 7 1 4 . 0 2 4 0 Append i x 6 . 4 : Trace e lement data of the s and fract i on { � 9/9 ) . Samp l e Cr V T1 T2 24 . 0 23 . 0 32 . 0 28 . 0 T3 T4 T5 1 4 . 0 1 6 . 0 24 . 0 18 . 0 1 9 . 0 3 3 . 0 T6 T7 TB 2 2 . 0 2 1 .0 23 .0 2 9 . 0 26 .0 24 .0 T9 T10 T1 1 T12 T 1 3 23 . 0 2 5 . 0 23 .0 20 . 0 22 . 0 2 7 . 0 28 . 0 26 .0 22 .0 24 . 0 B a 437 .0 463 . 0 543 .0 524 . 0 465 . 0 437 . 0 4 1 8 .0 4 1 9 . 0 44 1 . 0 438 . 0 435 . 0 437 .0 433 . 0 Se 5 .0 4 . 0 6 .0 5 . 0 5 . 0 4 .0 3 . 0 4 . 0 5 . 0 4 . 0 3 . 0 4 . 0 4 . 0 Mn 143 . 0 1 78 . 0 370 .0 3 1 5 . 0 230 . 0 1 78 .0 1 3 7 . 0 1 33 .0 1 4 2 . 0 1 4 1 .0 1 28 . 0 1 1 6 . 0 1 20 .0 Ti 1455 . 0 1 38 1 . 0 1 3 1 3 . 0 1 262 . 0 1 536 . 0 1 4 1 4 . 0 1 230 .0 1 169.0 1 3 1 9 . 0 1 342 . 0 1220 .0 1046 . 0 1 105 . 0 Zn 29 .0 26 . 7 44 . 7 3 7 . 2 28 . 4 23 . 3 2 1 . 6 20 . 9 2 1 . 6 22 . 2 20 .8 1 8 . 6 20 . 5 C u 1 4 . 8 7 . 3 1 5 . 6 8 . 2 5 . 7 6 . 1 4 . 6 7 . 5 8 . 6 4 . 7 6 . 1 5 . 9 5 . 2 N i 4 . 5 5 . 2 3 . 7 2 . 5 6 . 2 6 . 0 3 . 2 3 . 3 5 . 9 5 . 5 4 . 5 5 . 0 4 . 0 Nb Zr y 3 . 4 3 . 7 6 . 3 4 . 5 4 . 0 81 . 0 91 . 3 14 1 .0 1 1 7 . 2 86 . 7 9 . 3 1 1 . 7 2 2 . 2 1 8 . 5 1 2 . 8 4 . 0 3 . 7 2 . 2 80 . 3 74 . 2 72 .8 1 0 . 7 8 . 2 8 . 2 2 . 7 1 . 8 2 . 0 1 . 8 2 . 9 75 . 5 78 . 7 73 . 9 7 1 .8 75 . 6 8 . 4 8 . 8 8 . 3 6 . 9 7 . 8 Sr 248 . 2 23 1 . 3 147 . 1 1 70 .4 246 . 2 250 . 9 235 . 0 241 . 7 228 . 6 244 . 2 24 1 .4 24 1 . 6 248 . 6 Rb 57 . 8 65 . 1 95 . 0 91 . 1 68 . 0 60 . 4 53 . 3 52 . 5 5 2 . 9 5 5 . 8 5 1 . 7 49 . 3 50 . 6 P b 8 . 0 9 . 4 1 4 . 5 1 1 . 9 8 . 4 8 . 1 7 .8 7 . 5 7 . 6 8 . 4 7 . 6 6 . 8 8 . 5 Ga 9 . 7 1 0 . 0 1 3 . 7 1 2 . 8 1 1 . 8 1 0 . 0 9 . 6 8 . 8 8 . 4 8 . 9 8 . 7 7 . 9 7 . 6 Samp l e T 1 4 T 1 5 T16 T 1 7 T 1 8 T 1 9 T20 T2 1 T22 T23 . T24 T25 Cr 22 . 0 2 3 . 0 24 .0 26 .0 25 . 0 20 . 0 19 .0 1 9 . 0 24 . 0 26 . 0 2 5 . 0 26 .0 V 23 .0 2 5 . 0 26 .0 27 .0 26 . 0 22 . 0 1 7 . 0 1 7 . 0 2 2 . 0 29 . 0 28 . 0 30 .0 Ba 435 . 0 443 . 0 486 .0 576 .0 450 . 0 4 1 9 . 0 372 . 0 346 . 0 322 . 0 3 14 . 0 305 . 0 3 1 2 . 0 Se 3 . 0 2 . 0 2 . 0 2 . 0 2 . 0 2 . 0 2 . 0 2 . 0 4 . 0 5 .0 6 . 0 4 . 0 Mn 1 1 7 . 0 1 1 5 .0 1 26 .0 1 26 . 0 1 2 1 . 0 98 . 0 86 .0 1 22 .0 2 1 1 . 0 303 . 0 290 .0 285 .0 T i 1 086 . 0 1 043 . 0 1084 .0 1085 . 0 1052 . 0 9 1 1 .0 773 . 0 894 . 0 963 .0 1 1 29 . 0 1 1 26 . 0 1 180 .0 Zn 20 . 3 20 . 9 2 3 . 3 23 . 4 23 .8 1 7 .8 1 1 . 5 1 2 . 4 1 1 . 5 1 7 . 7 1 7 . 2 50 . 7 C u 5 . 0 5 . 5 5 . 0 5 . 4 6 . 9 5 . 3 8 . 3 5 . 5 7 . 8 7 .0 8 . 4 8 . 9 N i 3 . 0 4 . 2 3 . 1 5 . 0 2 . 6 1 . 7 0 . 3 2 . 5 2 . 7 5 . 5 4 . 3 2 . 3 N b 2 . 3 2 . 0 2 . 1 2 . 6 2 . 4 4 . 1 1 . 7 1 . 4 1 . 6 2 . 1 1 . 5 1 . 9 Zr 78 . 6 7 8 . 0 7 9 . 9 7 7 . 9 74 . 7 7 1 . 4 75 . 7 72 .2 82 . 9 92 . 2 1 07 . 3 94 . 2 y 7 . 7 7 . 7 8 . 2 6 . 6 7 . 5 5 . 3 5 . 7 5 . 8 6 . 4 7 . 1 7 . 3 7 . 4 S r 240 . 6 239 . 3 239 . 3 240 .8 234 . 5 223 .4 209 . 9 203 . 6 207 . 8 2 1 7 . 1 2 1 3 . 8 2 1 3 . 0 Rb 50 . 4 5 2 . 2 53 .0 54 . 2 52 . 9 48 .8 43 . 6 39 . 2 33 . 8 32 . 7 3 1 . 8 34 . 9 Pb 6 . 9 6 . 7 7 .0 8 . 9 8 . 3 7 . 1 6 . 2 5 . 5 7 . 3 6 . 4 6 . 1 1 6 . 6 Ga 8 . 1 7 . 6 8 . 6 8 . 5 8 . 4 8 . 5 7 . 0 5 . 8 6 . 4 5 . 5 7 . 0 5 . 8 2 4 1 Appendix 7 : Electron microprobe data of tephra minerals Sample local i ties . ( 1 ) Aokautere Ash , from the type section . 89 very f ine ash base . 90 coarse base of the graded uni t . 9 1 fine ash over lying the graded uni t . 2 4 2 9 2 upper part o f the graded uni t ( between samp les 90 and 9 1 ) . ( 2 ) Waimihia Tephra Formation , De Bretts section . sample numbers 1 0 and 19 . ( 3 ) Egmont tephras from Mangatoki S trean section ( Franks 1 9 84 ) . In s tratigraphic order : MnP Pumiceous b lock from the Manganui tephra . MnL L i thic crystals from the Manganui tephra . I l Inglewood tephra . 2 2 2 ( E 5 , Franks 1984 ) 2 2 8u ( E4 , Franks 1984 ) 2 2 8m 2 2 8 1 2 3 5 2 4 3 2 4 6 2 5 1 2 56 ( E 3 , Franks 1984 ) ( E2 , Franks 1 984 ) ( E l , Franks 1984 ) Mahoe tephra . Unamed lithic tephra directly above Aokautere Ash . ( 4 ) Okataina Volcanic Centre tephras . 84 Rotoma Ash , Kawerau ( ! . Nairn pers . comm . ) . 87 Whakatane Ash , Kawerau ( I . Nairn pers . comm . ) . Abbreviations : a - associated with b - brown c - c linopyroxene d - corona around f - olivine g - g lass h - hornblende i - inclusion k - core 0 - orthopyroxene p - plagioclase q - quartz r - r im s - selvedge t - t itanomagnetite z - zone n . d . not determined v - ves icular APPENDIX 7 . 1 : GLASS SaNple MnP MnP Code ih2 1t3 ""'p V ""'p st5 ""'p i t 7 2 4 3 ""'p ""'p ""'p ""'p ""'p ""'p ""'p ""'p 1 t8 sc10 se l l sh13 sh14 ic 15 i c 16 Si02 63 . 24 56 .43 61 . 22 61 .04 64 . 1 3 60 .35 64 . 60 61 .00 62 . 99 61 .81 61 .57 66 . 77 6 1 . 06 A lz03 16 .91 16 .35 16 .82 1 7 .25 1 6 . 35 1 6 . 40 16 .42 21 .22 1 6 . 72 1 7 .91 16 .64 13 .49 16 . 52 Ti02 0 .61 0 .92 0 . 59 0.46 0 . 58 0 . 73 0.49 0 .42 0 .5 1 0 . 72 O . S4 0.64 0 . 58 FeO* 3 . 56 5 .82 3 . 66 4 .39 3 . 7 3 5 . 25 2 .90 2 . 22 3 .47 4 . 31 3 .06 2.87 4 . 1 5 ""'0 0 .00 0 . 2 1 0 . 16 0 .23 0 . 10 0 . 14 0 . 1 7 0.00 0 . 1 7 0 .00 0 . 14 0 .00 0. 16 MgO 1 . 1 1 1 . 92 1 . 52 1 . 30 1 .08 1 . 70 0.95 0 . 72 1 . 15 1 . 44 0 .91 0 . 56 1 . 47 CaO 2 . 71 7 . 58 3 . 29 3 .07 2 .62 5 .96 2 .50 5 .99 2 .26 3 . 26 1 . 92 1 . 67 3 . 37 NazO 5 . 13 4 . 41 5 . 22 5 .35 5 . 1 4 4 . 52 4 . 73 5 .87 5 .00 5 . 18 4 .81 4 .01 5 . 52 K2o 4 .09 2 .38 4.08 4.08 3 . 50 2 . S4 4 . 40 2 .23 5 . 13 3 .90 4 .02 4 .43 3 . 60 Cl 0 . 35 0 . 13 0 . 16 0.26 0 . 1 5 0 . 10 0 . 1 1 0 . 10 0 . 19 0 . 18 0 . 19 0 .09 0 . 1 3 Total 97 .7 1 96 . 1 5 96 . 72 97 .43 97 .38 97 .69 97 . 27 99 . 77 97 . 59 98 . 71 93 .80 94 .53 96.56 SIIIP 1 e MnP ltll Code v 1 c 1 ""'l sc1 ""'l ltll 1t2 1 t3 ""'L ""'l 1t3 1 t4 Mnl 1t5 Mnl 1t6 ltll 1 t6 Mnl Mnl Mnl 1h9 1c1 1 sc12 Si02 61 .91 S4 . 1 6 53 .59 49 . 36 54 . 30 53.23 53.91 53.26 53.21 48 . 17 48.64 52.49 6 1 . 1 5 A 12o3 16.60 1 9 . 18 1 9 . 1 1 18. 1 5 1 5 . 65 18 .48 18 .48 18. 10 18. 18 1 7 . 65 16 .44 18.99 18 . 53 Ti02 0 .65 0 .89 0 .99 1 .03 1 . 1 7 0 . 97 0 .87 0.85 0 .99 1 . 10 1 .33 0 .89 0 . 56 FeO* 4 .01 7 . 78 8 . 12 7 . 68 9 . 50 8 . 46 8 . 15 8 .68 8.26 9 . 37 9 .55 6 . 70 3 . 18 MnO 0.00 0 . 16 0 . 1 3 0.00 0 . 24 0 .00 0.00 0.23 0. 1 3 0 . 24 0 .00 0.22 0.00 MgO 1 . 47 3 . 33 3 .48 3 .60 4 . 92 3 .69 3 .46 3 .29 3 .23 3 .85 5 .80 2 .97 0 .99 CaO 2 .67 7 .83 7 . 73 1 1 .02 7 .81 8 . 59 7 . 91 7 . 54 7 . 92 10 .62 9 .04 7 .36 4 . 74 Na2o 5 .37 3 .65 3 .89 2 . 7 1 3 .91 4 .47 4 .65 4 . 72 4 . 03 2 . 83 3 . 37 4 . 35 5 . 52 K2o 4 .26 2 .08 1 .96 1 . 33 2 .38 2 . 45 3 .07 2 .86 2.69 1 . 11 1 . 93 2 . 28 2 . 99 Cl 0 . 10 0.00 0 . 1 4 0 . 1 3 0 . 15 0 . 1 3 0 . 1 7 0 . 1 7 0 . 13 0 . 1 1 0 . 10 0 . 1 3 0 . 1 7 Total 97.04 99.06 99. 14 95 .01 100.03 100.47 100.67 99 . 70 98 . 7 7 95 .65 96.20 96 .38 97 .83 SIIIPle Mnl Code 1c1 Mnl 1t2 Mnl Mnl lng lng lng lng lng lng lng 1 c27 1c29 sh15 1h16 sh17 1h18 1h20 sh21 sc5 lng ln9 sc23 ic23 Si02 53.23 4 7 .99 52.87 53.27 69 . 70 67 .02 66.91 68.43 70 .88 70.46 7 1 .31 69.88 67 .73 Al2o3 19 . 19 1 7 .57 16 .59 19.07 1 5 . 10 1 5 .82 16.61 14 . 79 1 5 . 55 1 5 . 28 1 5 . 52 1 5 .25 14 .45 T1o2 o .87 1 .06 o .88 o.64 o . 28 o .29 o . 34 o .36 o .4 1 o .44 o .42 o. 37 o.42 feO* 7 .43 7 . 5 1 6 .85 7 .89 1 . 96 2 .30 1 .99 1 .85 1 .94 2 . 1 4 1 .86 2.00 1 .81 MnO 0 . 12 0 . 1 5 0 . 1 5 0 . 12 0.00 0 . 1 5 0 . 12 0 . 16 0 . 19 0 . 1 7 0 . 1 4 0.22 0 .00 MgO 3 . 30 3 .60 3 .40 2 .94 0 . 34 0 .49 0 .47 0 .43 0 . 35 0 .42 0.46 0.31 0 .30 CaD 7.87 10.84 6.32 7 .81 1 .85 2 . 5 1 3.04 1 . 57 1 .84 1 . 91 1 . 76 1 . 97 1 .66 NazO 4 .26 3 . 14 4 . 24 4 . 14 4 . 66 4 . 56 4 .93 4 . 18 4 . 74 4 . 59 4 . 91 4.69 4 . 1 7 kzO 2.02 1 . 53 2 . 70 2 . 1 6 4 .47 4 .05 3 . 75 4 . 49 4 . 39 4 . 4 7 4 . 40 4 .28 4 . 32 C l 0 . 12 0 . 12 0 .20 0 . 16 0 .21 0 . 16 0 .20 0 . 15 0 . 16 0 . 23 0.21. 0.23 0 .21 Total 98 .41 93 . 51 94.20 98 .20 98 .57 97 . 35 98.36 96.41 100.45 100 . 1 1 100.99 99 .20 95 .07 APPENDIX 7 . 1 : Continued . Sa.ple Jng lng Code Sc24 v l ng b2 l ng b2 lng sp6 l ng sh lng st8 222 222 222 222 222 222 2 4 4 b1c15 bic15 b 1c16 b 1 c 16 b 1 c 1 7 l c 1J S i02 70 .54 68 .95 7 1 . 1 9 69.93 70 .46 70.43 70 . 10 67 . 10 65.04 67 . 10 65 . 72 66 .82 68 . 68 Al2o3 1 5 . 25 14 .58 1 5 . 28 1 5 .09 15 .05 1 5 . 34 15 .22 1 4 . 39 18. 12 14 .57 1 4 . 62 1 3 . 95 13 .8 1 Ti02 0 .44 0 . 33 0 .46 0 .46 0 .39 0 .46 0 .48 0 .48 0 .29 0 . 39 0 . 45 0 .48 0 . 40 FeO* 1 . 95 1 . 76 1 . 70 1 . 73 2 . 14 1 .83 1 . 92 1 .88 1 . 52 2 . 19 2 . 26 2 .04 2 . 16 MnO 0 . 16 0 . 14 0 . 22 0 .00 0 .00 0.00 0 . 14 0 . 16 0 . 1 1 0 . 1 3 0 . 1 5 0.00 0.00 MgO 0.37 0 .42 0 . 35 0 . 39 0.41 0 .42 0 .40 0 .33 0.22 0 .38 0 . 42 0 . 44 0 . 30 CaO 1 . 92 1 . 64 1 . 7 7 1 . 76 1 .99 1 . 77 1 .80 1 . 26 3 . 54 1 . 59 1 . 6 1 1 . 45 1 . 1 7 Na2o 4 . 56 4 .49 4 . 7 7 4 . 31 4 .94 4 .82 4 . 72 3 . 97 4 .41 4 . 04 4 .04 3 . 70 3.87 K20 4.60 4 .45 4 . 44 4 . 54 4 . 39 4 .40 4.30 4.37 3.36 4 . 52 4 .47 4 .48 4 . 45 C l 0 .24 0 . 19 0 . 1 9 0 . 1 9 0 . 14 0 . 18 0 .22 0 . 1 7 0 . 14 0 . 18 0 . 18 0 . 16 0. 1 7 Tota l 100.03 96 .95 100.37 98.40 99.9 1 99 .65 99. 30 94. 1 1 96.75 95 .09 93 .84 93 . 52 95 .01 Saaple 222 222 222 222 222 222 222 Code sh18 sh19 sh20 1 c21 sc21 st23 s 222 222 222 222 222 222 1h25 1c26 1c26 1 c2 7 st28 sh9 Si02 70.42 70 . 78 68 .97 64 . 62 69.94 71 . 35 69 . 30 67 . 49 67 .85 67 . 14 68 . 75 69 . 30 70 .54 Al2o3 14 . 1 3 1 5 . 35 16 .08 12 .80 15 .05 14 .88 1 5 .05 1 4 . 73 14 .81 1 4 .88 1 4 . 49 1 5 .22 1 5 .30 T i02 0.44 0 .57 0 . 4 1 0 .42 0 .47 0 . 45 0 . 4 1 0 .36 0.41 0 .40 0 .36 0 .42 0.43 FeO* 1 .68 1 .94 2 .09 2 . 54 2 . 1 5 2 .02 2 . 18 2 . 1 1 1 . 76 2 . 10 2.04 2 . 48 1 .90 MnO 0 . 1 1 0 . 1 1 0 . 1 1 0 . 1 7 0 . 15 0 . 14 0 . 1 3 0 . 12 0.00 0 . 1 4 0 . 1 7 0 . 1 9 0 . 12 MgO 0.31 0 . 50 0.44 2 . 1 2 0 .5 1 0 .42 0.47 0 . 34 0.47 0 . 49 0 . 3 1 0.49 0 . 55 cao 1 . 21 1 .63 2 . 54 5 . 10 1 . 74 1 . 32 1 . 79 1 . 47 1 .53 1 .66 1 . 19 1 .58 1 . 60 Na2o 4 .01 4 . 65 4 . 64 3 . 76 4 . 60 4 . 79 4 . 77 4 .22 4 . 13 4 .03 4 .07 4 .97 4 .85 K20 4 .95 5 .01 4 . 37 4 .04 4 .94 4 . 85 4 .65 4 .60 4 .62 4 . 56 4 .61 4 .84 4 . 86 C l 0 . 1 1 0 . 14 0 . 16 0 . 18 0.21 0 . 1 5 0 . 19 0 . 18 0.06 0 .23 0 .20 0.20 0 . 1 7 Total 97 .37 100 .68 99 .81 95 .75 99 . 76 100.37 98.94 95 .62 95 .64 95.63 96 . 1 9 99.69 100.32 SiiiiiP le 222 Code sp l l 222 228u 228u 228u 228u 228u 228u 228u 228u 228u 228u 228u v st13 st 13 1 t25 st25 1 c26 1 c27 1·:27 sc27 sc29 1c29 1 c30 Sto2 7 1 . 57 67 .93 68 .59 69 .09 66 .78 68.64 66 . 76 67 .24 66 .96 68.53 67 .82 65 . 55 68 . 1 1 Alz03 1 5 . 19 1 4 . 1 8 1 5 .60 1 5 . 73 1 5 . 56 15 .89 1 4 . 73 1 3 . 94 14 .62 1 5 . 12 1 5 .45 1 5 .08 15 .67 Tto2 0 .36 0 .30 0 . 59 0 .4 1 0 .57 0 . 53 0 .40 0.33 0 .52 0.63 0 . 67 0 . 62 0.63 FeO* 1 . 74 1 . 33 2 .97 2 .81 3 . 27 2.68 2 .39 2.16 2 .42 2.30 2 . 1 2 2 .22 2 . 24 MnO 0 . 10 0 . 1 2 0 .00 0 .00 0 . 16 0.00 0 . 16 0.00 0 . 15 0 . 14 0 .00 0 . 1 7 0 . 1 3 MgO 0.47 0.27 0 . 62 0 . 60 0 .65 0 .62 0 .55 0 .44 0 .56 0 . 55 0 . 59 0 .64 0 .69 CaO 1 .40 1 .28 1 .80 1 . 75 2 .08 1 .84 2 . 12 1 . 75 1 .93 1 .61 1 . 7 5 1 . 7 1 1 . 78 NazO 4 .39 4 . 42 4 . 7 7 4 .8 1 4 . 53 5 . 02 3 . 78 3 .42 3 .98 4 . 4 1 5 .03 4 . 10 4 .90 K2o 4 .83 4 . 77 5 .01 4 . 74 4 .00 4 .83 4 . 56 4 .25 4 . 35 5 . 19 4 .88 4 . 59 4 .81 Cl 0.20 0 . 14 0 . 1 5 0 . 16 0 . 18 0 .20 0 .24 0.24 0.30 0 .24 0 . 14 0.07 0.06 Total 100.25 94 . 74 100.10 100.10 97 . 78 100.25 95.69 93 . 77 95 . 79 98 . 72 98.45 94. 75 99. 02 APPENDIX 7 . 1 : Con tinued . S.-ple 228u 228u 228u 228u 228u 22S. 228a 22S. 22S. 228a 22S. 22S. 22Bm Code i c30 ic32 i h33 sc34 s ic1 sc5 sf4 ic6 sc6 bic7 i t9 i t9 s;o2 66 .90 66 .51 64 . 77 67 . 99 67 . 59 66 .95 64 .91 64 . 80 68 .3 1 66 . 27 65 . 1 9 66.26 64 . 2 7 AlzOJ 15 .44 1 5 . 20 1 5 . 29 1 5 . 7 1 1 5 .87 14 . 28 16 .55 1 6 . 10 14 .01 1 5 . 50 14 . 73 1 5 .6 1 1 6 . 10 T i02 0 .57 0 .66 0 .49 0 . 7 1 0 . 70 0 . 29 0 . 39 0 . 58 0 . 33 0 .48 0 .40 0 .68 0 .50 rea* 2 . 28 2 . 59 3 .07 2 . 48 2 . 65 2 .98 1 .89 3 . 52 2 . 13 2 . 54 3 . 1 1 3 . 75 3 . 78 MnO 0.00 0 .00 0 .00 0 . 1 5 0 .00 0.25 0 . 19 0 . 1 3 0 .00 0.00 0 . 1 7 0 .00 0 . 1 1 NgO 0 . 50 0 .86 0 .87 0 . 58 0 . 72 0 .67 0 .43 1 .03 0. 53 0 .69 0 .90 0 .68 0 .80 c.o 1 . 57 2 .06 2 . 53 1 .83 2 . 31 2 .08 2 . 63 2 . 65 1 . 69 2 .05 2 .42 2 .38 2 . 70 .. 2o 4 . 78 4 . 49 4 . 2 1 4 . 92 4 .91 3 . 97 4 . 78 4 . 84 3 .96 4 . 53 4 .38 4 . 66 4 . 46 KzO 4 .68 4 .43 4 . 23 4 .87 4 . 58 4 .28 4 .08 4 . 39 4 . 27 4 . 29 3 . 66 4 . 1 3 4 .05 C l 0.28 0 . 1 7 0 . 24 0 . 20 0 . 19 0 . 16 0 . 1 1 0 .22 0 . 1 7 0 . 19 0 . 14 0 . 1 7 0 . 22 Total 97.00 96 .97 95 . 70 99 .44 99 . 52 95 .91 95 .96 98 . 26 95 . 40 96 . 54 95 . 10 98 . 32 96 . 99 s..ple 228m 22S. 228m 22S. 228l 228l 228l 228l 228l 228l 228l 228L 228l Code ic11 se l l sh12 ih13 i hl ih2 ic3 ic4 1c4 ic18 iclO st10 se Si02 67 .40 65.46 66 .29 67 . 19 65 .80 63 .52 64 . 16 66 . 25 66.03 64 . 16 66 . 24 68.25 68.09 A1203 14 . 74 15 .92 1 6 . 54 1 5 . 25 1 5 .59 16.87 1 5 . 72 15 .69 16.23 1 5 . 79 1 5 . 10 1 5 . 92 16 . 12 Ti02 0.52 0 . 50 0 . 48 0 .66 0 . 49 0 . 36 0.49 0.47 0.51 0 . 52 0 . 55 0 . 5 1 0 . 52 FeO* 2.51 2 . 75 2 .88 2 . 60 2 . 37 2 .69 2 . 30 2 . 28 2 . 39 2 . 67 2 . 35 3 .09 2 . 21 NnO 0.00 0 . 1 5 0 . 23 0 .00 0 .00 0 . 16 0 .00 0 . 1 7 0 .00 0.00 0 . 1 1 0 .00 0 . 1 2 NgO 0 . 71 0 . 74 0 . 74 0 . 56 0 .42 0 .46 0.71 0 . 57 0.65 0.87 0 .56 0 . 57 0 . 58 CaO 1 .87 2 .04 2 .45 1 . 90 1 .94 2 . 34 2 . 14 1 . 79 2 .02 2 . 56 1 .81 1 . 82 1 . 78 1a2o 4 . 30 4 . 55 2 .89 4 .84 5 .04 4 . 1 1 4 . 12 4 . 12 5 .03 4 . 20 4 .00 4 . 86 5 .06 lzO 4 . 32 4 .44 3 . 80 4 . 77 4 .42 4 .06 4 . 15 4 . 32 4 .63 4 .23 4 .63 4 . 70 4 .90 C l 0.00 0 . 16 0 . 1 9 0 . 20 0 .26 0 . 3 1 0.14 0 . 23 0.21 0 . 13 0 . 2 1 0 . 1 7 0 . 27 Total 96.37 96 . 7 1 96 .49 97 .97 96.33 94.88 93.93 95.89 97 . 70 95 . 13 95 .56 99 .89 99.65 s..ple 228l 228l 235 Code i c31 1p32 sh3 235 235 ic24 sh4 235 235 235 1116 sh6 1c25 235 so8 235 235 235 sc27 1c28 sh9 235 so1 1 Si02 65.43 67.62 69 . 16 65 . 97 68 .37 65.42 _64.52 67 . 37 67 .58 68.42 66.87 67 . 92 68.87 Al2o3 1 5 . 70 15 .98 16.00 15 .27 1 5 .88 15 .23 17 .94 1 5 .45 15 .98 16 . 16 15.57 15.98 16 . 1 5 1102 o .55 o .42 0 .47 o . 39 0 .42 0 .48 0.36 � .47 o.48 o.44 0.49 0 .46 o .44 FeO* 2.30 2 .09 2.43 2.47 2 .68 2 .24 1 .92 2 .85 2 . 70 2.51 2 .39 2.80 2 . 70 MnO 0. 14 0 .00 0 .00 0 .00 0. 14 0.12 0.00 0.00 0. 16 0 . 12 0.16 0. 12 0 . 1 3 MgO 0.53 0 .60 0 .58 0 . 56 0 .69 0.73 0.48 0 .61 0.65 0 .71 0.57 0. 72 0.61 c.o 1 .81 1 . 79 1 .90 1 .93 2 .43 1 . 93 3 .48 2 . 16 2 . 16 2 . 10 . 1 .83 2 . 18 1 .97 1a2o 4 .75 4 .62 4 .79 4.38 4 .54 3 . 75 4 .71 4 . 37 4.89 4 . 77 4 .63 4.71 4 .93 K20 4.42 4 . 75 4 .52 4 . 33 4 . 14 4 . 15 . 3 .46 4 .40 4 . 16 4 .39 4 .36 4 .44 4.69 Cl 0.20 0. 1 7 0 .20 0.21 0.24 0.18 0.11 0.21 0.16 0 . 19 0 . 15 O.ZO 0 .22 Total 95.83 98.04 100.05 95 .51 99.53 94 .23 96.98 97 .89 98.92 99.81 97.02 99.53 100.71 2 4 5 APPENDIX 7 . 1 : Continued . Sample 235 235 235 235 235 243 Code st20 st22 sp29 sp32 ip32 sc 1 243 ic2 243 ic3 243 sc4 243 243 i c6 sc7 243 y 2 4 6 243 ic8 Si02 67 o 75 67 o42 69 o40 69 o40 65 o 98 65 o 5 1 63 o40 63 o 56 63 oS8 66o43 65 o68 63 o 50 63 o 73 A lz03 1 6 o 24 1 5 o 96 1 5 o 85 15 o93 14 o 74 16o63 16 o28 1 6 o 26 16 o72 14 o94 16 o 36 1 9 o 33 1 5 o90 Ti02 O o 44 O o 54 O o42 O o 44 O o 38 O o 67 O o61 O o 54 O o64 O o 4 1 O o 59 O o43 O o 60 FeO* 3 o 06 3 o 19 2 o 29 2 o 55 2 o 74 3 o 28 3 . 21 3 o 07 3.26 2 .27 3 . 37 2 . 24 3 o 16 MnO 0 . 12 O o 12 O o 1 3 0.00 O oOO 0. 18 0 . 20 0 . 14 0 . 18 O o 1 3 0 .21 0 . 1 7 O o OO MgO O o61 O o 60 0 . 65 O o82 O o72 1 . 14 1 .00 O o 72 l o09 O o 56 0 .88 0.65 0 . 96 CaO 2 .21 2 o 14 1 o 96 1 o87 1 o89 2 o 75 2 o 60 1 o90 2.88 1 o89 2 o 39 4 o 62 2 o81 Na2o 4 o 82 4.26 4 o 74 4 .69 4 o 1 5 4.96 4 . 18 5 o 58 5 o 20 3 . 71 4 o 94 S o 48 4 . 30 K20 4 o 33 4 . 10 4 . 46 4 o28 4 o 66 4 .27 4 . 20 4 . 26 4 .23 4 .80 4 . 69 3 o 54 4 .44 C l 0 .23 0.21 0 . 19 0.20 0 .23 0 .23 O o 20 O o24 0.21 0 .26 0 . 25 O o 14 O o 24 Total 99 o81 98 o 54 100o09 100 . 18 95 o49 99 o62 95 .88 96 o27 97.99 95 .40 99 o 36 100o 10 96 o 14 Sample 243 243 243 243 246 246 Code sh9 tel l ic 12 i h 13 ip12 s 246 s 246 st1 246 246 246 246 246 1h15 1h16 bic17 sh17 b i c 18 S i02 64 .68 64 . 1 2 63 o 65 63 o 36 64 .03 65 . 78 65 .27 64 o60 64o68 63 o49 64 . 53 63 .57 62 . 1 2 Al2o3 1 6 o 37 16.50 1 6 0 44 1 6 o 52 16 o67 16 . 76 1 7 .08 16 o67 1 7 .02 16 o 32 15 .82 1 6 .80 1 5 o 95 Tt02 O o 70 0.58 0 .49 O o66 O o 59 0 .� 0 .69 0 .68 0.66 0 .65 0 .63 0 . 7 1 O o 63 FeO* 3 . 40 3 o 39 2 o 91 3 .02 3 . 18 3 .3 1 3 . 35 3 . 70 3 . 30 3 .07 3 o 1 1 3 .68 3 o 12 MnO 0.00 0 . 1 7 0 . 22 O o 1 3 O o 1 7 O o 14 0 . 1 7 0 .00 Oo20 0 . 12 0 .00 0 . 1 2 0 .00 MgO 1 .09 1 o 1 1 0 .90 Oo91 1 . 10 1 . 20 1 .21 1 .06 0.82 O o88 0.7 1 1 .08 1 .03 CaO 2.67 2 .42 2 . 50 2 o 30 2 o 96 2 064 2 . 55 2 0 56 2 . 53 2 . 20 2 . 99 2 .63 2 . 34 Na2o 5 . 18 5.61 4 . 76 4 o 76 4 .96 S o 14 5 . 12 S o 4 1 5 .82 5 .86 4 .07 5 . 77 S o08 K20 4 .55 4 .53 4 . 59 4 o 49 4 . 1 1 4 . 14 4 . 46 4 .65 4 . 72 4 . 25 4 . 52 4 . 31 4 . 33 C l O o 25 O o27 0 .25 0.25 0 .2 1 0 . 1 7 0 .22 0 .25 0.26 0.24 0.17 0.21 0 .2 1 Total 98.89 98.70 96 . 71 96 . 40 97 . 98 99 . 78 100.12 99 .58 100.01 97 .08 96. 55 98.88 94 .81 Sample 246 246 246 246 246 Code b1c18 b1c19 sc20 1c20 1o21 251 1c2 251 1c2 251 sc3 251 sc5 251 251 1c6 s 251 sc9 251 1c9 Si02 62.78 63 . 1 7 66 .46 64 . 52 65.02 61 .68 6 1 . 59 62 .43 63.75 61 .12 62.86 63.05 60. 14 Al2o3 16.02 16.53 1 5 . 77 16.57 15 .92 15.96 15 .87 16.41 16 .66 16o23 16.40 16 . 78 16.49 Tto2 o .s6 o.s1 o . 63 o .63 o·. s3 0.12 o.65 o .n o.74 0.12 0 .12 o. 11 o .66 FeO* 3 .22 3 . 30 3 .42 3 .07 3.08 3 .93 4 . 14 4 .00 3.82 3.86 3 . 75 3 .85 3 .96 MnO O o 1 2 0 .00 0 . 1 2 0 .00 0 . 12 0 .20 0 . 1 5 0 . 16 0. 16 0 . 1 3 0 .00 0 .00 0 . 1 7 MgO 0.96 1 .04 1 . 51 1 . 1 1 0 .82 1 .27 1 . 22 1 .42 1 . 1 7 1 .23 1 . 1 7 1 . 25 1 .46 CaO 2 .44 2 .56 2 . 1 1 2 .96 2.44 2 .85 2 . 75 3 . 12 2 .76 2 .87 2 .82 2.87 3 . 36 Na2o 4 .45 4.87 4 .83 5 .26 4 .69 4 .68 4 .84 5 . 25 4 .90 4 . 75 4 .96 5 . 45 4 . 40 K2o 4 .07 4 . 14 4 . 93 4 . 7 1 4 .25 4 .06 4 .04 4 .44 4 . 99 4 .40 4 .50 4 . 70 4 .02 C l 0.29 0.20 0 .24 0.23 0.22 0 . 15 0. 1 7 0 . 19 0 . 12 0.13 0 . 13 0 . 1 5 0. 16 Total 94.9 1 96 . 32 100.02 99 .06 97 .09 95.50 95 .42 98.19 99.07 95.44 97.31 98.81 94 .82 2 4 7 APPENDIX 7 . 1 : Continued . Samp le 251 251 251 251 251 251 Code io10 sel l i t22 i t20 st14 sp23 251 V 251 251 i p27 251 5 256 256 i f 1 ic39 S i 02 61 . 55 64 . 32 62 .24 62.03 61 .26 62 .99 60 .62 63.87 59.67 63 .46 53 . 06 59 . 1 1 A1 203 16:59 16 . 77 1 6 . 77 16 .67 16 . 12 16 .69 20 .46 16 .93 1 7 . 65 16 . 57 1 8 . 94 16 .87 Ti02 0 .68 0. 74 0 . 78 0 . 79 0.99 0 .66 0 . 53 0 . 74 0 . 72 0 . 79 0 .80 0 .80 Feo* 3 .47 3 . 85 4 . 26 5 .06 5 .25 3 . 7 1 2 .87 3 .54 3 . 36 3 . 59 5 . 38 4 . 47 MnO 0 .09 0. 18 0 . 16 0 . 1 7 0 . 1 5 0 . 1 7 0 . 1 4 0.00 0.00 0.00 0 . 2 1 0 . 1 3 M90 1 . 36 1 . 16 1 . 2 1 1 . 34 1 .20 1 . 26 1 . 15 1 .08 1 .04 1 . 20 2 .07 1 . 44 CaO 2 .65 2 . 70 2 . 95 3 .37 2 .64 2 .86 5 . 93 2 . 73 3 . 63 2 . 83 7 . 77 3 . 78 Na2o 4 . 7 1 4 . 93 4 .96 5 .02 4 . 98 5 .23 5 . 35 4 .99 4 . 79 4 . 99 4 . 4 1 4 . 50 K20 4 . 14 4 . 82 4 . 29 4 .63 4 .56 4 . 76 3 .04 4 . 29 3 . 99 4 .68 2 . 52 3 . 69 C l 0 . 16 0. 14 0 . 18 0.20 0. 19 0 . 16 0 .08 0 . 14 0 . 18 0 . 13 0 . 1 5 0 . 1 7 Total 95 . 40 99 .6 1 97 .80 99.28 97 .34 98 .49 100 . 1 7 98.31 95 .03 98.24 95 . 3 1 94 .96 Sample Code 256 5 256 256 256 256 256 256 256 256 256 sc14 sc44 ic45 i c46 sc46 1c47 1c48 ic49 ip7 256 V Si02 61 .83 62 . 14 60 .95 61 .67 65 .84 60. 78 59 .60 60 . 15 63.40 60.20 64 . 7 1 Al2o3 1 7 . 57 1 7 . 1 5 1 7 . 20 16 .99 1 3 . 95 1 7 . 28 1 6 . 76 16. 76 1 6 . 1 2 16.80 1 4 . 52 T i02 0 .68 0 . 76 0 . 75 0.61 0 . 35 0.63 0 . 65 0 .64 0 .49 0.66 0.65 FeO* 4 .85 4 . 55 5 .47 3.42 4 . 77 4 .87 4 .29 4 .44 4 .09 4 . 73 4 . 1 1 MnO 0 . 19 0 . 1 7 0 . 1 7 0 . 18 0.18 0 . 1 5 0 . 1 7 0. 1 3 0 . 1 1 0 . 1 1 0 . 16 MgO 1 .69 1 . 30 1 .48 0.86 0.93 1 .48 1 . 78 1 .23 0 .68 1 . 76 0 .83 CaO 4 .49 3 . 38 3 . 72 3 . 12 3 . 33 3 . 81 4 . 55 2 .96 2 .24 3.45 1 . 1 5 Na2o 5 . 54 5 . 21 5 .03 4 .67 3 . 32 5 . 1 3 4 . 72 4 .84 4 . 93 4 . 1 2 4 . 92 K20 3 . 15 4 . 32 4 . 10 3 .58 3 .26 3 . 75 3 .38 3.68 3 .89 3 .65 5 .58 C l 0 . 17 0 . 19 0 . 18 0.21 0 . 16 0 . 22 0 . 1 7 0 .20 0 . 1 5 0 . 1 7 0 . 14 Total 100. 16 99 . 1 7 99 .05 95.31 96.09 98 . 10 96 .07 95.03 96. 10 95 .65 96.77 APPENDIX 7 . 1 : Continued . Sample Code 19 i o l 19 to2 19 soZ 19 to3 19 t o3 19 so3 19 19 19 t o4 bto5 bto6 19 19 i o7 b ioS SiOz 76 . 27 72 . 96 76.81 72 . 77 74 .41 74 .06 74 .49 69.68 73 .00 74 . 77 73.28 Al203 1 2 . 79 12 .24 12.80 12 . 35 12 . 44 12 .24 12 .45 1 3 . 33 1 2 . 1 3 12 .49 12 .02 Ti02 0 . 1 7 0 .43 0.28 0 . 1 3 0 . 14 0.00 0.21 0 .40 0 . 1 3 0 .28 0 . 1 5 FeO* 2 . 28 2 . 52 1 .83 2 . 39 2 . 14 1 .80 2 .02 3 . 48 2 . 45 2 . 35 1 .86 MnO 0 . 1 7 0 . 18 0.00 0 . 1 5 0 .00 0.00 0.00 0 .00 0 . 10 0 .00 0 . 16 MgO 0 . 14 0 . 1 9 0.�5 0 . 1 6 0 . 1 3 0 . 1 7 0 . 10 0 . 49 0 . 23 0 . 13 0 . 1 5 CaO 1 . 25 1 .29 1 .29 1 . 26 1 . 24 1 . 29 1 . 26 2 . 34 1 .26 1 . 23 1 . 24 Na2o 4 .04 3 . 18 4 .29 2 . 44 3 .88 3 . 40 4 .02 3 .81 3 . 55 4 .08 3 . 15 K20 2 . 96 2.80 2 .87 2 .82 2 .89 2 .85 2 .85 2 .45 2 . 85 2 . 77 2 . 91 C l 0 . 12 0 . 1 3 0 . 1 1 0 .00 0 . 12 0 . 1 1 0 .00 0 . 14 0 . 12 0 . 1 3 0 . 10 Total 100 . 19 95 . 92 100.43 94.47 9 7 . 39 95 . 92 97 . 40 96 . 12 95 . 82 98.23 95.02 Sample Code 19 19 bio9 so9 19 19 19 19 19 19 toll so1 1 to 12 so12 sp25 g27 1 9 10 10 gZ8 bto41 bst42 St02 74 .06 75.44 73.44 76 . 2 1 75 . 23 76 . 19 75 .62 76 . 16 75 .36 73.90 76 .97 AlzOJ 12 . 19 1 2 . 36 12.04 1 2 . 54 1 2 . 53 12 .61 1 2 .20 12.49 1 2 . 45 1 2 . 35 12 .89 Tto2 o . 19 o . 15 0.09 0 . 1 4 0 . 1 1 0 . 1 1 0.21 0 .20 0 . 1 5 o.23 0 . 16 FeO* 1 .90 1 .87 2 .33 1 . 9 1 1 .87 1 .86 1 . 73 1 . 73 1 . 79 1 .82 1 .88 MnO 0 . 12 0.00 0 . 13 0 .00 0 .00 0.00 0.00 0.00 0.00 0.00 0.00 MgO 0 . 14 0 . 1 3 0 . 17 0 . 18 0 . 14 0 . 14 0 . 16 0 . 1 7 0 . 19 0 . 16 0 . 13 CaD 1 . 1 7 1 . 26 1 .25 1 .36 1 . 34 1 . 31 1 .20 1 . 24 1 . 34 1 . 1 7 1 . 29 Na2o 3 .92 4 . 26 3.42 4 .03 4 .06 3 .99 3 . 72 3 .90 3 . 79 3.91 4 . 27 K20 2 .80 2 . 73 2 .59 2 . 85 2 .88 2 .85 2.80 2 .80 2 .86 2.85 2 . 75 C l 0.08 0 . 1 3 0 . 1 1 0. 1 2 0 . 12 0 . 1 2 0 . 1 1 0 . 1 2 0 . 16 0 . 1 3 0 . 10 Total 96.57 98. 33 95.77 99 .34 98 . 34 . 99. 18 97 . 75 98.81 98.09 96. 52 100.44 2 4 8 APPENDIX 7 . 1 : Continued . Sample 10 Code bs t43 10 st43 10 10 10 10 10 10 10 10 st44 bio45 so45 b io46 bio80 so80 bit48 st48 10 s81 10 i82 S i 02 76 .29 76 .92 76 .46 74 .47 76 .52 73 .09 76 .57 76 .86 76 .05 75 .96 76 .21 73 .42 A 120 12 .62 1 2 . 78 1 2 .86 12.45 1 2 . 59 1 2 . 32 12 .69 12 .83 1 2 . 75 12 .6 1 12 . 78 12 .05 MnO C aO Na2o K20 C l 0.24 0 . 21 0 . 22 0 . 1 5 0 . 16 0 . 10 0 . 12 0 . 1 7 0 .36 0. 18 2 . 12 1 . 76 2 .00 2 . 20 1 . 78 2 .62 1 . 89 1 . 93 1 . 92 1 . 78 0.00 0 .00 0.00 0.00 0 .00 0 .00 0.00 0.00 0 . 14 0 .00 0 . 16 0 . 1 7 0 . 1 7 0 . 14 0 . 18 0 . 14 0 . 14 0 . 1 3 0 . 1 7 0 . 18 1 . 21 1 . 23 1 . 29 1 . 20 1 . 30 1 . 1 9 1 . 22 1 . 24 1 . 24 1 . 34 4 .22 4 . 50 4 . 36 4 . 29 4 . 36 4 .08 4 . 20 4 . 25 4 .49 4 . 28 2.80 2 . 92 2.91 2 . 79 2 .88 2 . 82 2 .94 2.94 2 . 70 3 .03 0 . 1 3 0 . 16 0 . 1 7 0 . 16 0. 1 5 0 . 1 3 0 . 1 5 0 . 14 0. 16 0 . 12 0 . 30 0.25 1 . 59 2 .00 0 .00 0 .00 0 . 20 0 . 1 5 1 . 27 1 . 17 4 .04 3 . 83 3 . 2 1 2 . 78 0 . 1 2 0 . 12 Total 99. 79 100 .65 100.44 97.85 99 . 92 96 . 49 99 . 92 100.49 99 .98 99.48 99 . 72 95 . 77 Saii!Ple Code 10 io83 10 10 so83 io49 10 so84 10 10 g50 bk50 10 g51 10 g52 10 b53 1 0 vS4 10 v56 Si02 75 .59 7 7 . 58 74 .89 76 .82 77 . 52 76 . 87 7 7 . 25 76.63 75 .95 76 . 73 76 .64 A l20 12 .64 12 .63 1 2 . 28 1 2 . 78 12 . 71 12.67 12 .86 12 . 33 12 .69 12 .67 1 2 .97 T i02 0 . 1 1 0 . 18 0 .24 0 .2 1 0 .22 0.25 0 . 12 0 . 23 0 . 19 0 .22 0 .23 FeO* 2.20 1 . 91 2 . 13 1 . 76 1 . 70 1 . 83 1 . 76 1 .81 1 . 72 1 . 79 1 . 7 7 MnO 0.00 0 .00 0 . 1 1 0 .00 0 .00 0. 12 0.00 0 .00 0.00 0 . 1 1 0 .00 MgO 0. 14 0 . 15 0 . 1 1 0 . 17 0 . 13 0 . 18 0 . 17 0 . 16 0 . 19 0. 19 0 . 18 CaO 1 . 28 1 . 32 1 . 15 1 .21 1 .46 1 .30 1 . 28 1 .32 1 . 28 1 . 32 1 .38 NazO 4 .27 4 . 22 3 . 71 4 . 1 5 3 . 73 4 .48 4 .28 4 .26 4 . 32 4 . 39 4 .38 KzO 2.64 2 . 78 3 .30 3 .02 3 .03 2 . 7 7 2 .89 3.07 2 . 78 2 .97 3 .06 C l 0.15 0 . 1 7 0. 17 0 . 1 3 0.00 0.07 0 . 1 1 0 . 13 0 . 1 1 0 . 1 1 0 .08 Total 99.02 100. 94 97 .09 100.25 100.50 99.54 100.72 99.94 99.23 100·.50 100.69 2 4 9 2 5 0 APPENDIX 7 . 1 : C on t inued . Sample 87 87 Code 1o14 g33 87 87 87 87 87 87 87 bv37 g38 87 87 87 87 b9kl4 b9k34 bgR34 bg35 v36 sp39 sq40 su4 1 i u41 S i02 74 . 78 78 .58 77.49 76 .94 77.03 78 . 70 78 . 29 78.88 79 .08 78.42 79 .37 79.01 74 .92 Al203 1 1 .71 1 2 . 03 1 1 .81 1 1 . 80 1 1 . 72 1 1 . 85 1 1 . 92 12 .41 1 1 .94 12 .00 1 2 . 1 2 1 2 . 02 1 1 .35 T i02 0 . 14 0 . 12 0 .08 0. 12 0.00 0. 12 0 .00 0 . 16 0. 14 0 .08 0 .00 0 . 09 0.00 Feo* 1 . 31 0 .85 1 . 1 3 0.84 0.93 0 . 78 0 . 77 0.90 0.92 o . 80 0 . 98 1 .04 1 . 59 MnO 0.04 0 .00 0.00 0.00 0.00 0.00 0 .00 0 . 13 0.00 0 . 12 0 .00 0 .00 0. 13 MgO 0 . 10 0 . 10 0 .2 1 0 .05 0 . 20 0 . 1 6 0 .09 0 . 10 0.09 0 . 14 0 . 10 0 . 07 0 . 13 CaO 0 .95 0 . 70 0 . 70 0 . 74 0 . 77 0 .90 0 . 64 0 .96 0 .59 0 .61 0 . 70 0 . 65 0.92 NazO 2 . 34 3 . 59 3 .30 3 . 73 3 . 36 5 . 55 3 . 62 4 . 26 3 .85 3 .84 3 . 75 3 . 58 2.97 K2o 3 . 02 3 . 58 3 . 97 3 .85 4 .03 1 .09 3 . 70 3 . 18 3.67 3 . 74 3 . 53 3.67 2 .97 C l 0 . 13 0 .08 0 . 1 2 0 . 1 3 0 .06 0.07 0 .05 0 .00 0 .00 0 . 10 0 . 10 0 . 10 0 .08 Total 94 .52 99 .63 98.81 98. 15 98 . 10 99.22 99 .08 100.98 100.28 99 .85 100.65 100.23 95 .06 Sa����> l e Code 84 84 84 84 84 84 i p30 b936 bsp37 9k39 gt39 gR39 84 9 84 84 gt40 gR40 84 84 v su42 84 V S i02 78 .64 79.21 64 .65 78 .37 77 . 10 76 .94 78.2 1 78 . 10 78 . 15 77 . 67 7 7 . 57 76 .46 Al2o3 1 1 .94 1 2 . 1 6 21 .03 12 . 12 1 1 .86 1 1 .97 1 2 .02 1 1 . 95 1 1 .83 12 .00 1 1 . 93 1 1 .63 Ti02 0 . 1 1 0 .00 0 .22 0. 16 0 . 13 0 . 13 0 . 12 0.00 0.07 0 . 12 0 . 15 0 .00 Feo* 0.89 0 . 35 0 .87 0 .97 0.93 0 . 84 0 .86 0 .9 1 0 .84 0.86 1 . 05 0 .91 MnO 0.00 0 .00 0.00 0.00 0 . 14 0.00 0 .00 0.00 0.00 0 .09 0 .00 0 .00 MgO 0 . 13 0 .08 0 . 1 3 0 . 10 0 . 1 1 0 . 1 3 0 . 14 0 .08 0 . 1 3 0 . 1 3 0 . 1 1 0 . 14 CaO 0 . 79 0 .90 5 . 76 0 .87 0 .76 0 . 77 0 .80 0 . 75 0.81 0 . 78 0 . 79 0 .82 Na2o 3 . 7 1 4 . 99 5 .97 3.81 3 .91 3 .99 3 . 66 3 .69 3 . 78 3 .82 3 . 78 3 .57 kzO 3 . 39 0 .69 1 .30 3 .26 3 .40 3 .38 3 . 40 3 .38 3.45 3 . 40 3 . 4 1 3 . 33 C l 0 . 12 0 .00 0 .00 0.00 0.08 0 .06 0 .00 0 . 10 0 . 10 0 .06 0 . 14 0 . 13 Total 99 . 72 98.38 99.93 99 .66 98.28 98.21 99 .21 98.96 99 . 16 98 .93 98.93 96 . 99 APPENDIX 7 . 1 : Con tinued . Sample 9<' Code 920 92 g1 92 g2 92 gJ 92 g4 92 g5 92 g7 92 g8 92 g9 92 92 g10 g1 1 92 g12 92 913 SiOz 75 . 24 75 . 64 75 .66 75 . 78 76 . 40 75 . 78 74 .30 75 . 33 75 .47 74 . 22 75 .98 75 . 1 7 75 . 47 A l 203 1 1 .43 1 1 . 78 1 1 .38 1 1 .87 1 1 . 53 1 1 .37 1 1 .50 1 1 . 26 1 1 . 44 1 1 . 36 1 1 . 33 1 1 . 1 1 1 1 . 46 Ti02 0 . 1 1 0 . 1 1 0 . 12 0 . 1 7 0 . 1 7 0 . 14 0 . 10 0 . 15 0 . 09 0 . 1 1 0 . 1 1 0 . 16 0 . 1 0 Feo* 1 . 14 1 . 18 1 .05 1 . 1 1 1 . 02 1 . 20 1 .03 1 .07 1 .05 1 .06 1 .09 1 . 1 3 1 . 26 MnO 0.00 0 .00 0.00 0 .00 0 .00 0 . 1 1 0 .09 0 .00 0 .00 0 .00 0.00 0 .00 0 . 1 3 M90 0 . 1 2 0 .09 0 . 1 3 0 . 1 4 0 . 10 0. 11 0 . 1 3 0 . 10 0 . 1 2 0. 1 1 0 .07 "0 . 1 2 0 . 1 1 CaO 1 .02 1 .03 0 .96 1 .0 1 0 .92 0 .97 0.94 0 . 92 0 .88 1 .01 1 .01 1 .01 0 . 93 Na20 3 . 1 1 3 . 34 3 .43 3 . 57 3 . 7 1 3.0i 3.44 3 .38 3 .47 3 .39 3 . 12 3 . 20 3 .30 K20 3 .02 3 . 1 1 2 .90 2 .89 2 .90 3 . 10 2 . 78 2 . 62 3 .08 2.67 2 . 57 3 . 02 2 . 93 C l 0 . 1 5 0 . 1 1 0 . 14 0 . 1 3 0 . 1 3 0 .20 0 . 15 0 . 1 2 0 . 16 0. 14 0 . 13 0 . 16 0 . 1 2 Total 95 . 34 96 . 39 95.77 96 .67 96 .88 95 .99 94.46 94 . 95 95 . 76 94.07 95 .41 95 .08 95 .8 1 Sample 92 Code g14 92 g15 92 916 92 g1 7 92 92 89 918 919 sh4 89 shS 89 89 89 89 89 i t 1 1 st14 sh24 1h29 b 1o32 5102 75 . 78 76.01 75 .65 7 5 . 59 75 .08 75 .99 75 .59 75 . 16 74 .02 73 .97 75 . 59 73 .33 65 . 26 A 1 2o3 1 1 . 31 1 1 . 37 1 1 .40 1 1 .47 1 1 . 38 1 1 . 38 1 2 . 13 1 1 . 70 1 1 . 39 1 1 .42 1 2 . 1 1 1 2 . 75 1 5 . 6 1 Ti02 0 .00 0 . 1 1 0 . 10 0 . 1 0 0 . 1 1 0 . 1 7 0 . 14 0 .00 0.49 0 . 1 2 0 . 10 0 . 1 3 0 . 97 reo* 1 . 33 1 .04 1 . 07 1 . 26 1 .04 0.85 1 . 22 1 . 23 1 . 76 1 . 1 1 1 . 21 1 . 16 3 . 39 MnO 0.00 0 .00 0.00 0 .00 0.00 0.00 0.00 0 .00 0 .00 0 .00 0.00 0 . 1 1 0.00 MgO 0. 14 0 . 1 1 0 .12 0 . 1 1 0.08 0.15 0 . 10 0 . 12 0 . 12 0. 1 1 0 . 12 0 . 1 7 1 . 14 CaD 1 .00 1 .08 1 .07 0 .98 0.97 0.92 1 . 1 1 1 . 18 0 .96 1 .06 1 . 02 1 . 10 3 . 39 NazO 3 . 4 1 3 . 19 3.61 3 . 4 1 3 . 35 3 . 36 3 . 19 3 . 40 2 . 97 2 . 53 3 . 37 3 . 2 1 5 . 16 K20 3.08 2 . 74 2 .90 2 . 72 3 . 1 7 3 .60 2 .75 2 . 98 2 .82 2 . 95 2 .83 2 . 79 1 .88 C l 0 . 16 0 . 1 6 0 . 1 2 0 . 16 0 . 14 0 . 1 3 0.09 0 .00 0.08 0 .00 0 .09 0 . 10 0 .08 Total 96 . 2 1 95 .81 96 .04 95 .80 95 .32 96.55 96.32 95 . 77 94 . 6 1 93 . 33 96 .44 94 .85 96 .88 5.-ple 89 89 89 Code bio39 b io39 so40 89 9 89 9 89 9 89 89 g g 89 89 9 g 89 9 89 9 89 9 Si02 58.67 58.85 73 .34 73 . 75 73 . 73 73 .62 74.82 74 .43 74 . 59 73 .88 73.82 73.89 74 . 4 1 A lz03 1 5.82 1 5 .38 1 1 . 52 1 1 .54 1 1 .85 1 1 .66 1 1 .66 1 1 .84 1 1 .38 1 1 .58 1 1 .37 1 1 . 54 1 2 .04 Ti02 0.98 1 .00 0 . 1 3 0 .07 0 . 1 3 0 . 16 0 .00 0.20 0 . 13 0 . 1 5 0 . 1 1 0 .00 0 . 1 3 FeO* 6 . 12 5 . 79 1 .49 1 . 14 1 . 18 1 . 14 1 . 19 1 .24 1 . 14 1 . 25 1 .05 1 . 18 1 . 15 MnO 0.00 0.00 0.09 0.09 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0 .00 0 .00 MgO 2 .02 2 . 19 0 . 1 1 0. 1 1 0 .09 0 . 1 7 0 . 1 3 0 . 1 3 0 . 1 3 0 . 1 3 0 .09 0 . 14 0 . 1 3 c.o 5 .05 5 . 23 0.99 0.98 1 .05 1 . 13 1 . 18 1 .20 1 .00 1 .01 0.88 1 .09 1 .08 NazO 3 .56 3 .67 3 .05 2 .56 3.01 3.39 3.41 3.46 3 . 1 9 3 . 35 2.94 3 .00 3.40 KzO 1 .98 1 .81 2.87 2 . 76 2 . 57 2.66 2.93 2.69 2 .83 2 . 71 2 .89 2 . 78 2 . 72 Cl 0 . 1 3 0.08 0. 1 1 0 . 1 1 0.07 0 . 11 0.13 0.08 0 .09 0 . 1 2 0.07 0 . 12 0 . 1 1 Total 94 .33 94 .00 93. 70 93. 1 1 93 .68 94. 10 95.45 95.27 94.48 94. 18 93.22 93 . 74 95 . 1 7 2 5 1 APP ENDIX 7 . 1 : Con t inued . 89 89 89 89 89 89 90 90 9 9 9 9 9 9 i h 1 sh7 90 90 90 sh 10 g g 2 5 2 Samp l e Code S i 02 74 . S2 73 . 62 74 .28 7 5 . 16 7 3 . 83 74 .00 7 1 . 1 4 72 . 8 1 7 3 . 4 3 7 3 . 49 73 . 14 A l 2o3 1 1 . 44 1 1 .48 1 1 . 7 1 1 1 . 50 1 1 . 50 1 1 . 55 1 1 .45 1 1 . 6 1 1 1 . 66 1 1 . 4 9 1 1 . 38 T i 02 0 . 00 0 . 1 1 0 . 08 0 . 1 2 0 . 14 0 . 1 1 0 . 24 0 . 1 3 0 . 2 1 0 . 1 5 0 . 1 0 F eo• o . 95 1 . 26 1 . 20 1 . 03 1 . 03 1 . 11 2. 19 1 . 04 1 . 26 1 . 09 1 . 09 HnO 0 . 1 2 0 . 00 0 . 00 0 . 00 0 . 00 0 .00 0 . 10 0 . 00 0 . 00 0 .00 0 . 00 HgO 0 . 1 1 0 . 1 3 0 . 1 3 0 . 1 3 0 . 1 0 0 . 1 1 0 . 58 0 . 0 9 0 . 0 9 0 . 0 9 0 . 1 5 CaO 0 . 95 1 . 1 1 1 . 05 0 . 99 1 . 07 0 . 98 1 . 49 0 . 95 0 . 94 1 . 02 1 . 03 Na2o 3 . 14. 3 . 06 3 . 22 3 . 39 2 . 92 3 . 27 3 . 2 1 3 . 52 3 . 42 2 . 94 3 . 33 K20 2 . 80 2 . 46 2 . 62 2 . 95 2 . 73 2 . 93 3 . 1 8 2 . 72 2 . 83 2 . 93 2 . 87 C l 0 . 10 0 . 1 2 0 . 1 5 0 . 1 2 0 . 1 2 0 . 10 0 . 1 1 0 . 1 5 0 . 07 0 . 08 0 . 1 1 Tot a l 94 . 1 3 93 . 35 94 . 44 95 .39 93 . 44 94 . 1 6 93 .69 93 . 02 93 . 9 1 93 . 29 93 . 20 Samp le Code 90 g 90 g 90 g 90 g 90 g 90 g 90 g 90 9 90 g 90 g 90 sol l S i 02 74 . 46 73 . 39 7 4 . 6 1 74 . 91 72 . 86 74 . 26 7 3 . 16 73 . 70 73 . 25 7 2 . 84 74 .40 A l 203 1 1 . 64 1 1 . 62 1 1 .49 1 1 . 37 1 1 . 74 1 1 . 5 1 1 1 . 5 7 1 1 . 64 1 1 . 63 1 1 . 85 1 1 .55 T i 02 0 . 1 1 0 . 12 0 . 1 3 0 . 1 1 0 . 1 7 0 . 09 0 . 12 0 . 1 5 0 . 1 0 0 . 1 0 0 . 1 5 reo• 1 . 05 1 . 07 1 . 08 1 . 1 7 1 . 19 1 . 1 2 1 . 1 2 1 . 06 1 . 09 1 . 07 1 . 27 MnO 0 . 00 0 .00 0 . 09 0 . 00 0 . 00 0 . 00 0 .00 0 . 00 0 . 00 0 . 00 0 .00 MgO 0 . 10 0 . 1 4 0 . 1 3 0 . 09 0 . 1 4 0 . 1 1 0 . 1 1 0 . 12 0 . 1 2 0 . 10 0 . 14 CaD 0 . 98 0 . 90 1 .06 1 . 00 1 . 0 1 0 . 94 1 . 02 0 . 95 1 . 10 1 . 05 1 . 02 Na2o 3 . 30 3 . 46 3 . 25 2 . 93 3 . 4 1 3 . 39 3 . 34 3 . 4 7 2 . 93 3 . 34 3 . 38 K20 2 . 8 1 3 . 0 1 2 . 73 2 . 96 2 . 79 3 . 07 2 . 63 2 . 97 2 . 88 2 . 66 2 . 43 ' C l 0 .00 0 . 1 1 0 . 00 0 . 09 0 . 08 0 . 09 0 . 00 0 . 10 0 . 09 0 . 09 0 .09 Tot a l 94 .45 93 . 82 94 . 5 7 94 .63 93 . 39 94 . 58 93 . 07 94 . 1 6 93 . 1 9 93 . 10 94 .43 Samp l e Code 90 90 90 90 90 90 90 90 90 io 12 st 15 sh 19 io20 io21 io22 i o23 i o23 sh27 90 i h S i 02 7 3 . 24 7 4 . 23 7 3 . 64 7 1 . 22 72 . 72 7 2 . 40 72 . 30 77 . 33 7 3 . 6 1 7 1 . 23 A l 203 1 1 . 66 1 1 . 56 1 1 . 57 1 2 . 88 1 1 . 75 1 1 . 7 1 1 1 . 70 1 1 .40 1 1 . 39 1 2 .84 T i 02 0 . 16 0 . 16 0 . 1 0 0 . 1 7 0 . 1 5 0 . 20 0 . 1 7 0 . 1 5 0 . 10 0 . 08 reo* 1 . 69 1 . 24 1 . 22 1 . 92 1 . 27 1 . 66 1 . 56 1 . 4 7 1 . 1 9 1 . 28 MnO 0 .00 0 . 00 0 .00 0 . 10 0 .00 0 .00 0 .00 0 . 00 0 .00 0 .00 MgO 0 . 1 3 0 . 1 1 0 . 1 3 0 . 1 5 0 . 1 5 0 . 1 2 0 . 14 0 . 1 3 0 . 1 3 0 . 1 9 CaO 0 . 99 0 . 99 1 .03 1 . 36 1 . 1 7 1 . 05 0 .95 0 . 89 1 . 04 0 . 90 Na20 3 . 39 3 . 35 3 . 12 3 . 03 2 . 96 7 . 8 7 2 . 92 2 . 9 1 2 . 99 3 . 49 K20 2 . 79 2 . 97 2 . 98 2 . 70 2 . 82 2 . 99 3 . 65 3 . 78 2 . 69 3 . 60 C l 0 . 1 1 0 . 1 2 0 . 73 0 . 00 0 . 1 2 0 .00 0 .00 0 . 09 0 . 08 0 . 09 Tota l 94 . 16 94 . 73 94 .02 9 3 . 53 93 . 1 1 9 3 .00 93 . 39 93. 15 9 3 . 22 93 . 70 APPENDIX 7 . 2 t AMPHIBOLES Sample MnP MnP MnP MnP MnP MnP MnP MnP MnP MnP MnP Mnl Code 1 f 1 26 27 2 - 1 3 14 31 a28 a29 a30 7 Mnl 10 Mnl 9 I L 1 I L 2 I L 10 I L 1 1 I L 1 2 I L 1 3 S i02 40 . 5 1 38 .86 39 .08 40 . 14 39 .45 40 . 27 39 . 85 40 . 04 40 . 30 39 . 99 39 . 7 7 40 .88 39 . 93 39 . 90 42 . 90 43 . 39 42 . 38 43 . 1 5 4 3 . 1 0 44 . 46 Al2o3 1 3 . 62 14 .06 14 . 63 1 3 . 37 14 . 74 1 3 . 14 1 4 . 59 1 3 .8 1 1 3 .65 1 4 . 19 1 4 . 25 1 4 . 02 1 4 . 14 1 4 . 68 1 0 . 67 1 0 . 00 1 1 . 4 1 1 0 . 75 1 0 . 88 9 . 83 T i02 1 . 57 2 . 66 2 .41 2 .69 2 . 30 2 . 70 2 . 33 2 . 10 2 . 55 2 . 1 0 2 . 35 2 . 79 2 . 82 2 . 30 3 . 1 1 2 . 9 1 2 . 79 3 .40 2 . 97 2 . 85 reo• 9 . 20 1 2 . 58 1 1 . 53 1 1 .83 1 1 . 03 1 2 . 05 1 1 . 1 7 9 . 75 1 1 .42 10 .08 1 1 . 10 10 .48 1 0 . 56 10 .82 1 2 . 93 1 2 . 64 1 3 . 70 1 0 . 93 1 2 . 55 1 1 . 69 MnO 0 . 10 0 . 22 0 . 1 2 0 . 2 1 0 . 14 0 . 20 0 . 00 0 . 00 0 . 1 7 0 . 00 0 . 00 0 . 00 0 . 00 0 . 00 0 . 4 7 . 0 . 50 0 .45 0 .29 0 . 39 0 . 4 1 MgO 1 6 . 31 1 2 .84 1 3 . 97 1 3 . 62 1 3 . 95 1 3 . 78 1 3 . 82 1 5 . 1 1 1 3 . 60 14 .43 1 3 . 59 14 . 38 14 . 37 1 3 . 77 1 3 . 04 1 3 . 65 1 2 . 6 7 14 . 4 1 1 3 .48 1 4 . 20 CaO 1 1 .45 1 2 . 2 1 12 .42 1 2 . 19 1 2 . 49 1 2 . 13 1 2 . 31 1 2 . 35 1 2 .06 1 2 . 27 1 2 . 22 1 2 . 06 1 1 .89 1 2 . 3 1 1 1 . 52 1 1 . 54 1 1 .49 1 1 . 54 1 1 . 93 1 1 .80 Na2o 2 . 58 2 . 49 2 . 30 2 .49 2 . 38 2 . 48 2 . 34 2 . 18 2 .42 2 . 16 2 . 24 2 . 53 2 .46 2 . 39 2 . 39 2 . 38 2 . 5 1 2 . 56 2 . 38 2 . 28 K2o 0 . 92 0 . 93 1 .00 0 . 94 0 . 88 0 . 94 0 . 93 1 . 19 0 . 90 1 . 12 0 . 94 0 . 93 0 .89 1 .00 1 . 1 7 0 .87 1 .07 0 . 83 1 .00 0 . 93 Total 96 . 26 96 . 85 97 . 46 97 .48 9 7 . 36 97 . 69 97 . 34 96 . 53 97 .07 96 . 34 96 .46 98 . 07 9 7 . 06 97 . 1 7 98 . 20 97 .88 98 .47 97 .86 98 . 68 98 .45 Cat i ons on the bas i s of 23 oxygens S1 6 . 040 5 . 860 5 . 822 5 .979 5 . 861 5 . 990 5 . 914 5 . 963 6 . 004 5 . 968 5 . 952 5 . 992 5 . 923 5 . 923 6 . 350 6 .422 6 . 277 6 . 335 6 . 332 6 . 500 Al 2 . 370 2 .499 2 . 569 2 . 347 2 . 581 2 . 304 2 . 552 2 . 424 2 . 397 2 . 496 2 . 5 14 2 .422 2 .472 2 . 568 1 .861 1 . 744 1 . 992 1 .860 1 .884 1 . 694 Ti 0 . 1 77 0 . 302 0 . 270 0 , 301 0 . 257 0 . 302 0 . 260 0 . 235 0 . 286 0 . 236 0 . 265 0 . 308 0 . 3 1 5 0 . 257 0 . 346 0 . 324 0 . 3 1 1 0 . 375 0 . 328 0 . 3 1 3 Fe 1 . 1 28 1 . 587 1 . 437 1 .474 1 . 371 1 . 499 1 . 386 1 . 2 14 1 .423 1 . 258 1 . 389 1 . 285 1 . 3 1 0 1 . 343 1 . 60 1 1 . 565 1 . 697 1 . 342 1 . 542 1 . 429 Mn 0 . 012 0 .028 0 .0 15 0 . 026 0 . 018 0 . 025 0 . 000 0 . 000 0 .021 0 . 000 0 .000 0 .000 0 .000 0 . 000 0 . 059 0 . 063 0 . 056 0 . 036 0 .049 0 . 05 1 Mg 3 . 598 2 . 886 3 . 102 3 . 024 3 . 089 3 . 055 3 . 056 · 3 . 354 3 . 020 3 . 209 3 .031 3 . 14 1 3 . 1 77 3 .047 2 .876 3 . 0 1 1 2 . 797 3 . 1 53 2 .952 3 . 094 ea 1 .822 1 . 973 1 .983 1 . 946 1 . 988 1 . 933 1 . 957 1 . 971 1 . 925 1 . 962 1 . 960 1 .894 1 .890 1 . 958 1 .827 1 .830 1 .824 1 .8 1 5 1 .878 1 .848 Na 0 . 750 0 . 728 0 . 664 0 . 7 19 0 . 686 0 . 7 1 5 0 . 673 0 . 630 0 . 699 0 . 625 0 . 650 0 . 71 9 0 . 708 0 .688 0 . 686 0 . 683 0 . 72 1 0 . 729 0 . 6 78 0 . 646 K 0 . 1 76 0 . 1 79 0 . 190 0 . 1 79 0 . 167 0 . 1 78 0 . 1 76 0 . 226 0 . 1 7 1 0 . 2 1 3 0 . 1 79 0 . 1 74 0 . 1 68 0 . 189 0 . 22 1 0 . 164 0 . 202 0 . 155 0 . 187 0 . 1 73 Mg No. 0 . 761 0 . 64 1 0 . 681 0 . 668 0 . 690 0 . 667 0 .688 0 . 734 0 . 676 0 . 7 18 0 . 686 0 . 7 10 0 . 708 0 . 694 0 . 634 0 . 649 0 . 6 1 5 0 . 696 0 .650 0 . 676 N U1 w APPENDIX 7 . 2 : Continued. Sample IL Code 15 IL 16 IL 17 IL 18 222 K6 222 Z6 222 Z6 222 Z6 222 Z6 222 R6 222 7 222 8 222 9 222 K 10 222 Z 10 222 Z 10 222 R 10 222 1 1 222 25 s 1o2 43 . 78 42 . 68 4 1 .42 44 .27 43 . 76 4 1 . 84 43 . 30 42 . 29 46 .06 43 . 40 40 . 79 4 3 . 30 43 . 1 3 43 .39 42 .67 43 . 57 43 . 5 5 41 . 38 41 . 40 A 12o3 10 . 2 1 1 1 .48 1 2 . 7 7 9 .43 9 . 87 1 1 . 10 9 . 7 1 10 .86 8 . 50 10 . 1 1 1 2 . 36 1 0 . 35 1 0 . 36 1 0 . 33 . 10 .97 1 0 . 28 9 . 88 1 3 . 14 1 1 . 78 1 102 3 . 1 7 2 .96 2 . 53 3 . 20 2 . 88 3 . 32 2 . 93 3 . 16 2 . 1 5 3 . 36 3 . 05 3 . 37 3 . 5o 2 . 93 3 .47 3 . 32 3 . 34 2 . o8 3 . 59 Feo* 1 2 . 09 13 . 02 1 3 . 16 1 1 . 6 1 1 1 . 38 1 2 . 55 1 1 . 66 1 2 . 2 1 1 0 . 96 1 1 . 7 1 1 1 . 95 1 1 . 58 1 1 . 52 1 1 . 55 1 1 . 48 1 1 . 1 6 1 1 . 4 1 9 . 88 1 1 . 75 MnO 0 . 4 1 0 . 33 0 . 32 0 . 00 0 . 44 0 . 45 0 . 34 0 . 55 0 . 36 0 . 48 0 . 36 0 . 29 0 . 29 0 . 27 0 . 39 0 . 3 1 0 . 38 0 . 00 0 . 31 MgO 14 . 14 1 3 . 56 1 2 . 45 14 .42 1 4 . 66 1 3 . 38 14 . 32 1 3 . 30 1 5 . 57 1 4 . 1 2 1 3 . 3 7 14 . 42 1 4 . 08 1 4 . 62 14 . 1 3 1 4 . 59 14 . 35 1 5 . 20 1 3 . 73 CaO 1 1 . 59 1 1 . 42 1 1 . 82 1 1 .08 1 1 . 52 1 1 . 5 7 1 1 . 42 1 1 . 60 1 1 . 50 1 1 . 42 1 1 .90 1 1 . 5 1 1 1 .25 1 1 . 58 1 1 . 6 1 1 1 . 59 1 1 . 40 1 2 . 18 1 1 . 64 Na2o 2 . 42 2 . 37 2 . 57 2 . 4 1 2 . 39 2 . 49 2 .40 2 . 4 1 2 . 10 2 . 41 2 .40 2 . 45 2 . 40 2 . 40 2 . 52 2 . 54 2 . 50 2 . 47 2 . 54 K20 0 . 93 1 .01 0 . 93 0 . 1 9 0 . 86 0 . 95 0 .85 0 . 93 0 . 76 0 . 90 0 .83 0 . 93 0 . 91 0 .85 0 .9 1 0 . 90 0 .88 1 . 1 1 0 . 94 Total 98 . 74 98 .83 97 .97 96 . 6 1 97 . 76 97 .65 96 . 93 97 . 3 1 97 .96 97 .91 97 .01 98 . 20 97 . 44 97 . 92 98 . 1 5 98 .26 97 . 69 97 . 44 97 . 68 Cat 1 ons on the bas i s of 23 oxygens 5 1 6 . 403 6 . 266 6 . 1 54 6 . 546 6 . 44 1 6 . 227 6 . 439 6 . 300 6 . 709 6 . 394 6 .098 6 . 356 6 . 373 6 . 38 1 6 . 275 6 . 379 6 . 4 1 9 6 . 093 6 . 1 39 Al 1 . 760 1 . 986 2 . 236 1 . 643 1 . 7 12 1 . 947 1 . 702 1 . 907 1 . 459 1 . 755 2 . 1 78 1 . 79 1 1 .804 1 . 790 1 . 901 1 . 774 1 . 7 16 2 . 280 2 . 059 Tl 0 . 349 0 . 327 0 . 283 0 . 356 0 . 3 19 0 . 372 0 . 328 0 . 354 0 . 236 0 . 372 0 . 343 0 . 372 0 . 389 0 . 324 0 . 384 0 . 366 0 . 370 0 . 230 0 . 400 Fe 1 . 479 1 . 599 1 . 635 1 . 436 1 . 401 1 . 562 1 . 450 1 . 521 1 . 335 1 . 443 1 . 494 1 . 422 1 . 424 1 . 420 1 . 4 1 2 1 . 366 1 . 407 1 . 2 1 7 1 . 457 Mn 0 .051 0 . 04 1 0 . 040 0 . 000 0 . 055 0 . 05 7 0 . 043 0 .069 0 . 044 0 . 060 0 .046 0 . 036 0 . 036 0 . 034 0 . 049 0 . 038 0 .047 0 . 000 0 . 039 Mg 3 . 082 2 . 967 2 . 757 3 . 1 78 3 . 216 2 . 968 3 . 1 74 2 . 953 3 . 380 3 . 100 2 . 979 3 . 155 3 . 100 3 . 204 3 .097 3 . 183 3 . 1 52 3 . 336 3 . 034 ea 1 .8 16 1 . 796 1 . 882 1 . 755 1 .8 1 7 1 . 845 1 .820 1 .852 1 . 795 1 .803 1 . 906 1 .810 1 . 781 1 . 825 1 . 829 1 .818 1 . 800 1 . 922 1 . 849 Na 0 . 686 0 .675 0 . 740 0 . 691 0 . 682 0 . 7 1 9 0 . 692 0 . 696 0 . 593 0 . 688 0 . 696 0 . 697 0 . 688 0 . 684 0 . 7 19 0 . 721 0 . 7 1 5 0 . 705 0 . 730 K 0 . 1 74 0 . 189 0 . 1 76 0 . 036 0 . 162 0 . 180 0 . 161 0 . 1 77 0 . 14 1 0 . 169 0 . 1 58 0 . 1 74 0 . 1 72 0 . 159 0 . 1 7 1 0 . 168 0 . 1 65 0 . 209 0 . 1 78 Mg No . 0 . 668 0 . 644 0 . 622 0 . 689 0 . 688 0 . 647 0 . 680 0 . 650 0 . 7 10 0 . 674 0 .659 0 . 684 0 . 680 0 . 688 0 . 680 0 . 694 0 . 684 0 . 733 0 . 670 N LT1 "" APPENDIX 7 . 2 : Continued . Samp le 228u 228u 228u 228u 228u 228m 228m 228m 228m 228m 228m 228l 228L 228l 22�l 228l 228l 228l 228L Code 33 37 31 38 39 2 12 13 14 1 5 . 21 22 i c4 24 25 26 27 28 K29 s1o2 41 . 79 43 .6� 42 . 99 40 . 9o 42 . 19 40 .02 42 . 42 42 . 09 39 . 33 43 . 5 1 40 . 1 1 43 .83 40 .60 44 . 1 3 40 . 44 42 .63 41 . 75 41 . 70 41 . 26 A 1 2o3 1 1 . 72 9 . 72 10 . 50 1 2 . 8 7 1 1 . 52 14 . 14 1 0 . 6 1 10 .47 1 3 .62 1 0 . 24 1 3 . 42 9 . 7 1 1 2 .03 9 . 09 1 3 . 23 10 .65 1 1 . 44 1 1 . 00 1 1 .82 r1o2 3 . 04 3 . 10 3 . 79 2 . 98 2 .09 2 . 42 3 .4 7 2 . 5 1 2 . 78 2 .89 2 . 55 2 . 35 3 . 1 7 2 .83 2 . 73 3 . 38 2 . 93 3 .42 2 . 95 Feo* 1 2 . 62 1 1 . 66 1 0 . 94 1 1 . 55 9 . 85 1 3 . 03 1 2 . 1 2 1 3 . 44 1 2 . 74 1 1 . 14 1 2 . 28 1 2 . 5 7 1 1 . 84 1 1 . 25 1 1 . 76 1 1 . 48 1 1 . 79 1 1 . 05 1 2 . 22 MnO 0 . 28 0 . 37 0 .33 0 . 21 0 . 1 3 0 . 1 5 0 . 39 0 . 34 0 . 26 0 . 34 0 . 18 0 . 42 0 . 43 0 . 50 0 . 21 0 . 28 0 . 36 0 . 3 7 0 . 36 MgO 1 3 . 59 1 4 . 46 1 4 . 60 1 3 . 28 1 5 . 35 1 2 . 9 1 1 3 . 9 1 1 2 . 08 1 2 .43 1 4 . 74 1 3 . 20 1 3 . 23 1 3 . 65 1 5 . 03 1 3 .45 14 . 48 1 4 . 1 6 1 4 . 70 1 4 . 06 CaO 1 1 . 7 5 1 1 .44 1 1 . 60 1 1 . 97 1 2 . 08 1 2 . 0 1 1 1 . 08 1 1 .45 1 2 . 2 1 1 1 . 39 1 1 . 76 1 1 . 4 7 1 1 . 75 1 1 . 4 7 1 1 . 78 1 1 . 59 1 1 . 7 5 1 1 . 38 1 1 . 78 Na20 2 . 62 2 . 3 1 2 . 67 2 . 50 2 . 5 1 2 . 34 2 . 43 2 .04 2 . 37 2 . 39 2 .40 2 . 14 2 . 58 2 . 29 2 . 52 2 . 55 2 . 49 2 . 43 2 .46 K20 0.85 0 . 93 0 .95 0 . 97 1 . 09 0 . 9 1 0 . 96 1 . 05 1 . 01 0 .89 0 .89 0 . 94 1 .01 0 . 83 0 . 90 0 . 96 0 . 92 0 . 98 0 . 94 Total 98 . 26 9 7 . 78 98 . 3 7 97 .23 96 . 8 1 97 . 93 97 . 39 95 .47 96 . 75 97 . 53 96 . 79 96 . 66 97 . 06 97 . 42 9 7 . 02 98 . 00 97 . 59 97 .03 97 .85 Cat ions on the bas i s of 23 oxygens S i 6 . 1 78 6 . 444 6 . 296 6 . 087 6 . 253 5 . 95 1 6 . 300 6 . 4 1 5 5 . 938 6 .409 6 .0 1 5 6 . 550 6 . 080 6 . 51 2 6 .037 6 . 28 1 6 . 195 6 . 203 6 . 1 25 A l 2 . 042 1 . 690 1 .8 12 2 . 258 2 .012 2 .478 1 . 857 1 . 88 1 2 .423 1 . 7 78 2 . 372 1 . 71 0 2 . 1 23 1 . 58 1 2 . 328 1 . 849 2 .001 1 . 928 2 .068 ·r1 0 . 338 0 . 344 0 . 4 1 7 o . 334 0 . 233 0 . 211 0 . 388 o . 288 0 . 31 6 0 . 320 0 . 288 0 . 264 0 . 357 0 . 3 14 o . 306 0 . 375 0 . 327 0 . 383 o . 329 Fe 1 . 560 1 . 438 1 . 340 1 . 438 1 . 221 1 . 621 1 . 505 1 . 7 1 3 1 . 609 1 . 3 72 1 . 540 1 . 5 7 1 1 . 483 1 . 388 1 . 468 1 . 4 1 5 1 . 463 1 . 375 1 . 5 1 7 Mn 0 .035 0 .046 0 . 041 0 . 026 0 . 0 16 0 .0 19 0 . 049 0 . 044 0 . 033 0 . 042 0 . 023 0 . 053 0 . 055 0 . 062 0 . 027 0 . 035 0 . 045 0 . 047 0 . 045 Mg 2 . 994 3 . 179 3 . 186 2 . 946 3 . 390 2 . 86 1 3 . 079 2 . 744 2 . 797 3 . 236 2 . 950 2 . 946 3 . 046 3 . 305 2 . 992 3 . 1 80 3 . 1 32 3 . 259 3 . 1 10 Ca 1 . 86 1 1 . 808 1 . 820 1 . 909 1 . 9 18 1 . 914 1 . 763 1 . 870 1 . 975 1 . 798 1 . 890 1 .837 1 . 885 1 . 814 1 . 884 1 . 830 1 . 868 1 . 8 14 1 . 874 Na 0 . 75 1 0 . 661 0 . 758 0 . 72 1 0 . 721 0 . 675 0 . 700 0 . 603 0 . 694 0 .683 0 . 698 0 . 620 0 . 749 0 . 655 0 . 729 0 . 729 0 . 7 1 6 0 . 701 0 . 708 K 0 . 1 60 0 . 1 75 0 . 1 77 0 . 184 0 . 206 0 . 1 73 0 . 182 0 . 204 0 . 195 0 . 167 0 . 1 70 0 . 1 79 0 . 1 93 0 . 1 56 0 . 1 7 1 0 . 180 0 . 1 74 0 . 186 0 . 1 78 Mg No . 0 . 652 0 . 682 0 . 698 0 . 668 0 . 733 0 .636 0 . 665 0 . 6 10 0 . 630 0 . 696 0 . 654 0 .645 0 . 665 0 . 695 0 . 667 0 . 687 0 . 675 0 . 696 0 . 666 IV (.J1 (.J1 APPENDIX 7 . 2 : Con t inued . Sample 228l 228l 228L 228l 228L 235 Code Z29 Z29 Z29 1 2 1 235 2 235 3 235 235 4 ' 5 235 6 235 9 235 10 243 14 243 15 243 16 243 1 3 s 1o2 41 . 56 41 .93 4 1 .9 1 39 . 7 1 39 .89 43 . 24 42 . 79 40 . 16 4 1 . 70 42 . 79 4 2 . 8 7 42 . 18 42 .68 4 3 . 0 1 42 . 16 42 . 73 43 . 10 A 1 2o3 1 1 . 75 10 .95 10 .97 1 3 . 70 1 3 . 70 10 . 24 1 0 . 73 1 3 .29 1 1 . 38 1 1 . 1 4 1 0 . 42 1 0 . 92 10 .45 1 0 . 54 1 1 . 1 1 1 1 . 3 1 1 1 . 08 r1o2 2 . 97 3 . 22 3 . 30 2 .85 2 . 6 1 3 . 35 3 . 16 2 . 38 2 . 79 3 . 02 3 . 05 2 .88 3 . 44 3 .07 3 . 82 3 .45 3 . 82 Feo* 1 1 . 52 10 .90 1 1 . 91 1 2 .05 1 1 .92 10 .98 1 1 .95 12 .06 12 .03 1 1 . 58 1 0 . 82 1 1 .43 1 1 . 10 12 .37 10 .91 1 1 .04 10 . 52 MnO 0 . 35 0 . 24 0 . 40 0 . 1 9 0 .00 0 . 38 0 . 38 0 . 1 7 0 . 24 0 . 39 0 . 29 0 . 3 1 0 . 34 0 . 34 0 . 28 0 . 24 0 . 32 M90 1 3 .87 1 4 . 58 1 3 . 72 1 3 . 42 1 3 . 54 1 5 .07 14 . 33 13 . 32 1 3 . 95 1 4 . 32 1 4 . 29 1 4 . 36 14 . 76 1 3 . 62 14 . 1 3 1 4 . 54 1 4 . 87 CaO 1 1 . 75 1 1 . 84 1 1 . 56 1 1 . 93 1 2 . 23 1 1 .44 1 1 .44 1 1 . 99 1 1 .83 1 1 . 53 1 1 . 30 1 1 . 77 1 1 . 5 1 1 1 .46 1 1 . 36 1 1 . 58 1 1 . 46 Na2o 2 . 47 2 . 48 2 . 48 2 . 5 7 2 . 5 7 2 . 48 2 .39 2 . 33 2 . 39 2 .4 1 2 . 30 2 . 4 7 2 . 38 2 . 36 2 . 5 7 2 . 4 7 2 . 5 7 K20 0 .98 0 .9 1 0 . 96 0 . 94 0 . 94 0 . 91 0 . 86 0 .89 0 . 82 0 .84 0 .82 0 . 7 7 0 .83 1 . 19 1 .01 0 . 94 0 . 96 Tota l 97 . 22 97 .05 97 . 2 1 97 . 36 97 .40 98 .09 98 .03 96 . 59 97 . 1 3 98 .02 96 . 16 97 .09 97 .49 9 7 . 96 97 . 35 98 . 30 98 . 70 Cat ions on the bas i s of 23 oxy9ens 5 1 6 . 184 6 .231 6 .246 5 . 929 5 . 947 6 . 341 6 . 305 6 .031 6 . 2 16 6 . 293 6 . 394 6 . 270 6 . 303 6 . 360 6 . 238 6 . 254 6 . 268 Al 2 .061 1 . 918 1 . 927 2 . 4 1 1 2 .407 1 . 7 70 1 . 863 2 . 352 1 . 999 1 . 931 1 . 832 1 . 9 13 1 .8 19 1 . 837 1 . 938 1 . 951 1 . 899 Tf . 0 . 332 0 . 360 0 . 370 0 . 320 0 . 293 0 . 369 0 . 350 0 . 269 0 . 3 1 3 0 . 334 0 . 342 0 . 322 0 . 382 0 . 341 0 . 425 0 . 380 0 . 4 18 Fe 1 . 434 1 . 355 1 . 484 1 . 505 1 . 486 1 . 347 1 . 473 1 . 5 15 1 . 500 1 . 424 1 . 350 1 . 421 1 . 3 7 1 1 . 530 1 . 350 1 . 351 1 . 280 Mn 0 . 044 0 . 030 0 .050 0 . 024 0. 000 0 .047 0 .047 0 . 022 0 .030 0 . 049 0 .037 0 . 039 0 . 043 0 . 043 0 .035 0 . 030 0 . 039 M9 3 .076 3 . 229 3 .047 2 . 986 3 . 008 3 . 294 3 . 147 2 . 981 3 . 099 3 . 1 38 3 . 1 76 3 . 181 3 . 248 3 .002 3 . 1 16 3 . 1 7 1 3 . 223 ea 1 . 873 1 . 885 1 . 846 1 . 909 1 . 954 1 . 798 1 . 806 1 . 929 1 . 890 1 . 81 7 1 . 806 1 . 875 1 . 821 1 . 8 16 1 . 801 1 . 8 16 1 . 786 Na 0 . 7 1 3 0 . 7 15 0 . 7 1 7 0 . 744 0 . 743 0 . 705 0 . 683 0 . 678 0 . 691 0 . 687 0 . 665 0 . 7 1 2 0 . 68 1 0 . 677 0 . 737 0 . 701 0 . 725 K 0 . 186 0 . 1 73 0 . 183 0 . 1 79 0 . 1 79 0 . 1 70 0 . 1 62 0 . 1 7 1 0 . 156 0 . 1 58 0 . 1 56 0 . 1 46 0 . 1 56 0 . 225 0 . 19 1 0 . 1 76 0 . 1 78 M9 No . 0 . 675 0 . 700 0 . 665 0 . 66 1 0 . 669 0 . 703 0 . 674 0 . 660 0 . 669 0 . 68 1 0 . 696 0 . 685 0 . 697 0 . 656 0 . 692 0 .697 0 . 7 10 rv U1 0\ APPENDIX 7 . 2 : Continued . Samp le 246 Code 23 246 1 5 246 16 246 246 246 1 7 df27 df27 251 33 251 34 251 35 251 36 251 37 256 18 256 19 256 20 256 2 1 256 23 256 25 256 256 25 df31 256 e32 s io2 42 . 75 42.33 42.49 42.64 40 . 84 40.23 40 . 37 42 .45 39 . 98 40 . 70 40 . 72 4 1 . 2 7 42 . 1 1 40.44 4 1 .28 42 . 02 4 1 . 24 4 1 . 50 41 . 55 42 .26 A 12o3 1 1 .08 1 2 . 20 1 1 . 3 1 1 0 . 92 1 3 . 7 1 1 3 . 95 14 . 1 3 1 1 . 1 4 1 3 . 54 1 3 . 72 1 2 . 9 1 1 1 .49 1 1 .82 1 4 . 50 1 3 .26 1 1 . 59 1 2 . 96 1 2 . 66 1 3 . 35 1 1 . 38 Tio2 3 . 7o 2 . 56 3 . 74 3 . 83 2 . 5o 2 . 16 2 . 75 3 .66 2 .66 2 . 75 2 . 83 3 . 76 3 . 8 7 2 . 16 2 .45 3 . 9o 2 . 1 1 2 . 59 2 . 34 3 . 57 Feo* 1 1 . 83 1 1 .46 1 1 . 33 1 1 .22 10 .44 10 . 4 1 1 1 .63 1 1 .0 1 1 1 . 2 1 1 1 . 58 1 1 . 38 1 2 .01 1 1 .44 10 . 5 1 1 2 . 85 1 1 . 79 1 2 . 76 1 2 . 29 9 . 66 1 1 . 16 MnO 0 . 29 0 . 1 6 0 . 22 0 . 28 0 . 1 4 0 . 14 0 . 1 3 0 . 2 7 0 . 00 0 .00 0 . 18 0 . 20 0 . 1 7 0 . 20 0 . 1 8 0 . 34 0 . 25 0 . 27 0 .00 0 . 26 M90 1 4 . 3 1 1 4 . 5 1 1 4 . 9 1 1 4 . 74 14 .27 1 4 . 5 7 1 4 .0 1 14 .8 1 1 3 .83 1 3 . 66 1 3 . 79 1 3 .87 14 . 33 1 3 .63 1 3 .68 1 3 .87 1 3 . 00 1 3 . 52 1 5 . 23 1 4 . 1 5 CaO 1 1 . 36 1 1 . 76 1 1 . 1 9 1 1 . 3 1 1 1 . 76 1 2 . 22 1 2 . 26 1 1 . 62 1 2 . 20 1 2 . 1 3 1 2 .07 1 1 . 36 1 1 . 4 1 1 1 .83 1 2 . 34 1 1 . 3 7 1 2 . 10 1 1 . 72 1 1 . 40 1 1 . 36 Na2o 2 . 56 2 . 5 7 2 . 6 1 2 . 59 2 . 50 2 .43 2 . 52 2 . 5 7 2 . 27 2 . 43 2 .4 1 2 .62 2 . 71 2 . 36 2 . 38 2 . 75 2 .55 2 . 59 2 . 6 1 2 .66 K20 1 .00 0 . 94 1 . 03 0 . 99 0 . 98 0 . 97 0 .83 0 .88 0 .86 0 . 98 0 . 88 1 .06 0 . 93 0 . 92 0 . 90 0 . 90 0 .9 1 0 . 76 0 . 92 0 . 95 Tota l 98 .88 98 .49 98 .83 98 . 52 97 . 14 9 7 . 08 98 . 63 98 . 4 1 96 .61 97 . 95 97 . 1 7 97 . 70 98 . 79 96 . 55 99.32 98 . 53 98 .48 97 . 90 97 .06 97 . 75 Cations on the bas i s of 23 oxy9ens S i 6 . 246 6 . 197 6 . 199 6 . 239 6 . 043 5 . 970 5 . 926 6 . 2 1 4 5 . 980 6 . 008 6 . 059 6 . 1 31 6 . 1 5 1 6 . 0 1 7 6 . 044 6 . 1 70 6 .090 6 . 1 39 6 . 1 1 3 6 . 230 Al 1 . 908 2 . 105 1 . 945 1 .883 2 . 391 2 . 440 2 . 445 1 . 922 2 . 387 2 . 387 2 . 264 2 .012 2 .035 2 . 543 2 . 288 2 . 006 2 .256 2 . 207 2 . 3 1 5 1 . 977 T i 0 . 407 0 . 282 0 .4 10 0 . 42 1 0 . 278 0 .241 0 . 304 0 . 403 0 . 299 0 . 305 0 .3 1 7 0 .420 0 . 425 0 . 242 0 .270 0 . 431 0 . 301 0 . 288 0 . 259 0 . 396 Fe 1 . 446 1 . 403 1 . 382 1 . 373 1 . 292 1 . 292 1 . 428 1 . 348 1 . 410 1 . 430 1 . 416 1 . 499 1 . 398 1 . 308 1 . 5 74 1 . 448 1 . 576 1 . 520 1 . 189 1 . 376 Mn 0 . 036 0 .020 0 .027 0 . 035 0 . 0 18 0 . 0 18 0 .016 0 . 033 0 . 000 0 . 000 0 . 023 0 . 025 0 .021 0 . 025 0 . 022 0 . 042 0 . 031 0 .034 0 . 000 0 .032 Mg 3 . 1 16 3 . 166 3 . 242 3 . 214 3 . 147 3 . 222 3 . 065 3 . 231 3 . 083 3 . 005 3 .058 3 .071 3 . 120 3 . 022 2 . 985 3 . 035 2 .861 2 . 980 3 . 339 3 . 109 ea 1 . 779 1 . 845 1 . 749 1 . 773 1 . 864 1 . 943 1 . 928 1 . 823 1 . 955 1 . 9 19 1 . 924 1 . 808 1 . 786 1 . 886 1 . 936 1 . 789 1 . 9 1 5 1 . 858 1 . 797 1 . 795 Na 0 . 725 0 . 729 0 . 738 0 . 735 0 . 7 1 7 0 . 699 0 . 7 1 7 0 . 730 0 . 658 0 . 696 0 . 695 0 . 755 0 . 768 0 . 68 1 0 . 676 0 . 783 0 . 730 0 . 743 0 . 745 0 . 760 K 0 . 186 0 . 1 76 0 . 1 92 0 . 185 0 . 185 0 . 184 0 . 1 55 0 . 164 0 . 164 0 . 185 0 . 167 0 . 201 0 . 1 73 0 . 1 75 0 . 168 0 . 1 69 0 . 1 7 1 0 . 143 0 . 1 73 0 . 1 79 Mg No. 0 . 678 0 . 690 0 . 697 0 .695 0 . 706 0 . 7 1 1 0 . 680 0 . 701 0 . 686 0 . 678 0 . 680 0 . 668 0 . 687 0 . 694 0 . 652 0 . 671 0 . 640 0 . 657 0 . 737 0 . 688 N V1 -.J APPENDIX 7 . 2 : Continued . Samp le 89 Code 1 89 2 89 3 89 4 89 8 89 9 89 10 89 18 89 19 89 20 89 2 1 89 22 tiY 23 1:1� 24 Cl!# 28 89 30 89 Ro35 S io2 46 . 10 44 . oo 47 . 58 47 . 36 45 .86 4 7 . 6 1 4 3 . 86 43 .95 42 . 90 46 . 6 1 4 5 . 82 46 . 43 4 3 . 90 44 . 85 44 . 1 2 44 . 04 45 . 7 1 A 1203 7 . 03 8 . 98 5 . 92 6 . 23 7 .46 6 . 60 8 . 78 9 . 3 1 9 . 96 6 . 62 7 . 40 6 . 80 8 . 58 8 .09 8 . 74 8 . 70 8 . 05 r1o2 1 . 4 1 2 . 31 1 . 18 1 . 28 1 . 67 1 . 44 2 . 10 2 . 54 2 . 12 1 . 34 1 . 76 1 . 55 2 . 21 1 . 12 2 . o8 2 . 35 1 . 77 Feo* 18 . 62 1 5 . 09 1 5 . 00 1 7 . 44 1 8 . 52 1 5 . 7 7 1 6 . 89 14 . 32 1 4 . 39 1 6 . 34 1 6 . 50 1 5 . 98 1 6 . 70 1 8 . 09 1 7 .45 1 5 . 14 1 1 . 92 MnO 0 .43 0 . 43 0 . 38 0 .45 0 . 55 0 . 49 0 . 5 1 0 .47 0 . 5 3 0 . 43 0 .47 0 . 38 0 .49 0 . 43 0 . 59 0 . 38 0 . 24 MgO 1 1 . 63 1 2 . 60 14 . 04 1 2 . 38 1 1 . 4 1 1 3 .00 1 1 .43 1 3 . 1 7 13 . 09 1 3 .02 1 2 . 52 1 2 . 98 1 2 .00 1 1 .03 1 1 .44 1 2 . 86 1 4 . 96 CaO 1 0 . 38 10 . 73 1 0 . 64 10 .4 1 1 0 . 3 1 10 . 6 7 1 0 . 80 10 . 79 1 1 . 1 1 1 0 . 55 1 0 . 70 10 .86 1 0 . 23 1 0 . 48 1 0 . 3 7 10 .82 1 1 . 29 Na2o 1 . 5 1 2 . 14 1 . 34 1 . 5 1 1 . 79 1 . 45 2 . 02 2 . 21 2 . 49 1 . 5 1 1 . 69 1 . 53 2 .00 1 . 76 1 . 96 2 . 10 3 . 48 K20 0 . 37 0 . 3 1 0 .40 0 . 25 0 . 25 0 . 33 0 . 34 0 . 27 0 . 26 0 . 33 0 . 32 0 . 32 0 . 31 0 . 32 0 . 28 0 . 3 1 0 . 3 1 Tota l 9 7 . 48 96 .69 96 .48 9 7 . 3 1 97 .82 97 . 36 96 . 73 9 7 .03 9 7 . 45 96 . 75 97 . 19 96 .83 96 . 48 96 . 77 97 .03 96 . 70 97 . 73 - Cations on the bas i s of 23 oxy9ens Si 6 . 937 6 . 6 19 7 .099 7 . 080 6 . 879 7 . 06 1 6 . 648 6 . 561 6 .408 6 . 991 6 . 864 6 . 954 6 . 654 6 . 802 6 . 669 6 . 622 6 . 720 Al 1 . 247 1 . 592 1 . 041 1 . 098 1 . 3 19 1 . 1 54 1 . 568 1 . 638 1 . 753 1 . 1 70 1 . 307 1 . 200 1 . 533 1 . 446 1 . 557 1 . 542 1 . 395 Ti 0 . 1 60 0 . 26 1 0 . 1 32 0 . 144 0 . 188 0 . 16 1 0 . 239 0 . 285 0 . 306 0 . 1 5 1 0 . 198 0 . 1 75 0 . 259 0 . 196 0 . 236 0 . 266 0 . 196 Fe 2 . 343 1 . 899 1 . 872 2 . 180 2 . 323 1 . 956 2 . 14 1 1 . 788 1 . 798 2 . 050 2 .067 2 . 002 2 . 1 1 7 2 . 294 2 . 206 1 . 904 1 . 466 Mn 0 . 055 0 . 055 0 . 048 0 .057 0 .070 0 . 062 0 . 065 0 .059 0 .067 0 . 055 0 . 060 0 . 048 0 . 063 0 . 055 0 .076 0 . 048 0 . 030 Mg 2 . 608 2 . 825 3 . 1 22 2 . 758 2 . 55 1 2 . 873 2 . 582 2 . 930 2 . 914 2 . 910 2 . 795 2 .897 2 . 7 1 1 2 . 493 2 . 577 2 . 882 3 . 278 ea 1 . 674 1 . 730 1 . 701 1 . 667 1 . 657 1 . 696 1 . 754 1 . 726 1 . 7 78 1 . 695 1 . 7 18 1 . 743 1 . 661 1 . 703 1 . 680 1 . 743 1 . 778 Na 0 . 44 1 0 . 624 0 . 388 0 .438 0 . 521 0 . 4 1 7 0 . 594 0 . 640 0 . 721 0 . 439 0 . 491 0 . 444 0 . 588 0 . 5 1 8 0 . 574 0 . 6 1 2 0 . 992 K 0 .0 7 1 0 . 059 0 . 076 0 . 048 0 . 048 0 . 062 0 . 066 0 .05 1 0 . 050 0 .063 0 . 06 1 0 .061 0 . 060 0 . 062 0 . 054 0 . 059 0 . 058 M9 No . 0 . 521 0 . 591 0 . 6 1 9 0 . 552 0 . 5 16 0 . 587 0 . 539 0 . 6 1 3 0 . 6 1 0 0 . 580 0 . 568 0 . 586 0 . 554 0 . 5 1 5 0 . 530 0 . 596 0 . 68 7 tv V1 CO APPENDIX 7 . 2 : Continued . Samp le 89 Code a38 90 1 90 1 90 2 90 4 90 5 90 7 90 8 90 9 90 10 90 18 90 19 90 24 90 18 90 27 90 29 90 32 S io2 45 . 99 43 .98 45 .48 44 . 72 43 . 46 43 .88 42 .66 46 . 12 46 . 64 45 . 1 6 4 5 . 68 46 .84 46 . 79 45 .55 46 . 55 42 .65 4 7 . 54 A l2o3 8 . 56 9 . 38 7 . 42 8 . 46 9 . 05 9 . 91 1 0 . 87 7 . 24 6 . 64 7 . 72 7 . 1 5 6 . 44 6 .87 7 . 38 6 . 54 1 0 . 60 6 . 29 T io2 1 . 76 2 . 19 1 . 78 2 . 1 5 2 . 34 2 . 47 2 .69 1 . 62 1 . 55 1 .8 1 1 . 59 1 . 32 1 . 6o 1 . 76 1 . 54 2 .88 1 . 1 1 Feo* 1 3 .82 1 5 . 70 1 6 . 26 1 5 . 16 1 5 . 85 1 3 .8 1 1 2 . 70 1 7 . 23 1 5 . 36 1 7 . 4 7 16 . 84 1 5 . 1 7 1 5 . 73 1 6 . 74 1 5 . 40 1 2 . 38 1 6 .28 MnO 0 . 30 0 . 36 0 . 48 0 .48 0 .4 1 0 . 36 0 . 36 0 . 58 0 . 33 0 .42 0 . 5 1 0 . 32 0 . 43 0 . 4 1 0 . 30 0 . 25 0 . 38 MgO 1 4 . 26 1 2 . 19 1 2 . 58 1 2 . 79 1 2 . 27 1 3 . 38 1 3 .87 1 1 . 76 1 3 . 79 1 2 . 3 1 1 2 . 09 1 3 . 1 2 1 2 . 8 1 1 2 .42 1 2 . 84 1 3 . 95 1 3 . 4 1 CaO 10 .97 10 . 79 1 0 . 58 10 . 76 1 0 . 48 1 1 . 00 1 1 .07 1 0 . 64 1 1 .04 10 .85 10 .57 10 .98 10 .8 1 10 .48 1 0 . 88 1 1 . 1 9 1 0 . 23 Na2o 1 . 62 2 . 2 1 1 . 68 1 . 92 2 . 10 2 . 29 2 .46 1 . 63 1 . 46 1 . 7 7 1 . 67 1 . 44 1 . 63 1 . 63 1 . 54 2 . 32 1 . 25 K20 0 .43 0 . 34 0 . 24 0 . 2 7 0 . 28 0 . 3 1 0 .24 0 . 35 0 . 32 0 . 37 0 . 38 0 . 35 0 . 32 0 . 30 0 . 36 0.23 0 . 3 1 Total 97 . 7 1 97 . 14 96 . 50 96 . 7 1 96 . 24 9 7 . 4 1 96 . 92 97 . 1 7 97 . 1 3 9 7 . 88 96 . 48 95 . 98 96 . 99 96 .67 95 . 95 96 .45 96 . 86 Cat i ons on the bas i s of 23 oxygens S i 6 . 762 6 . 596 6 . 854 6 . 708 6 . 586 6 . 5 1 1 6 . 347 6 . 928 6 . 944 6 . 763 6 . 907 7 . 044 6 . 983 6 . 863 7 . 0 1 5 6 . 365 7 . 088 Al 1 . 483 1 . 658 1 . 318 1 . 496 1 . 6 16 1 . 733 1 . 906 1 . 282 1 . 165 1 . 363 1 . 274 1 . 14 1 1 . 208 1 . 3 10 1 . 1 62 1 . 864 1 . 105 Ti 0 . 195 0 .247 0 . 202 0 . 243 0 . 267 0 . 276 0 . 301 0 . 183 0 . 1 74 0 . 204 0 . 181 0 . 149 0 . 180 0 . 199 0 . 1 75 0 . 323 0 . 1 3 1 Fe 1 . 699 1 . 969 2 . 049 1 . 902 2 . 009 1 . 7 14 1 . 580 2 . 165 1 . 9 13 2 . 188 2 . 1 29 1 . 908 1 . 963 2 . 109 1 . 94 1 1 . 545 2 .030 Mn 0 . 037 0 . 046 0 . 061 0 . 061 0 . 053 0 . 045 0 . 045 0 . 074 0 . 042 0 .053 0 . 065 0 .041 0 . 054 0 . 052 0 . 038 0 . 032 0 . 048 Mg 3 . 125 2 . 725 2 .825 2 .859 2 . 77 1 2 . 959 3 .076 2 . 633 3 .060 2 . 74 7 2 . 724 2 . 940 2 . 849 2 . 789 2 . 884 3 . 103 2 . 980 ea 1 . 728 1 . 734 1 . 708 1 . 729 1 . 702 1 . 749 1 . 765 1 . 7 1 3 1 . 76 1 1 . 74 1 1 . 7 12 1 . 769 1 . 729 1 . 692 1 . 757 1 . 789 1 . 634 Na 0 . 462 0 .643 0 . 491 0 . 558 0 . 6 1 7 0 . 659 0 . 710 0 . 475 0 . 421 0 . 5 1 4 0 . 490 0 . 420 0 .472 0 .476 0 . 450 0 . 671 0 . 361 K 0 . 08 1 0 . 065 0 . 046 0 .052 0 . 054 0 . 059 0 . 046 0 .067 0 .061 0 .071 0 . 073 0 .067 0 .061 0 . 058 0 . 069 0 .044 0 . 059 Mg No. 0 . 643 0 . 575 0 . 572 0 . 593 0 . 573 0 . 627 0 . 654 0 . 540 0 . 610 0 . 55 1 0 . 554 0 . 601 0 . 585 0 . 563 0 . 593 0 . 663 0 . 589 I'V (.J1 10 APPENDIX 7 . 2 : Continued . Samp le 84 Code 1 1 84 K 1 2 84 R 1 2 84 1< 1 2 84 R 1 2 84 1 5 84 18 84 19 87 1 7 87 1<18 87 R 18 87 19 87 21 s to2 49 . 1 7 46 . 10 48 . 4 1 4 7 . 87 48 .23 48 .69 44 .25 4 5 . 09 48 . 40 48 . 36 44 . 98 48 . 70 48 .07 A l2o3 5 . 2 1 7 . 35 5 . 73 6 . 37 5 . 84 5 . 76 7 . 91 7 .8 1 6 .4 7 6 . 25 9 . 20 6 .04 6 . 64 T io2 o .94 1 . 67 1 . 16 1 . 23 1 . 1 4 1 . 09 2 .00 1 . 64 1 . 46 1 . 43 2 .09 1 . 3 7 1 . 47 Feo* 1 4 . 45 1 5 .06 1 4 . 96 1 4 . 5 7 1 5 . 05 1 3 . 86 1 8 . 44 1 7 . 38 14 .41 15 .00 1 6 . 09 1 4 . 32 1 4 . 18 HnO 0 . 87 0 . 67 0 . 6 7 0 . 53 0 .6 1 0 . 79 0 .83 0 . 44 0 . 64 0 .45 0 . 49 0 .67 0 . 57 MgO 1 4 . 84 1 2 . 7 7 1 3 . 72 1 3 . 97 1 3 . 73 14 . 68 1 0 . 95 1 1 . 3 1 1 3 .97 1 3 . 72 1 1 . 9 1 14 .04 14 . 10 CaO 9 . 70 1 0 . 38 1 0 . 1 8 1 0 .45 1 0 . 53 1 0 . 38 10 . 1 7 1 0 . 55 1 0 . 52 1 0 . 5 7 1 0 . 73 10 . 39 1 0 . 60 Na2o 1 . 3 1 1 . 66 1 . 37 1 . 46 1 . 37 1 . 34 1 . 72 1 . 62 1 .04 1 .05 1 . 27 1 . 1 3 1 . 46 1<20 0 . 1 7 0 . 29 0 . 1 9 0 . 20 0 . 2 7 0 . 18 0 . 43 0 . 55 0 . 2 7 0 . 3 1 0 . 49 0 . 25 0 . 3 1 Total 96 . 48 95 .69 96 . 39 96 . 65 96 . 77 96 . 77 96 . 70 96 .39 97 . 18 97 . 14 97 . 25 96 . 9 1 9 7 . 40 Cat i ons on the bas i s of 23 oxygens S 1 7 . 265 6 .938 7 . 203 7 . 101 7 . 1 64 7 . 184 6 . 750 6 . 848 7 . 122 7 . 1 38 6 . 7 1 6 7 . 180 7 . 068 A l 0 . 907 1 . 304 1 . 005 1 . 1 14 1 . 022 1 . 002 1 . 422 1 . 398 1 . 1 22 1 . 087 1 . 6 19 1 . 050 1 . 1 51 T 1 0 . 1 04 0 . 189 0 . 1 30 0 . 137 0 . 127 0 . 12 1 0 .229 0 . 187 0 . 1 62 0 . 1 59 0 . 235 0 . 1 52 0 . 163 Fe 1 . 785 1 . 896 1 . 862 1 . 808 1 . 870 1 . 7 10 2 . 353 2 . 20 7 1 . 7 73 1 . 852 2 .009 1 . 766 1 . 744 Mn 0 . 109 0 . 085 0 . 084 0 .06 7 0 .077 0 . 099 0 . 107 0 .057 0 . 080 0 .056 0 . 062 0 . 084 0 .071 Mg 3 . 268 2 . 864 3 . 042 3 . 088 3 . 039 3 . 228 2 . 489 2 . 560 3 . 064 3 . 018 2 . 650 3 . 085 3 . 090 ea 1 . 536 1 . 6 74 1 . 623 1 . 661 1 . 676 1 . 641 1 . 662 1 . 7 1 7 1 . 659 1 . 672 1 . 7 1 7 1 . 64 1 1 . 670 Na 0 . 375 0 . 484 0 . 395 0 . 420 0 . 395 0 . 383 0 . 509 0 . 477 0 . 297 0 . 300 0 . 368 0 . 323 0 . 4 16 K 0 .032 0 . 056 0 . 036 0 . 038 0 . 05 1 0 . 034 0 . 084 0 . 107 0 . 05 1 0�058 0 . 093 0 .047 0 . 058 Mg No . 0 . 633 0 . 591 0 . 6 1 0 0 . 622 0 .6 10 0 .641 0 . 503 0 . 531 0 . 623 0 . 6 1 3 0 . 56 1 0 . 625 0 .630 N 0\ 0 APPENDIX 7 . 3 : CLINOPYROXENE Samp l e MnP Code 25 MnP 10 MnP 1 1 MnP 1 1 MnP 1 5 MnP 16 MnP 1 6 MnP K32 MnP R32 MnP 33 MnP 34 MnP MnP MnP MnP Mnl 24 i h 1 0 Mnl 1( 1 3 r·1n l Z 1 3 Mnl Z 1 3 S i 02 4 9 . 02 50 . 5 7 48 . 90 4 9 . 75 5 1 . 06 n . d . 5 1 . 33 5 1 . 4 7 50 . 39 50 . 10 48 . 38 48 . 5 7 52 . 1 9 50 . 1 0 4 7 . 4 5 A l z03 4 . 55 2 . 68 4 . 32 3 . 59 2 . 33 1 . 00 1 . 35 2 . 2 1 3 . 45 3 . 36 5 . 58 5 . 08 1 . 90 3 . 44 6 . 3 1 T i 02 0 . 60 0 . 40 0 . 5 7 0 . 4 7 0 . 54 n . d . 0 . 1 9 0 . 4 7 0 . 56 0 . 53 0 . 93 0 . 63 0 . 40 0 . 68 0 . 98 Feo* MnO 6 . 29 7 . 58 7 . 04 7 . 1 4 7 . 4 2 1 3 . 76 1 1 . 58 7 . 24 7 . 87 8 . 2 1 8 . 0 7 7 . 4 1 7 . 56 6 . 7 7 7 .85 0 . 00 0 . 42 0 . 1 8 0 . 1 3 0 . 33 0 . 33 0 . 4 7 0 . 48 0 . 29 0 . 46 0 . 1 7 0 . 1 5 0 . 4 1 0 . 26 0 . 00 n . d . 5 1 . 02 4 9 . 5 5 50 . 1 9 4 . 62 3 . 76 5 . 2 1 4 . 3 ( 0 . 70 0 . 79 0 . 96 G . ia 6 . 90 7 . 7 7 7 . 05 8 . 2 1 0 . 25 0 . 24 0 . 00 0 . 2 7 M90 1 4 . 56 1 5 . 46 1 3 . 4 7 1 4 . 4 1 1 5 . 4 7 1 1 . 2 7 1 2 . 66 1 4 . 78 1 3 . 8 1 1 3 . 99 1 2 . 90 1 4 . 1 6 1 6 . 1 5 1 4 . 34 1 3 . 66 14 . 5 1 14 . 5 7 1 4 . 1 5 1 3 . 89 CaO 23 . 4 2 2 1 . 80 23 . 30 23 . 27 2 1 . 86 20 . 58 20 . 99 22 . 52 22 . 69 2 1 . 03 22 . 79 2 3 . 33 20 . 59 22 . 4 1 23 . 3 1 23 . 07 2 1 . 7 7 23 . 26 22 . 23 Na2o 0 . 29 0 . 45 0 . 28 0 . 27 0 . 30 n . d . 0 . 3 1 0 . 3 5 0 . 43 0 . 34 0 . 30 0 . 26 0 . 30 0 . 32 0 . 30 Tota l 98 . 7 3 99 . 36 98 . 06 99 . 03 99 . 3 1 Cat i ons on the bas i s of 6 oxy9ens Si 1 . 846 1 . 896 1 . 861 1 . 874 1 . 9 1 1 ' Al 0 . 202 0 . 1 18 0 . 1 94 0 . 1 59 0 . 103 Ti 0 .0 1 7 0 . 01 1 0 . 0 1 6 0 . 0 1 3 0 . 0 1 5 F e 0 . 1 98 0 . 238 0 . 224 0 . 225 0 . 232 Mn 0 . 000 0 . 0 1 3 0 . 006 0 . 004 0 . 01 0 M9 0 . 8 1 7 0 . 864 0 . 764 0 . 809 0 .863 ea 0 . 945 0 . 876 0 . 950 0 . 939 0 .8 7 7 Na 0 . 021 0 . 033 0 . 02 1 0 . 020 0 . 022 Sum 4 . 04 7 4 . 050 4 . 036 4 . 043 4 . 033 Wo En F s 48 .2 44 . 3 4 9 . 0 4 7 . 6 44 . 5 4 1 . 7 43 . 7 39 . 4 4 1 . 0 4 3 . 8 10 . 1 1 ? . 0 1 1 . 6 1 1 . 4 1 1 . 8 98 . 88 99 . 52 99 . 49 98 . 02 99 . 1 0 99 . 59 99 . 50 98 . 32 99 . 86 1 . 961 1 . 924 1 . 891 1 . 904 1 . 827 1 . 824 1 . 940 1 . 892 1 . 782 0 . 06 1 0 . 097 0 . 1 53 0 . 1 50 0 . 248 0 . 225 0 . 083 0 . 1 53 0 . 279 0 . 005 0 . 01 3 0 . 01 6 0 . 0 1 5 0 . 026 0 .0 18 0 . 0 1 1 0 . 0 1 9 0 . 028 0 . 370 0 . 226 0 . 24 7 0 . 26 1 0 . 255 0 . 233 0 . 235 0 . 2 1 4 0 . 24 7 0 . 0 1 5 0 . 0 1 5 0 . 009 0 . 01 5 0 . 005 0 . 005 0 . 0 1 3 0 . 008 0 . 000 0 . 72 1 0 .823 0 . 7 72 0 . 792 0 . 726 0 . 793 0 .895 0 . 807 0 . 765 0 . 859 0 . 902 0 . 9 1 3 0 .856 0 . 922 0 . 939 0 . 820 0 . 907 0 . 938 0 . 023 0 . 025 0 . 03 1 0 . 025 0 . 022 0 . 0 1 9 0 . 022 0 . 023 0 . 022 4 . 0 1 5 4 . 027 4 . 032 4 . 0 18 4 . 033 4 . 055 4 . 0 1 8 4 . 024 4 . 06 1 4 3 . 8 44 . 1 46 . ? 33 . 4 37 . 0 4 2 . 2 22 . 9 1 9 . 0 1 1 . 6 4 7 . 2 4 4 . 8 48 . � 40 . 0 4 1 . 5 38 . 1 1 2 . 8 1 3 . 7 1 3 . 4 4 7 . R 40 .4 1 1 . 8 4 ? . 1 45 . 9 1 2 . 1 4 7 . 0 4 1 . 9 1 1 . 1 48 . 1 39 . 2 1 ? . 6 n . d . 0 . 4 3 0 . 26 0 . 36 4 7 . 4 4 1 . 5 1 1 . 1 1 00 . 35 1 00 . 44 100 . 2 1 1 . 889 1 . 836 1 . 869 0 . 1 64 0 . 228 0 . 1 90 0 . 022 0 . 027 0 . 02 1 0 . 24 1 0 . 2 18 0 . 256 0 . 008 0 . 000 0 . 009 0 . 804 0 . 78 1 0 . 7 7 1 0 . 864 0 . 924 0 . 887 0 . 03 1 0 . 0 1 9 0 . 026 4 . 0?7. 4 . 03J 4 . o?n 4!> . 3 4 ? . 1 1 ? . 6 411 . 0 40 . 6 1 1 . 4 46 . 4 40 . 3 1 3 . a N 0'1 � APPENDIX 7 . 3 : Continued . Samp l e Mnl Code Z 1 3 Mnl Z 1 3 Mnl Mnl Z 13 · R 1 3 Mnl 1 4 Mnl 18 Mnl 20 Mnl 25 Mnl 25 Mnl 26 Mnl R 1 Mnl 1 2 Mnl 1 1 Mnl 8 Mnl 27 Mnl 28 Mnl 29 I L 1 4 I L K26 S i02 5 1 . 54 48 . 99 n . d . 50 .88 49 . 1 1 48 . 30 50 . 1 9 48 . 1 6 49 . 56 4 9 . 63 48 . 58 5 1 . 73 48 . 98 48 . 79 49 . 53 46 . 94 50 .69 5 3 . 78 n . d . A l 2o3 3 . 29 5 . 55 3 . 8 1 4 . 48 5 . 56 6 . 42 4 . 66 4 . 54 5 .09 4 . 95 5 . 58 2 . 1 4 5 . 10 5 . 59 4 . 78 6 . 94 3 . 94 0 . 7 1 1 . 4 1 T i 02 0 . 5 7 1 . 1 8 0 . 58 0 . 66 0 .85 0 .86 0 . 85 1 . 20 0 . 7 3 0 . 75 0 . 8 1 0 . 49 0 . 84 1 . 26 0 . 82 1 . 1 7 0 . 44 0 . 18 0 . 26 Feo* 5 . 90 7 . 86 6 . 46 6 . 93 8 . 32 8 . 32 6 . 7 1 7 . 83 7 . 50 7 . 04 8 .02 7 . 59 8 . 16 8 . 0 1 7 . 1 3 8 . 39 6 . 52 7 . 03 7 . 86 MnO 0 . 1 2 0 . 1 7 0 . 1 3 0 . 1 6 0 . 2 1 0 . 24 0 . 00 0 . 25 0 . 00 0 . 1 7 0 . 1 7 0 . 4 1 0 . 18 0 . 1 6 0 . 00 0 . 00 0 . 1 7 0 . 90 0 . 72 MgO 1 5 . 1 4 1 3 . 80 1 5 . 4 7 1 4 . 7 1 1 3 .09 1 3 . 1 9 1 4 . 36 1 3 . 33 1 4 . 33 1 4 . 38 1 3 . 5 1 1 5 . 09 1 3 . 40 1 3 . 59 1 4 . 49 1 2 . 64 1 4 . 73 1 5 . 1 2 1 4 . 7 7 CaO 23 . 1 2 22 . 54 22 . 96 22 . 80 23 . 10 22 .63 23 . 44 2 1 .04 22 . 1 1 22 . 4 5 23 .02 22 . 26 22 . 3 7 22 . 20 22 . 34 22 . 1 2 2 2 . 59 22 .84 22 . 40 Na20 0 . 20 0 . 39 n . d . 0 . 32 0 . 34 0 . 38 0 . 3 1 0 . 42 0 . 33 0 . 33 0 . 40 0 . 34 0 . 45 0 . 40 0 . 30 0 . 33 0 . 32 0 . 33 0 . 44 Total 99 .88 1 00 . 48 100 . 94 100 . 58 100 . 34 1 00 . 52 96 . 7 7 99 . 65 99 . 70 1 00 . 09 1 00 .05 99 . 48 1 00 . 00 99 . 39 98 . 53 99 . 40 100 .89 Cat ions on the bas i s of 6 oxygens $ 1 A I T i Fe Mn Mg Ca Na Sum Wo En Fs 1 . 905 1 . 82 1 0 . 1 43 0 . 243 0 .0 16 0 .033 0 . 182 0 . 244 0 . 004 0 . 005 0 . 834 0 . 765 0 . 9 1 6 0 . 898 0 . 0 14 0 . 028 4 . 0 1 5 4 .038 4 7 . 4 4 3 . 2 9 . 4 4 7 . 1 40 . 1 1 2 . 8 46 . 4 4 3 . 5 1 0 . 2 1 . 870 1 . 830 1 . 804 1 . 855 1 . 856 1 . 849 1 . 850 1 . 8 1 9 1 . 924 1 . 84 1 1 . 823 1 . 85 1 1 . 785 1 . 888 1 . 979 0 . 1 94 0 . 244 0 . 283 0 . 203 0 . 206 0 . 224 0 . 2 1 7 0 . 246 0 . 094 0 . 226 0 . 246 0 . 2 1 1 0 . 3 1 1 0 . 1 73 0 . 03 1 0 .0 18 0 . 024 0 . 024 0 . 024 0 . 035 0 . 020 0 . 02 1 0 . 023 0 .0 1 4 0 . 024 0 . 035 0 . 023 0 . 033 0 .0 12 0 . 005 0 . 2 1 3 0 . 259 0 . 260 0 . 207 0 . 252 0 . 234 0 . 2 19 0 . 2 5 1 0 . 236 0 . 257 0 . 250 . 0 . 223 0 . 26 7 0 . 203 0 . 2 16 0 . 005 0 .007 0 . 008 0 . 000 0 . 008 0 . 000 0 . 005 0 . 005 0 . 0 1 3 0 . 006 0 . 005 0 . 000 0 . 000 0 . 005 0 . 028 0 . 806 0 . 727 0 . 734 0 . 79 1 0 . 765 0 . 797 0 . 799 0 . 7 54 0 . 836 0 . 75 1 0 . 757 0 . 807 0 . 7 1 6 0 . 8 18 0 . 829 0 . 898 0 . 922 0 . 905 0 . 928 0 . 869 0 . 884 0 . 897 0 . 923 0 . 887 0 . 90 1 0 . 889 0 . 895 0 . 90 1 0 . 902 0 . 90 1 0 . 023 0 . 025 0 . 028 0 . 022 0 . 03 1 0 . 024 0 . 024 0 . 029 0 . 025 0 . 033 0 . 029 0 . 022 0 . 024 0 . 023 0 . 024 4 .026 4 . 037 4 . 045 4 .03 1 4 . 022 4 . 03 1 4 . 032 4 . 050 4 . 028 4 . 038 4 . 033 4 . 03 1 4 . 038 4 . 025 ' 4 . 0 1 2 46 . 8 48 . 3 4 2 . 0 38 . 1 1 1 . 1 1 3 . 6 4 7 . 7 38 . 6 1 3 . 7 48 . 2 46 . 0 46 . 2 4 6 . 8 4 1 . 1 40 .6 4 1 . 6 4 1 . 7 1 0 . 8 1 3 . 4 1 2 . 2 1 1 . 5 4 7 . 9 39 . 1 1 3 . 0 4 5 . 3 4 7 . 2 42 . 7 39 . 3 1 2 . 0 1 3 . 4 46 . 9 46 . 5 39 . 9 4 1 . 9 1 3 . 2 1 1 . 6 4 7 . 8 46 . 9 38 . 0 42 . 5 1 4 . 2 1 0 . 6 46 . 3 42 . 6 1 1 . 1 4 5 . 6 4 1 . 9 1 2 . 5 N 0'1 N APPENDIX 7 . 3 1 Continued . Samp l e I L Code Z26 IL Z26 I L Z26 I L Z26 I L R26 IL K 1 4 I L S 14 I L Z 14 I L Z 1 4 I L Z 1 4 I L R 1 4 I L 22 IL 22 I L 23 I L 24 I L 25 222 df1 222 2 222 K3 S i02 n . d . n . d . 5 1 . 83 n . d . 53 . 20 5 2 . 26 53 . 34 5 2 . 80 n . d . n . d . 53 . 26 5 1 .87 5 3 . 3 7 n . d . 53 .02 52 . 68 5 2 . 8 1 52 . 1 3 52 . 2 7 A l z03 2 .83 2 . 03 2 . 70 1 . 4 5 1 . 25 2 . 23 1 . 2 1 1 . 62 0 .89 1 . 1 5 1 . 1 3 2 . 30 1 . 1 7 1 . 62 1 . 39 1 . 72 1 . 54 2 . 2 7 1 . 62 T iOz o . 54 o . 44 o . 5o o . 3 7 o . 28 o . 5o o . 33 o . 37 o . 3o 0 . 2 1 o . 3o 0 .49 o. 1 9 o . 32 o . 3o 0 . 38 0 . 40 0 . 5 7 0 . 45 7 . 4 1 7 . 78 7 . 39 Feo* 7 . 94 8 . 32 8 . 63 7 . 66 6 . 95 7 . 90 7 . 23 7 . 67 7 . 38 7 . 1 7 7 . 04 7 . 63 8 . 1 3 8 . 44 7 . 50 7 . 52 MnO 0 . 33 0 . 5 7 0 . 48 0 . 67 0 . 6 7 0 .68 0 .85 0 . 7 1 0 . 6 7 0 . 75 0 . 68 0 . 59 0 . 70 0 . 72 0 . 66 0 . 68 0 . 72 0 . 46 0 . 79 MgO 1 4 . 23 1 3 . 96 1 3 . 4 2 1 4 . 69 1 5 . 20 1 4 . 33 1 5 . 2 7 1 4 . 52 1 5 . 72 1 5 . 24 14 . 96 1 4 . 59 1 4 . 62 1 4 . 27 14 . 7 7 1 4 . 25 1 5 . 55 1 4 . 74 1 5 . 57 CaO 2 3 . 16 22 . 7 7 2 2 . 87 22 . 56 2 2 . 90 2 2 . 46 22 . 3 1 22 . 58 22 . 22 22 . 6 1 22 .83 2 2 . 49 22 . 1 6 22 . 33 22 . 1 9 22 .07 2 1 . 9 1 22 . 50 2 1 . 47 Na2o 0 . 3 1 0 . 46 0 . 39 0 . 40 0 . 39 0 . 44 0 . 38 0 . 42 0 . 37 0 . 36 0 . 35 0 . 4 7 0 . 54 0 . 53 0 . 42 0 . 5 1 0 . 39 0 . 36 0 . 39 Tota l 100 . 82 Cat ions on the bas i s of 6 oxygens S i A l T 1 Fe Mn Mg ea Na .Sum llo En F s 47 . 1 40 . 3 1 2 . 6 46 . 8 39 . 9 1 3 . 3 1 . 923 0 . 1 18 0 . 0 14 0 . 268 0 .0 1 5 o . 742 0 . 909 0 . 028 4 . 0 18 4 7 . 4 46 . 1 38 . 7 4 1 . 7 14 . 0 1 2 . 2 100 .84 100 . 80 100 . 92 100 . 69 1 . 959 1 . 933 1 . 962 1 . 952 0 .054 0 . 097 0 . 052 0 . 07 1 0 . 008 0 .0 14 0 . 009 0 .0 10 0 . 2 14 0 . 244 0 . 222 0 . 23 7 0 .021 0 .021 0 . 026 0 . 022 0 .834 0 . 790 0 .837 0 . 800 0 . 903 0 . 890 0 . 879 0 . 895 0 . 028 0 . 032 0 . 027 0 . 030 4 . 021 4 . 02 1 4 . 016 4 . 0 1 7 46 . 3 42 . 7 1 1 . 0 46 . 3 4 5 . 4 4 1 . 0 4 3 . 2 1 2 . 7 1 1 . 5 46 . 3 4 1 . 4 1 2 . 3 44 . 6 4 3 . 9 1 1 . 6 100 . 55 100 . 4 3 100 . 88 1 . 966 1 . 924 1 . 970 0 . 049 o . 101 0 . 05 1 0 . 008 0 . 0 14 0 . 005 0 . 2 1 7 0 . 237 0 . 2 5 1 0 . 02 1 0 .0 19 0 . 022 0 . 823 0 . 807 0 . 804 0 . 903 0 . 894 0 . 876 0 . 025 0 . 034 0 . 039 4 .0 13 4 . 029 4 . 0 19 45 .8 46 . 5 46 . 1 45 . 4 42 . 9 42 . 3 4 1 . 6 4 1 . 6 1 1 . 3 1 1 . 2 1 2 . 2 1 3 . 0 100 . 25 99 . 8 1 100 . 73 100 .81 99 . 50 1 . 964 1 . 96 1 1 . 947 1 . 925 1 . 942 0 . 06 1 0 .075 0 . 067 0 . 099 0 .0 7 1 0 . 008 0 . 0 1 1 0 . 0 1 1 0 . 0 1 6 0 . 01 3 0 . 232 0 . 234 0 . 228 0 . 240 0 . 230 0 . 02 1 0 . 02 1 0 . 022 0 . 0 1 4 0 . 025 0 . 8 1 5 0 . 79 0 . 854 0 . 8 1 1 0 .862 0 . 881 0 . 880 0 . 865 0 . 890 0 . 855 0 . 030 0 . 037 0 . 028 0 . 026 0 . 028 4 . 0 1 2 4 . 009 4 . 023 4 . 022 4 . 024 4 5 . 8 45 . 7 40 . 7 42 . 3 1 3 . 5 1 2 . 0 46 . 2 4 1 . 5 1 2 . 3 44 . 4 43 . 9 1 1 . 7 4 5 . 8 4 1 . 8 1 2 . 4 43 . 9 44 . 3 1 1 . 8 IV 0\ w APPENDIX 7 . 3 s Continued. Samp le 222 Code K4 222 K5 222 Z5 222 zs 222 Z5 222 Z5 222 RS 222 12 222 1 3 222 16 222 K21 222 228u 27 K 1 6 228u 228u 228u 228u 228u 228u Z 1 6 Z 1 6 Z 1 6 R 1 6 34 32 S f 02 5 3 . 05 52 .43 50 . 3 1 52 . 28 50 . 5 1 50 .42 53 .02 52 . 1 9 5 2 . 49 5 2 . 5 7 5 1 . 24 5 3 . 01 n . d . n . d . 53 . 45 n . d . n . d . 52 . 20 5 1 . 9 1 A 1 2o3 1 . 40 1 . 54 3 . 40 1 . 79 2 . 5 1 3 .0 1 1 . 35 1 . 8 1 1 . 05 1 . 86 2 . 7 7 1 . 62 2 . 18 1 . 23 1 . 38 1 . 3 1 1 . 5 1 1 . 87 1 . 77 r 1 o2 o . 4 7 o . 5o o . 75 o . 4 1 o . 52 o . 55 o . 33 o . 3 1 o . 36 o .46 o . 6o o . 4 1 0 . 29 o . 38 o . 3 1 o . 34 o . 34 o . 57 o . 5o Feo* 7 . 67 7 . 5 1 8 . 46 7 . 83 8 . 10 7 .85 7 . 28 8 . 62 7 . 20 7 . 62 7 . 62 7 . 10 8 . 80 6 . 95 7 . 30 7 . 1 2 7 . 1 5 7 . 22 7 .09 MnO 0 . 60 0 . 5 1 0 . 33 0 . 5 1 0 . 1 7 0 . 3 1 0 . 6 1 0 . 75 0 . 77 0 . 66 0 . 28 0 . 60 0 . 78 0 . 5 1 0 . 4 7 0 . 72 0 . 5 1 0 . 65 0 . 60 MgO 1 5 . 66 1 6 . 08 1 3 . 59 1 4 .89 1 4 . 36 1 4 . 33 1 5 .43 1 4 .62 1 5 . 4 1 1 5 . 18 1 4 . 2 1 1 5 . 5 1 1 4 . 6 1 1 5 . 55 1 5 . 92 16 .03 1 6 . 00 1 5 . 50 1 5 . 4 1 CaO 2 1 . 42 2 1 . 38 2 2 . 5 6 2 1 . 97 2 2 . 47 22 . 68 2 1 . 5 7 20 . 4 4 2 1 . 70 2 1 . 53 23 . 1 5 2 1 . 60 2 1 . 35 2 1 . 75 2 1 . 62 2 1 . 42 2 1 . 74 2 1 .49 2 1 . 79 Na2o 0 . 3 5 0 . 38 0 . 28 0 . 29 0 . 3 1 0 . 27 0 .43 0 . 57 0 . 32 0 . 44 0 . 32 0 . 4 1 0 . 5 1 0 . 3 1 0 . 43 0 . 33 0 . 35 0 . 38 0 . 42 Tota l 100 . 62 100 . 33 99 . 68 99 . 9 7 98 . 95 99.42 100 . 02 99 . 3 1 99 . 30 100 . 32 100 . 19 100 . 26 Cat ions on the bas i s of 6 oxygens S i A l T f Fe Mn Mg ea Na Sum Wo En Fs 1 . 955 1 . 938 1 . 889 1 . 944 1 . 907 1 . 894 1 . 963 1 . 955 1 . 96 1 1 . 945 1 . 907 1 . 956 0 . 06 1 0 .067 0 . 1 50 0 . 078 0 . 1 1 2 0 . 1 33 0 . 059 0 . 080 0 . 046 0 . 081 0 . 1 22 0 .070 0 . 0 1 3 0 . 0 1 4 0 .021 0 . 0 1 1 0 . 0 1 5 0 .0 16 0 .009 0 . 009 0 . 0 10 0 .0 1 3 0 . 0 1 7 0 . 0 1 1 0 . 236 0 . 23 2 0 . 266 0 . 244 0 . 256 0 . 24 7 0 . 225 0 . 270 0 . 225 0 . 236 0 . 237 0 . 2 1 9 0 . 0 19 0 . 0 1 6 0 .0 10 0 .0 16 0 . 005 0 . 0 10 0 .0 19 0 . 024 0 . 024 0 . 02 1 0 . 009 0 . 0 1 9 0 . 860 0 . 886 0 . 760 0 . 825 0 . 808 0 . 802 0 .85 1 0 . 8 1 6 0 . 858 0 . 837 0 . 788 0 .853 0 . 846 0 .847 0 . 908 0 . 875 0 . 909 0 . 9 13 0 .856 0 . 82 1 0 . 869 0 .854 0 . 923 0 . 854 0 . 025 0 . 027 0 . 020 0 .021 0 . 023 0 . 020 0 . 03 1 0 . 04 1 0 . 023 0 . 032 0 . 023 0 . 029 4 . 0 14 4 . 028 4 .025 4 . 0 15 4 .034 4 . 034 4 . 0 14 4 . 0 1 7 4 . 01 7 4 . 0 1 7 4 . 027 4 . 0 1 2 43 . 5 4 3 . 1 44 . 3 45 . 1 1 2 . 2 1 1 . 8 46 ;9 4 5. 0 46 . 1 46 . 5 44 . 3 39 . 3 4 2 . 4 4 1 . 0 40 . 9 44 . 1 1 3 . 7 1 2 . 5 1 3 . 0 1 2 . 6 1 1 . 7 4 3 . 0 44 . 5 44 . 3 4 7 . 4 4 2 . 8 4 4 . 0 43 . 5 40 . 4 1 4 . 2 1 1 . 5 1 2 . 2 1 2 . 2 44 . 3 44 . 0 44 . 3 4 1 . 9 1 1 . 4 1 4 . 2 100 .88 1 . 960 0 . 060 0 . 009 0 . 224 0 . 0 1 5 0 . 870 0 .850 0 . 03 1 4 . 0 1 7 44 . 6 43 . 7 43 . 5 44 . 3 44 . 8 4 5 . 2 1 1 . 1 1 1 . 5 1 1 . 3 99 .88 99 .49 1 . 938 1 . 936 0 . 082 0 .078 0 .0 16 0 . 0 1 4 0 . 224 0 . 22 1 0 . 020 0 .0 1 9 0 . 857 0 .857 0 . 855 0 . 8 7 1 0 . 027 0 . 030 4 . 0 19 4 . 026 4 3 . 9 44 . 1 44 . 9 44 . 3 1 1 . 3 1 1 . 6 44 . 7 44 . 0 1 1 . 3 1\J 0'1 � APPENDIX 1 . 3 : Continued . Samp l e 228u 228u Code 29 30 228m 228m 228m 228m 228m 228m 228m 228m 228m 228m 228m 228m 228m 228m 228m 228L 228L 16 18 1 3 5 6 7 8 1 1 24 25 K31 Z 3 1 Z 3 1 R 3 1 18 1 9 S i02 49 . 74 52 . 66 52 . 54 5 1 . 36 52 . 26 5 1 . 99 50 . 23 52 . 74 5 1 . 2 1 50 .8 1 52 .01 5 1 . 54 5 1 .09 5 1 .89 49 . 00 50 . 92 5 1 . 2 7 5 1 . 94 52 . 4 1 A 1 2o3 4 . 42 2 . 04 T i02 0 . 83 0 . 55 Feo* 8 . 29 7 . 38 MnO 0 . 29 0 . 53 1 . 4 7 2 . 1 6 1 . 05 1 . 58 3 . 28 1 . 28 2 .87 2 .97 1 . 1 4 2 . 26 2 . 39 1 . 30 4 . 1 1 3 .04 2 . 59 1 . 90 1 . 7 7 0 . 29 0 . 49 0 . 24 0 . 40 0 . 64 0 . 33 0 . 64 0 . 60 0 . 24 0 . 70 0 . 56 0 . 25 0 . 70 0 . 54 0 . 42 0 . 50 0 .4 1 7 . 5 1 7 .02 8 . 07 7 . 53 7 . 80 7 . 79 7 . 4 1 7 . 1 6 7 . 36 6 . 5 7 7 . 62 7 . 60 9 .03 7 . 72 7 . 70 7 . 1 7 7 . 34 0 . 74 0 .44 0 .69 0 . 48 0 . 1 7 0 . 74 0 . 45 0 . 35 0 . 64 0 . 34 0 . 3 1 0 . 76 0 . 44 0 . 28 0 . 3 1 0 . 43 0 . 5 1 MgO 1 3 . 52 1 5 . 1 2 1 5 . 32 1 5 . 08 1 5 . 30 1 5 . 63 1 5 . 36 1 5 . 93 1 4 .42 1 4 . 56 1 5 . 35 1 5 . 50 1 5 .03 1 5 .05 1 3 . 35 1 4 . 23 1 4 . 58 1 5 . 49 15 .83 C aO 23 . 1 7 2 1 . 85 2 1 .32 2 1 . 64 2 1 . 68 2 1 .26 22 .03 2 1 . 1 5 2 1 . 5 7 22 .34 2 1 . 6 7 22 . 1 9 22 . 85 2 1 . 75 22 . 24 22 . 37 22 . 78 22 . 78 22 . 18 Na2o 0 . 37 0 . 4 1 0 . 40 0 . 32 0 . 39 0 . 40 0 . 1 7 0 . 34 0 . 38 0 . 28 0 . 36 0 . 37 0 . 26 0 . 5 1 ' 0 . 33 0 . 30 0 . 3 1 0 . 36 0 . 42 Tot a l 100 . 63 100 . 54 99 . 59 98 . 5 1 99 .68 99 . 27 99 . 68 1 00 . 30 98 . 95 99 .07 98 . 7 7 99 . 4 7 100. 1 1 99 . 1 1 99 . 20 99 . 40 99 . 96 100 . 5 7 100 . 87 Cat i ons on the bas i s of 6 oxygens S 1 1 . 853 1 . 942 1 . 957 1 . 932 1 . 954 1 . 943 1 . 8 77 1 . 952 1 . 920 1 . 906 1 . 956 1 . 9 1 9 1 . 904 1 . 950 1 . 857 1 . 907 1 . 9 1 2 1 . 92 1 1 . 930 A l 0 . 1 94 0 . 089 0 .065 0 . 096 0 . 046 0 .070 0 . 1 44 0 . 056 0 . 1 27 0 . 1 3 1 0 . 05 1 0 . 099 0 . 105 0 . 058 0 . 184 0 . 1 34 0 . 1 1 4 0 . 083 0 .0 7 7 T i 0 . 023 0 .0 1 5 0 . 008 0 .0 1 4 0 .007 0 . 0 1 1 0 .0 18 0 . 009 0 .018 0 .0 1 7 0 . 007 0 . 020 0 .016 0 . 007 0 .020 0 .015 0 .0 1 2 0 .014 0 . 0 1 1 Fe 0 . 258 0 . 228 0 . 234 0 . 22 1 0 . 252 0 . 235 0 . 244 0 . 24 1 0 . 232 0 . 225 0 . 23 1 0 . 205 0 . 237 0 . 239 0 . 286 0 . 242 0 . 240 0 . 222 0 . 226 Mn 0 .009 0 .0 1 7 0 .023 0 . 014 0 . 022 0 .0 1 5 0 . 005 0 . 023 0 . 0 14 0 . 0 1 1 0 . 020 0 . 01 1 0 . 0 10 0 . 024 0 . 0 1 4 0 . 009 0 . 0 10 0 . 0 1 3 0 .0 1 6 Mg 0 . 75 1 0 . 831 0 . 850 0 .845 0 .853 0 . 87 1 0 .855 0 . 879 0 . 806 0 . 8 1 4 0 . 860 0 . 860 0 .835 0 . 843 0 . 754 0 .. 794 0 . 8 10 0 . 854 0 . 869 ea 0 . 925 0 . 863 0 . 85 1 0 . 872 0 .869 0 .851 0 . 882 0 .839 0 .867 0 . 898 0 .873 0 . 885 0 . 9 1 2 0 . 876 0 . 903 0 . 898 0 .9 10 0 . 903 0 . 875 Na 0 . 027 0 . 029 0 . 029 0 . 023 0 . 028 0 . 029 0 .0 1 2 0 . 024 0 . 028 0 . 020 0 . 026 0 . 027 0 . 019 0 . 03 7 0 . 024 0 . 022 0 .022 0 . 026 0 . 030 Sum 4 .040 4 . 0 1 3 4 . 0 1 7 4 . 0 18 4 .030 4 . 025 4 . 039 4 . 023 4 .0 1 2 4 . 022 4 . 025 4 . 025 4 .037 4 . 033 4 . 043 4 . 02 1 4 . 031 4 . 036 4 . 035 Wo En Fs 4 7 . 8 44 . 9 38 .8 43 . 2 1 3 . 4 1 1 . 8 44 .0 4 5 . 0 4 3 . 9 4 3 . 6 1 2 . 1 1 1 . 4 44 . 0 43 . 5 43 . 2 44 . 5 1 2 . 8 1 2 . 0 4 4 . 5 43 . 2 1 2 . 3 4 2 . 8 44 . 9 1 2 . 3 45 . 5 4 2 . 3 1 2 . 2 46 . 4 44 . 4 45 . 4 42 .0 43 . 8 44 . 1 1 1 . 6 1 1 . 8 1 0 . 5 46 .0 42 . 1 1 2 . 0 44 . 7 43 . 1 1 2 . 2 46 . 5 38 .8 1 4 . 7 46 . 4 4 1 . 1 1 2 . 5 46 . 4 4 1 . 3 1 2 . 2 4 5 . 6 43 . 2 1 1 . 2 44 . 4 44 . 1 1 1 . 5 N Cl' \.11 APPENDIX 7 . 3 : Continued . Samp le 228L Code 20 228L 228L 228L 228L 228L 228L 228L 228L 21 22 23 K30 Z30 Z30 Z30 R30 228L 3 228L 228L 4 30 235 7 235 e22 235 16 235 24 235 25 235 26 235 R27 235 28 S i Oz 5 1 .6 1 52 . 10 5 1 . 92 50 .44 52 . 33 5 1 . 97 50 .25 5 1 . 64 5 1 .97 5 1 . 1 4 52 . 1 1 5 2 . 06 52 . 1 3 52 . 1 3 5 1 .83 52 . 09 50 . 78 5 1 . 97 52 .08 5 1 . 6 1 A 12o3 1 . 87 no2 0 . 49 Feo* 7 . 1 5 MnO 0 . 6 1 1 . 99 1 . 40 3 . 26 0 . 78 1 . 7 5 3 . 28 1 . 78 1 . 46 0 . 42 0 .32 0 . 58 0 . 22 0 . 39 0 . 54 0 . 42 0 . 43 7 . 52 7 . 93 7 .84 8 . 1 9 6 .82 7 . 76 7 . 08 6 . 78 0 . 46 0 . 8 1 0 . 22 0 . 80 0 . 5 1 0 . 18 0 . 44 0 . 53 2 . 42 1 . 40 1 . 30 0 . 54 0 . 34 0 . 33 7 .80 7 . 64 6 . 86 0 . 34 0 . 6 7 0 . 64 1 . 86 1 . 62 1 . 83 1 . 5 1 3 . 1 5 1 . 79 1 . 95 1 . 7 1 0 . 48 0 . 36 0 . 49 0 . 40 0 . 49 0 . 43 0 . 52 0 . 44 7 . 99 7 . 63 8 . 02 7 . 7 7 7 . 90 8 . 1 3 8 .03 7 . 73 0 . 44 0 . 45 0 . 53 0 . 62 0 . 33 0 .49 0 . 76 0 . 56 MgO 1 5 . 75 1 4 . 6 5 1 4 . 7 7 1 4 . 00 1 4 . 94 1 5 . 75 1 4 .26 1 5 . 49 1 5 . 6 7 1 5 . 69 1 5 . 58 1 5 . 9 1 1 5 . 22 1 5 . 52 1 5 . 20 1 5 . 43 1 4 . 1 9 1 5 . 04 1 5 .82 1 5 . 68 CaO 2 1 . 4 7 23 . 04 22 . 40 23 . 10 2 1 . 99 22 . 06 22 .9 7 22 . 1 3 22 . 23 2 1 . 95 2 1 . 72 22 .04 2 1 . 54 2 1 . 04 20 . 96 2 1 . 1 7 22 . 9 7 2 1 . 42 20 . 24 20 .93 Na2o 0 . 39 0 . 35 0 . 4 1 0 . 32 0 . 34 0 . 43 0 . 25 0 . 33 0 . 34 0 . 28 0 . 4 7 0 . 3 1 0 . 40 0 . 35 0 . 37 0 . 3 7 0 . 25 0 .42 0 . 36 0 . 33 Tota l 99 . 34 100.53 99 . 96 99 . 76 99 . 59 99 . 6 7 99 .49 99 . 3 1 99 . 4 1 100 . 16 99 . 93 99 . 45 100 . 06 99 . 10 99 . 23 99 . 36 100 .06 99 . 69 99 . 76 98 . 99 Cat ions on the bas i s of 6 oxy9ens Si 1 . 928 1 . 93 1 1 . 94 1 1 . 889 1 . 962 1 . 933 1 . 886 1 . 931 1 . 939 1 . 902 1 . 94 1 1 . 942 1 . 937 1 . 949 1 . 940 1 . 94 7 1 . 895 1 . 940 1 . 937 1 . 936 ·A l 0 . 082 0 . 08 7 0 . 062 0 . 1 44 0 .034 0 .077 0 . 1 45 0 .078 0 . 064 0 . 106 0 .061 0 . 057 0 . 08 1 0 . 0 7 1 0 . 08 1 0 .067 0 . 1 39 0 . 079 0 . 085 0 .076 Ti 0 . 0 1 4 0 . 0 1 2 0 . 009 0 . 016 0 . 006 0 . 0 1 1 0 . 0 1 5 0 .0 1 2 0 . 0 1 2 0 . 0 1 5 0 .0 10 0 . 009 0 .0 13 0 .0 10 0 .0 1 4 0 .0 1 1 0 .0 14 0 .0 1 2 0 . 0 1 5 0 .0 1 2 Fe 0 . 223 0 . 233 0 . 248 0 . 246 0 . 257 0 . 2 1 2 0 . 244 0 . 22 1 0 . 2 1 2 0 . 243 0 . 238 0 . 2 14 0 . 248 0 . 239 0 . 25 1 0 . 243 0 . 24 7 0 . 254 0 . 250 0 . 242 Mn 0 . 0 19 0 . 0 1 4 0 . 026 0 . 007 0 . 025 0 . 0 1 6 0 . 006 0 . 0 14 0 . 0 1 7 0 . 0 1 1 0 . 02 1 0 . 020 0 .0 1 4 0 . 0 1 4 0 . 0 1 7 0 . 020 0 .010 0 . 0 1 5 0 . 024 0 .0 18 Mg 0 .877 0 . 809 0 .823 0 . 782 0 . 835 0 . 873 0 . 798 0 .863 0 . 8 7 1 0 . 869 0 .865 0 . 885 0 .843 0 .865 0 . 848 0 . 860 0 . 789 0 . 837 0 . 8 7 7 0 . 877 Ca 0 . 859 0 . 9 1 5 0 .897 0 . 927 0 . 883 0 . 879 0 . 924 0 . 887 0 . 889 0 .875 0 . 86 7 0 .881 0 . 858 0 . 843 0 . 84 1 0 . 848 0 . 9 19 0.857 0 . 806 0 . 84 1 Na 0 . 028 0 . 025 0 . 030 0 .023 0 . 025 0 . 03 1 0 .0 18 0 . 024 0 . 025 0 . 020 0 .034 0 . 022 0 . 029 0 . 025 0 .027 0 .027 0 .0 18 0 . 030 0 . 026 0 . 024 Sum 4 .031 4 . 026 4 . 034 4 . 034 4 .027 4 . 033 4 . 035 4 . 030 4 . 029 4 . 040 4 .036 4 . 03 1 4 . 023 4 . 0 1 7 4 . 0 1 9 4 . 022 4 . 03 1 4 . 024 4 . 0 19 4 . 026 Wo En Fs 4 3 . 9 44 . 7 1 1 . 4 46 . 7 4 1 . 3 1 1 . 9 4 5 . 6 4 7 . 4 4 1 . 8 40 . 0 1 2 . 6 1 2 . 6 44 . 7 4 4 . 8 4 2 . 3 4 4 . 4 1 3 . 0 1 0 . 8 4 7 . 0 45 .0 45 . 1 40 . 6 43 . 8 44 . 2 1 2 . 4 1 1 . 2 10 . 7 4 4 . 0 44 .0 43 . 8 43 . 9 1 2 . 2 1 2 . 1 4 4 . 5 4 4 . 7 1 0 . 8 44 .0 43 . 3 1 2 . 7 43 . 3 4 4 . 4 1 2 . 3 43 . 3 43 . 7 1 2 . 9 43 . 5 44 . 1 1 2 . 5 4 7 . 0 40 . 4 1 2 . 6 44 . 0 4 3 . 0 1 3 .0 4 1 . 7 45 . 4 1 2 . 9 42 . 9 44 . 7 1 2 . 4 1\.) 0\ 0\ APPENDIX 1 . 3 r Continued . Samp le 243 Code i 243 243 i h9 12 243 243 243 1 7 18 19 243 2 243 4 243 1 1 243 24 S i02 5 1 . 94 5 1 . 74 52 . 1 3 53 .07 5 1 . 99 52 .07 52 . 48 52 . 1 1 52 . 33 5 2 . 32 246 K22 246 Z22 246 Z22 246 Z22 246 R22 246 24 246 2 1 246 K25 n . d . 52 . 25 n . d . 5 1 . 53 n . d . 53 . 35 52 . 30 5 1 . 96 A12o3 2 . 36 1 . 68 1 . 85 1 . 44 1 . 94 1 . 98 1 . 93 3 . 05 2 . 1 1 2 . 1 5 2 . 72 2 . 70 1 . 79 3 . 42 2 . 4 1 1 . 48 1 . 79 2 . 39 T i02 0 . 50 0 . 44 0 . 33 0 . 38 0 . 5 1 0 . 4 7 0 . 39 0 . 68 0 . 4 7 0 . 69 0 . 66 0 . 55 0 . 46 0 . 6 1 0 . 5 1 0 . 37 0 . 39 0 . 40 Feo* 7 . 5 1 7 . 89 8 .03 7 . 63 7 .83 8 . 01 7 . 1 1 7 . 79 7 . 38 8 . 60 7 . 86 7 . 54 7 . 69 7 .84 7 . 69 6 . 96 7 . 7 1 7 . 56 MnO 0 . 39 0 . 5 7 0 . 59 0 . 68 0 . 53 0 . 52 0 . 35 0 . 45 0 . 48 0 . 4 1 0 . 50 0 . 35 0 . 52 0 . 28 0 . 42 0 . 59 0 . 5 1 0 . 35 MgO 1 5 .62 1 5 .0 1 1 4 . 75 1 5 . 89 1 5 .42 1 5 . 1 1 1 5 . 6 7 1 4 . 90 1 5 . 34 1 5 . 6 7 1 5 . 62 14 .69 1 5 .83 14 .48 1 5 . 64 1 5 .03 1 5 . 1 7 1 4 . 92 C aO 2 1 . 35 20 . 79 21 . 43 2 1 . 36 20 . 9 1 2 1 . 46 22 . 20 21 . 31 2 1 . 48 20 . 76 2 1 . 60 22 . 10 2 1 .82 22 . 42 22 . 1 7 22 . 58 22 . 2 1 2 2 . 86 Na20 0 . 40 0 .43 0 . 48 0 . 34 0 . 37 0 . 30 0 . 38 0 . 40 0 . 4 5 0 . 38 0 . 4 7 0 . 35 0 . 36 0 . 30 0 .43 0 . 40 0 . 44 0 . 4 1 Tota l 100 . 0 7 98 . 55 99 . 59 100 . 79 99 . 50 99 . 92 1 00 . 5 1 100 . 69 100 .04 1 00 . 98 Cat i on s on the bas i s of 6 oxygens S i A I T i Fe Mn Mg ea Na Sum Wo En Fs 1 . 924 1 . 949 1 . 947 1 . 952 1 . 938 1 . 937 1 . 935 1 . 9 19 1 . 938 1 . 926 0 . 103 0 . 07 5 0 .081 0 . 062 0 . 085 0 . 087 0 . 084 0 . 132 0 . 092 0 . 093 0 . 01 4 0 . 01 2 0 . 009 0 .0 1 1 0 .0 14 0 . 0 1 3 0 . 0 1 1 0 . 0 1 9 0 . 0 1 3 0 . 0 19 0 . 233 0 . 249 0 . 25 1 0 . 235 0 . 244 0 . 249 0 . 2 1 9 0 . 240 0 . 229 0 . 265 0 . 0 1 2 0 . 018 0 .0 19 0 .021 0 . 0 1 7 0 .016 0 . 0 1 1 0 . 0 1 4 0 . 0 1 5 0 .0 1 3 0 .862 0 . 843 0 .82 1 0 .87 1 0 .857 0 . 838 0 . 86 1 0 . 818 0 .847 0 . 860 0 . 84 7 0 .839 0 . 858 0 . 842 0 . 835 0 . 855 0 .877 0 .841 0 . 852 0 . 8 19 0 . 029 0 . 03 1 0 . 035 0 . 024 0 .027 0 . 022 0 . 027 0 . 029 0 . 032 0 . 027 4 .025 4 . 0 1 7 4 .020 4 .018 4 .018 4 . 0 1 7 4 . 026 4 . 0 1 1 4 .0 19 4 . 022 43 . 6 43 . 5 44 . 4 44 . 4 43 . 7 4 2 . 6 1 2 . 0 1 2 . 9 1 3 .0 4 3 . 2 43 . 1 44 .0 44 .8 44 . 7 44 . 2 43 . 1 44 . 0 1 2 . 1 1 2 . 6 1 2 . 8 1 1 . 2 44 . 3 43 . 1 1 2 . 6 44 . 2 42 . 1 43 . 9 44 . 2 1 1 . 9 1 3 . 6 1 00 . 35 1 . 928 0 . 1 1 7 0 . 0 1 5 0 . 233 0 .0 1 1 0 . 808 0 .874 0 . 025 4 . 0 1 1 43 . 7 4 5 . 6 43 . 9 4 2 . 2 1 2 . 4 1 2 . 2 100 . 88 1 . 900 . 0 . 149 0 .0 1 7 0 . 242 0 . 009 0. 796 0 . 886 0 . 021 4 . 019 4 3 . 8 46 . 1 44 . 2 4 1 . 4 1 2 . 0 1 2 . 6 100 . 76 100 . 52 100 . 85 1 . 962 1 . 936 1 . 9 19 0 .064 0 .078 0 . 104 0 .0 10 0 . 0 1 1 0 . 0 1 1 0 . 2 14 0 . 239 0 . 233 0 .0 18 0 . 016 0 . 01 1 0 .824 0 .837 0 . 82 1 0 . 890 0 . 88 1 0 . 904 0 . 029 0 . 032 0 . 029 4 . 010 4 .030 4 . 033 44 . 4 46 . 2 4 3 . 6 42 . 7 1 2 . 0 1 1 . 1 4 5 . 0 42 . 8 1 2 . 2 46 . 2 4 1 . 9 1 1 . 9 N 0\ -.J APPENDIX 7 . 3 a Continued . Sample Code 246 Z25 246 246 Z25 R25 246 20 246 19 246 K 1 8 246 1 78 251 251 i p27 38 251 z 251 K41 251 Z41 251 Z41 251 Z41 251 R41 251 1 1 25 1 9 251 6 s 1o2 50 . 79 5 1 .94 5 1 . 64 52 .42 52 .44 5 2 . 49 5 1 .45 50 . 22 52 . 09 52 . 36 5 1 . 48 5 1 . 50 52 . 1 5 5 1 . 80 52 . 68 5 1 . 72 5 1 . 34 5 1 . 7 1 A 1 2o3 3 . 0 7 2 .42 2 . 18 1 . 8 1 1 . 62 1 . 85 2 . 98 2 . 63 1 . 79 2 . 1 2 3 . 18 2 . 68 2 .45 2 . 19 1 . 76 2 .05 2 . 61 2 . 1 1 r 1o2 o . 69 o . 6o o . 59 o . 42 o . 44 o . 53 o .48 o . 7 7 o . 48 o . 55 o . 68 o . 59 o .45 o . 53 o . 52 o . 53 o . 58 o .6o Feo* 8 .08 7 . 74 7 . 56 7 . 5 7 7 . 66 7 . 1 2 8 . 73 7 . 78 7 . 75 7 . 85 7 . 70 7 . 57 7 . 39 7 . 1 3 7 . 64 7 . 53 7 . 40 7 . 45 MnO 0 . 3 7 0 .42 0 . 25 0 . 58 0 . 54 0 .40 0 . 5 1 0 . 3 7 0 . 47 0 .49 0 . 34 0 . 36 0 . 36 0 .44 0 . 50 0 .43 0 . 26 0 . 3 1 M90 14 . 72 1 5 . 1 3 1 5 . 73 1 5 . 6 1 1 5 . 50 16 . 1 7 1 3 . 6 7 1 5 . 23 1 5 .82 1 5 .40 14 . 94 1 5 . 44 1 5 . 52 1 5 . 5 1 1 5 . 89 1 5 . 9 7 1 5 . 49 1 5 . 7 1 CaO 22 .07 2 1 . 93 2 1 . 52 2 1 .42 2 1 . 72 2 1 . 55 22 . 26 2 1 . 32 20 . 65 2 1 . 39 22 . 02 2 1 . 78 22 . 18 2 1 . 10 20 . 70 20 . 84 22 . 3 7 2 1 . 6 7 Na2o o . 4 1 o . 4 1 o . 4o o . 33 o . 38 o . 34 o . 58 o . 48 o . 36 o . 4 1 o . 35 o . 35 o . 32 o . 38 o . 3 7 o .4o o . 3 1 o . 39 Tota l 1 00 . 20 100 . 59 99 . 8 7 100 . 1 6 100. 30 100 .45 100 .66 98 . 80 99 . 4 1 100 . 5 7 100 . 69 100.27 100.82 99 .08 1 00 . 06 99 . 4 7 100 . 36 99 . 95 Cat i ons on the bas i s of 6 oxygens S i � .892 1 . 920 1 . 9 19 1 . 941 1 . 942 1 . 934 1 . 9 1 3 1 . 894 1 . 941 1 . 933 1 . 900 1 . 908 1 . 920 1 . 934 1 . 948 1 . 927 1 . 902 1 . 920 A l 0 . 1 35 0 . 105 0 . 095 0 .079 0 . 07 1 0 . 080 0 . 1 3 1 0 . 1 1 7 0 .079 0 . 092 0 . 1 38 0 . 1 1 7 0 . 1 06 0 . 096 0 . 077 0 . 090 0 . 1 14 0 . 092 T1 0 . 0 1 9 0 .0 1 7 0 .016 0 .0 12 0 .012 0 . 0 1 5 0 .0 1 3 0 . 022 0 .0 1 3 0 .015 0 .0 19 0 .0 16 0 .0 12 0 . 01 5 0 . 014 0 . 0 1 5 0 . 016 0 . 0 1 7 Fe 0 . 252 0 . 239 0 . 235 0 . 234 0 . 237 0 . 2 1 9 0 . 27 1 0 . 245 0 . 242 0 . 242 0 . 238 0 . 235 0 . 228 0 . 223 0 .236 0 . 235 0 . 229 0 . 23 1 Mn 0 .0 12 0 . 0 1 3 0 . 008 0 .0 18 0 .0 1 7 0 .0 12 0 .016 0 . 0 12 0 .0 1 5 0 .015 0 . 0 1 1 0 . 0 1 1 0 .0 1 1 0 .0 14 0 .0 16 0 . 0 14 0 . 008 0 . 010 Mg 0 . 8 1 7 0 . 833 0 . 8 7 1 0 .86 1 0 .855 0 . 888 0 . 757 0 . 856 0 .879 0 . 847 0 . 822 0 . 853 0 .851 0 .863 0 .876 0 . 887 0 .855 0 .870 Ca 0 . 88 1 0 . 869 0 .857 0 . 850 0 . 862 0 . 85 1 0 .887 0 . 862 0 . 825 0 . 846 0 .87 1 0 . 865 0 .875 0 . 844 0 . 820 0 .832 0 . 888 0 . 862 Na 0 . 030 0 . 029 0 . 029 0 .024 0 . 027 0 . 024 0 . 042 0 . 035 0 . 026 0 . 029 0 . 025 0 . 025 0 . 023 0 . 028 0 . 027 0 . 029 0 . 022 0 . 028 Sum 4 . 036 4 .026 4 . 031 4 . 020 4 . 024 4 .023 4 . 030 4 . 043 4 .019 4 .021 4 . 024 4 .030 4 . 026 4 .0 1 7 4 . 0 1 3 4 . 028 4 . 036 4 .03 1 Wo En Fs 45 . 2 44 . 7 43 . 7 41 . 9 42 . 9 44 . 4 1 2 . 9 1 2 . 3 1 2 . 0 43 . 7 44 . 1 43 .4 44 . 3 4 3 . 8 45 . 3 1 2 . 0 12 . 1 1 1 . 2 46 . 3 39 . 5 14 . 2 43 . 9 4 3 . 6 12 . 5 42 .4 45 .2 1 2 . 4 43 . 7 4 3 .8 1 2 . 5 45 . 1 42 . 6 1 2 . 3 44 . 3 44 .8 43 . 7 43 . 7 43 .6 44 . 7 1 2 . 0 1 1 . 6 1 1 . 5 42 . 4 45 . 3 12 . 2 42 .6 45 .0 43 .9 4 5 . 4 43 .4 44 . 3 1 2 . 0 1 1 . 6 1 1 . 8 N "' CD APPENDIX 7 . 3 : Continued. Samp le 256 Code 1 1 256 256 256 256 256 256 1 6 256 256 256 256 256 256 256 256 1 7 26 28 K29 Z29 Z29 Z29 Z29 256 256 256 Z29 Z29 R29 7 K 1 2 R 1 2 1 3 1 5 s 1o2 48 . 3 1 5 2 . 23 n . d . 5 1 . 1 3 5 1 . 72 5 1 . 93 5 2 . 0 7 49 .88 52 . 1 2 5 1 . 27 50 . 2 1 48 . 76 5 1 . 09 5 1 . 75 50 . 36 50 .89 51 . 20 5 1 . 8 7 A12o3 5 .86 2 . 53 2 . 52 2 .92 2 . 90 2 . 54 2 . 7 1 4 . 55 1 . 8 7 2 . 73 4 . 73 5 . 34 2 .92 3 . 00 3 . 73 3 . 09 3 . 32 2 .93 Tio2 0 .82 o .62 o . 6 7 o .6 7 o .69 o . 55 o . 62 o . 66 o . 5o o . 5 7 o . 6 1 o . 8 1 o . 56 o . 5o o . 68 o . 6 1 o . 59 o . 57 Feo* 8 . 00 7 . 72 8 . 1 7 8 . 38 8 .05 7 . 7 1 7 .86 7 .68 7 . 38 7 . 8 7 6 . 99 8 . 10 7 . 53 7 . 75 7 . 9 7 7 . 78 8 . 03 7 . 44 MnO 0 . 2 1 0 . 36 0 . 35 0 . 35 0 . 38 0 . 29 0 . 35 0 . 30 0 . 4 1 0 . 4 1 0 . 00 0 . 24 0 . 33 0 . 29 0 . 28 0 . 3 1 0 . 32 0 . 4 7 M90 1 2 . 96 1 5 . 46 1 5 . 40 1 5 . 05 1 4 . 86 1 5 . 1 9 1 4 . 92 1 3 .42 1 5 .89 1 5 .25 1 4 .25 1 3 . 43 1 4 . 99 1 4 . 9 1 1 4 . 64 1 4 . 79 1 4 . 59 1 5 . 08 CaO 22 . 62 2 1 . 1 4 2 1 . 55 2 1 . 3 1 2 1 . 35 21 .64 20 .84 22 . 59 21 .23 21 . 39 23 . 64 22 . 44 2 1 . 95 21 . 72 2 1 . 59 21 . 69 2 1 . 34 21 . 52 Na2o 0 . 21 0 . 38 0 . 53 0 .48 0 . 40 0 . 39 0 . 43 0 . 38 0 . 36 0 .42 0 . 27 0 . 3 7 0 . 3 7 0 . 4 1 0 . 4 1 0 . 42 0 .4 7 0 . 36 Tota l 99 . 05 1 00 . 44 100 .29 100 . 35 100 .24 99 .80 99 .46 99 . 76 99 . 91 1 00 . 70 99 .49 99 . 74 100 . 33 99 . 66 99 . 58 99 . 86 100.24 Cations on the bas i s of 6 oxy9ens S1 1 . 824 1 . 926 A l 0 . 26 1 0 . 1 10 T1 0 . 023 0 . 0 1 7 Fe 0 . 253 0 . 238 Mn 0 . 007 0 . 0 1 1 M9 0 . 729 0 .850 ea 0 . 9 1 5 0 .835 Na 0 . 020 0 . 027 Sum 4 .032 4 .0 1 5 1 . 900 1 . 9 1 5 1 . 922 1 . 932 1 . 870 1 . 935 1 . 908 1 . 855 1 .833 1 . 904 1 . 9 15 1 . 882 1 . 90 1 1 . 906 1 . 918 0 . 1 28 0 . 127 0 . 1 1 1 0 . 1 19 0 . 20 1 0 . 082 0 . 1 20 0 . 206 0 . 23 7 0 . 1 28 0 . 1 3 1 0 . 1 64 0 . 1 36 0 . 146 0 . 1 28 0 .0 19 0 . 0 1 9 0 . 0 1 5 0 . 0 1 7 0 . 0 1 9 0 .0 14 0 .0 16 0 . 0 1 7 0 . 023 0 .0 16 0 . 0 1 4 0 .0 1 9 0 . 0 1 7 0 . 0 1 7 0 .0 16 0 . 260 0 . 249 0 . 239 0 . 244 0 . 24 1 0 . 229 0 . 245 0 . 2 1 6 0 . 255 0 . 235 0 . 240 0 . 249 0 . 243 0 . 250 0 . 230 0 . 0 1 1 0 . 0 1 2 0 . 009 0 . 0 1 1 0 .0 10 0 . 0 1 3 0 . 0 1 3 0 . 000 0. 008 0 . 0 10 0 .009 0 . 009 0 .0 10 0 .010 0 . 0 1 5 0 . 833 0 . 820 0 . 838 0 .825 0 . 750 0 .879 0 .846 0 . 785 0 . 753 0 . 833 0 . 822 0 . 8 1 5 0 . 823 0 . 809 0 . 83 1 0 . 849 0 .847 0 . 858 0 . 828 0 . 907 0 . 845 0 . 853 0 . 936 0 . 904 0 . 8 7 7 0 .861 0 . 864 0 . 868 0 . 85 1 0 .853 0 . 035 0 .029 0 . 028 0 .031 0 .028 0 . 026 0 . 030 0 .0 19 0 . 027 0 .027 0 . 029 0 . 030 0 . 030 0 . 034 0 . 026 4 .035 4 . 0 1 7 4 . 02 1 4 . 007 4 . 025 4 . 023 4 .031 4 . 034 4 .039 4 . 029 4 . 021 4 . 032 4 .029 4 . 022 4 .0 1 5 Wo En Fs 48 . 2 4 3 . 4 43 . 7 43 . 7 44 . 2 44 . 4 43 . 7 4 7 . 8 38 . 4 44 . 2 4 3 . 4 4 2 . 9 42 .8 43 . 3 43 . 5 39 . 5 1 3 . 3 1 2 . 4 1 2 . 9 1 3 . 4 1 3 . 0 1 2 . 3 1 2 . 9 12 . 7 43 . 2 4 3 . 9 4 5 . 0 43 . 5 1 1 . 7 1 2 . 6 48 . 3 40 . 5 1 1 . 2 4 7 . 3 39 .4 1 3 . 3 45 . 1 44 . 8 44 .8 42 . 8 42 .8 42 . 3 1 2 . 1 1 2 . 5 1 2 . 9 44 . 9 42 . 6 1 2 . 6 44 . 6 42 . 4 1 3 . 1 44 . 6 43 .4 1 2 .0 1\J 01 -o APPENDIX 7 . 3 s Continued . Sample 256 256 256 256 256 256 256 256 256 256 256 256 256 256 Code K30 Z30 Z30 Z30 Z30 Z30 Z30 R30 eh32 et42 K49 48 47 46 256 44 256 4 1 256 s1o2 52 . 12 50 .95 50 . 1 3 5 1 . 36 50 . 4 7 51 . 2 1 51 . 4 7 51 .43 5 1 . 32 n . d . 53 . 1 5 5 1 .85 5 1 . 1 1 5 1 . 69 51 . 7 1 5 1 . 52 50 . 5 7 A1 2o3 1 . 95 2 . 84 3 .89 2 . 70 3 . 56 3 . 00 2 .89 2 . 72 2 . 54 2 . 08 1 . 40 2 . 22 3 . 2 7 2 . 54 2 .83 2 . 99 3 .94 ' r1o2 o .45 o . 54 o .59 o .53 o . 7o o . 6o o . 6 1 o . 53 o .69 o . 5o 0 . 20 o . 52 0 . 12 o . 5o o . 59 o . 5 7 o . 56 Feo* 7 . 69 8 .6 1 8 . 37 7 .8 1 7 . 99 7 . 76 7 .97 7 . 47 8 . 00 8 .47 7 . 81 7 . 50 8 . 23 8 . 26 7 . 92 7 . 58 6 .42 MnO 0 . 34 0 . 29 0 . 29 0 . 30 0 . 26 0 .4 1 0 . 39 0 . 30 0 .42 0 . 38 0 . 62 0 . 33 0 . 3 7 0 . 38 0 . 39 0 . 35 0 . 00 MgO 1 5 . 56 1 4 .87 14 . 1 6 1 5 . 22 1 4 . 52 1 5 . 1 5 1 5 .05 1 4 . 92 1 5 . 18 1 5 . 6 1 1 4 .29 1 5 . 39 1 4 . 91 1 4 .88 1 5 .0 1 1 5 . 08 1 4 . 53 CaO 2 1 .49 2 1 . 33 21 .45 2 1 . 70 2 1 . 67 21 .83 2 1 .43 22 . 04 2 1 . 53 2 1 . 05 23 .01 2 1 . 54 2 1 .49 21 . 6 1 21 . 39 2 1 . 66 23 . 48 Na2o 0 . 39 0 . 39 0 . 39 0 . 4 1 0 . 44 0 . 39 0 . 38 0 . 38 0 . 39 0 .42 0 . 44 0 . 38 0 . 43 0 . 36 0 . 42 0 .40 0 . 26 Tota l 99 . 99 99 .82 99 . 27 100 .03 99 . 6 1 100 . 35 100 . 1 9 99 . 79 100 .07 Cations on the bas f s of 6 oxygens S f 1 . 934 1 .904 1 .883 1 . 909 1 .887 1 .899 1 . 910 1 . 914 1 . 909 Al 0 . 085 0 . 1 25 0 . 1 72 0 . 1 18 0 . 157 0 . 1 3 1 0 . 1 26 0 . 1 19 0 . 1 1 1 T 1 0 .013 0 . 01 5 0 .017 0 .015 0 .020 0 .0 1 7 0 . 01 7 0 .015 0 . 01 9 Fe 0 . 239 0 . 269 0 . 263 0 . 243 0 . 250 0 .24 1 0 . 247 0 . 233 0 . 249 Mn 0 . 0 1 1 0 . 009 0 . 009 0 . 009 0 .008 0 . 0 13 0 . 012 0 .009 0 .0 1 3 Mg 0 . 86 1 0 . 828 0 . 793 0 . 843 0 . 809 0 .837 0 .832 0 . 828 0 . 842 ea 0 . 855 0 . 854 0 . 863 0 .864 0 . 868 0 . 867 o .852. 0 .879 0 . 858 Na 0 . 028 0 . 028 0 . 028 0 .030 0 . 032 0 . 028 0 . 027 0 .027 0 . 028 Sum 4 .025 4 .033 4 .028 4 .032 4 . 03 1 4 .033 4 . 024 4 .025 4 .030 100 . 92 99 . 73 100 . 53 100 . 22 100 . 26 100 . 1 5 99 . 76 1 . 962 1 . 928 1 .894 1 . 920 1 . 9 1 6 1 . 909 1 .880 0 . 06 1 0 . 097 0 . 143 0 . 1 1 1 0 . 1 24 o . 1 3 1 0 . 1 73 0 . 006 0 .0 1 5 0 . 020 0 .0 14 0 .0 16 0 . 016 0 . 0 16 0 . 24 1 0 . 233 0 . 255 0 . 257 0 . 245 0 . 235 0 . 200 0 . 0 19 0 . 010 0 . 012 0 . 0 1 2 0 .0 1 2 0 .01 1 0 . 000 0 . 786 0 . 853 0 .823 0 . 824 0 . 829 0 .833 0 . 805 0 . 9 10 0 . 858 0 . 853 0 . 860 0 . 849 0 . 860 0 . 935 0 . 03 1 0 . 027 0 . 03 1 0 . 026 0 .030 0 .029 0 .0 19 4 . 01 7 4 . 022 4 . 030 4 . 023 4 .021 4 . 024 4 .027 Wo En Fs 43 . 7 44 . 0 1 2 . 2 4 3 . 8 4 5 . 0 44 . 3 45 . 1 44 .6 44 . 1 42 . 4 4 1 . 3 4 3 . 2 42 . 0 43 .0 43 . 1 1 3 . 8 1 3 . 7 1 2 . 4 1 3 .0 1 2 . 4 1 2 . 8 45 . 3 42 . 7 1 2 .0 44 . 0 4 2 . 6 4 7 . 0 4 3 . 2 44 . 0 40 . 6 1 2 . 8 1 3 . 4 1 2 . 4 44 . 1 44 . 2 4 3 . 9 42 . 6 1 2 . 0 1 3 . 2 44 . 3 42 . 5 1 3 . 2 44 . 1 43 . 1 12 . 8 44 .6 43 . 2 1 2 . 2 48 . 2 4 1 . 5 10 . 3 IV --.1 0 2 7 1 APPENDIX 7 . 3 : Continued . Samp l e 89 90 90 90 84 84 84 84 Code 36 25 1 3 6 1 0 1 1 K 1 2 R 1 2 S i 02 49 . 70 50 . 6 1 52 . 27 53 . 24 5 1 . 9 7 52 . 1 7 52 . 6 3 5 1 . 69 Al 203 2 . 95 2 . 68 2 . 48 2 . 5 5 1 . 5 2 1 . 5 1 1 . 32 2 . 06 T i02 0 . 38 0 . 79 0 . 2 1 0 . 24 0 . 43 0 . 35 0 . 34 0 . 50 Feo* 7 . 49 1 2 . 05 4 . 8 1 5 . 4 7 1 0 . 37 9 . 50 9 . 32 9 . 06 M nO 0 . 1 6 0 . 26 0 . 1 8 0 . 00 0 . 63 0 . 6 1 0 . 59 0 . 45 M gO 1 6 . 04 1 4 . 53 1 7 . 08 1 7 . 68 1 4 . 02 1 3 . 94 1 5 . 2 5 1 4 . 7 1 C aO 20 . 1 8 1 8 . 6 3 2 1 . 9 1 20 . 6 1 20 . 30 2 1 .0 1 1 9 . 52 1 9 . 85 Na20 0 . 38 0 . 43 0 . 24 0 . 30 0 . 3 1 0 . 34 0 . 23 0 . 28 C r203 0 . 28 0 . 1 8 0 . 25 0 . 1 7 0 . 00 0 . 00 0 . 00 0 . 00 Tota l 97 . 56 99 . 56 99 . 43 1 00 . 26 99 . 55 99 .43 99 . 20 98 . 70 Cat i ons on the b as i s of 6 oxygens S i 1 . 890 1 . 902 1 . 926 1 . 938 1 . 956 1 . 96 1 1 . 9 70 1 . 948 A l 0 . 1 32 0 . 1 1 9 0 . 1 08 0 . 1 09 0 . 06 7 0 . 067 0 . 058 0 . 092 T i 0 . 0 1 1 0 . 022 0 . 006 0 . 007 0 . 0 1 2 0 . 010 0 . 0 1 0 0 . 0 1 4 Fe 0 . 238 0 . 37 9 0 . 1 48 0 . 1 6 7 0 . 326 0 . 299 0 . 292 0 . 286 Mn 0 . 005 0 . 008 0 . 006 0 . 000 0 . 020 0 . 0 19 0 . 0 1 9 0 . 0 1 4 Mg 0 . 909 0 . 8 1 4 0 . 938 0 . 959 0 . 786 0 . 781 0 . 8 5 1 0 . 826 C a 0 . 822 0 . 7 50 0 . 865 0 . 804 0 . 8 1 9 0 . 846 0 . 783 0 . 802 Na 0 . 028 0 . 0 3 1 0 . 0 1 7 0 . 02 1 0 . 023 0 .025 0 . 0 1 7 0 .020 Cr 0 . 008 0 . 00 5 0 . 007 0 . 005 0 . 000 0 . 000 0 . 000 0 . 000 Sum 4 . 043 4 . 030 4 . 020 4 . 009 4 . 0 1 0 4 . 008 3 . 999 4 . 002 Wo 41 . 7 38 . 6 44 . 3 4 1 . 7 42 . 4 43 . 9 40 . 7 4 1 . 9 En 46 . 2 4 1 . 9 48 . 1 49 . 7 40 . 7 40 . 6 44 . 2 43 . 2 F s 1 2 . 1 1 9 . 5 7 . 6 8 . 6 1 6 . 9 1 5 . 5 1 5 . 2 1 4 . 9 APPENDIX 7 . 4 z ORTHOPYROXENE Sample 256 251 251 25 1 246 243 235 235 235 22&n 228u 228u 222 s1o2 52 .9 1 54 . 18 53 . 77 54 . 14 54 . 60 53 . 78 5 3 . 34 53 .08 53 . 42 54 . 38 - - 54 . 16 Al 2o3 1 .82 1 .02 1 . 22 0 .89 0 . 86 1 .40 0 . 72 1 . 29 0 . 74 0 . 55 0 . 84 0 . 99 1 . 10 no2 0 . 28 0 . 31 0 . 29 0 . 1 7 0 . 20 0 . 28 0 .24 0 . 2 1 0 . 20 0 . 1 1 0 . 1 5 0 .00 0 . 20 FeO* 1 6 . 27 1 5 . 04 1 5 . 5 7 1 4 . 97 16 .08 1 4 . 65 1 6 . 38 1 6 . 04 1 6 . 42 16 . 35 1 5 . 90 1 5 .06 1 3 . 95 MnO 0.83 0 .83 0 . 73 0 . 7 7 0 .87 0 . 80 0 . 98 0 .94 1 .04 1 . 27 0 . 92 0 . 69 1 . 20 MgO 26 .01 27 . 14 26 . 69 27 . 12 26 . 99 26 . 7 1 25 . 75 26 . 35 25 . 79 26 . 68 2 7 . 45 28 . 88 28 .07 CaO 1 . 38 1 . 39 1 . 43 1 . 26 1 . 1 7 1 . 35 1 . 35 1 . 24 1 . 28 1 .08 1 .06 0 . 82 0 . 92 Tota l 99 . 50 99 .9 1 99 . 70 99 .32 100 . 7 7 98 . 9 7 98 . 76 99 . 1 5 98 . 98 100.42 - - 99 . 60 Cat i ons on the bas i s of 6 oxygens S i 1 . 936 1 . 960 1 .954 1 . 968 1 . 965 1 . 960 1 . 96 7 1 . 947 1 . 968 1 . 971 - - 1 . 956 AI 0 .078 0 . 043 0 .052 0 .038 0 . 036 0 . 060 0 .03 1 0 . 056 0 .032 0 .023 - - 0 .047 T1 0 .008 0 .008 0 .008 0 . 005 0 .005 0 .008 0 .007 0 .006 0 .006 0 . 003 - - 0 .006 Fe 0 .498 0 . 455 0 .473 0. 455 0 . 484 0 .447 0 . 505 0 .492 0 . 506 0 .496 - - 0 . 42 1 - Mn 0 .026 0 .025 0 .022 0 .024 0 .027 0 .025 0 . 031 0 . 029 0 .032 0 .039 - - 0. 037 Mg 1 .4 18 1 . 463 1 . 446 1 . 469 1 . 448 1 . 45 1 1 . 4 16 1 . 441 1 . 4 1 6 1 . 441 - - 1 . 5 1 1 ea 0.054 0 .054 0 .056 0 .049 0 . 045 0 . 053 0 .053 0 . 049 0 . 05 1 0 .042 - - 0 .036 Sum 4 .0 1 7 4 .010 4 .0 12 4 . 008 4 .01 1 4 . 002 4 .010 4 .0 19 4 .010 4 .015 - - 4 .014 En 74 .0 76 . 3 75 . 3 76 . 3 74 . 9 76 . 5 73 . 7 74 . 5 73 . 7 74 . 4 75 .5 77 .4 78 . 2 N -.J N APPENDIX 7 . 4 1 Continued. SIIIIPle 90 90 90 90 90 90 90 90 90 90 90 89 89 89 89 89 89 89 89 89 S io2 50 .81 50 . 97 50 . 28 5 1 . 25 50 .88 52 .25 50 . 1 3 50 . 89 50 .99 5 1 .21 52 .47 51 . 58 5 1 . 79 52 . 50 50 .81 53 . 1 3 50 . 98 52 .38 5 1 .85 51 . 05 Al203 no2 FeO !linO M90 CaO 0 . 32 0 .44 0 .4 1 0 . 10 0 . 1 5 0 . 1 2 0 .47 0 . 3 1 0 . 1 1 0 . 00 0 . 1 9 0 .39 0 .00 0 . 1 0 0 . 39 0 . 00 2 7 . 59 27 . 18 28 .62 28 .38 2 7 . 97 26 . 37 28 . 14 27 .68 1 . 33 1 . 37 1 .44 1 . 52 1 . 3 7 1 .40 1 .60 1 . 37 1 7 . 84 1 7 .69 16 .93 1 6 .8 1 1 7 . 08 1 8 .09 1 7 . 19 1 7 . 64 0 . 78 1 . 14 0 .95 1 . 05 1 . 1 3 0 . 74 0 . 81 1 .00 0 .42 0 . 2 7 1 . 16 0 .88 1 .85 1 .44 0 . 95 0 . 90 0 .45 2 . 77 0 . 33 0 .42 o .oo o.oo o . 29 0 . 1 2 o .4 1 o . 34 o . 24 0 . 1 1 o . 1 3 0 . 20 · o .oo o . oo 2 7 . 3 7 26 .07 22 . 23 25 .49 20.45 1 6 . 33 25 .21 1 7 .20 26 .00 1 6 . 57 2 7 . 30 26 .40 0 . 99 1 . 33 0 . 98 1 . 34 0.43 0 .42 1 . 1 5 0 . 79 1 . 33 0 . 31 1 .45 1 . 1 9 18 . 72 1 8 . 75 2 1 . 78 19 .06 22 . 72 25 . 52 1 8 . 30 23 . 88 18 .89 25 . 64 1 8 . 27 1 8 . 73 1 . 16 0 . 75 1 . 30 1 .00 1 . 77 2 . 1 5 1 . 1 1 0 .97 0 . 93 1 . 31 0 . 73 0 . 82 Total 98 . 77 98 .94 98. 75 99 . 59 98 . 74 99 .04 98 . 36 98 . 97 99 .65 98 . 38 100.21 99 .47 99 .42 98 . 70 97 . 77 97 . 1 0 98 . 7 1 99 . 18 99 . 93 98 .6 1 Cations on the bas i s of 6 oxy9ens Si 1 . 980 1 .980 1 . 973 1 . 988 ·1 . 988 2 .012 1 .973 1 . 981 1 . 966 1 .988 1 . 959 1 . 973 1 . 934 1 . 940 1 . 977 1 . 995 1 . 974 1 . 920 1 .990 1 . 980 Al 0 .015 0 .020 0 .019 0 .021 0 .014 0 .009 0 .0 18 0 .018 0 . 019 0.012 0 .051 0 .040 0 .081 0 .063 0 .044 0.040 0 .02 1 0 . 120 0 .0 15 0 .019 Ti 0 .003 0 .004 0 .004 0 .003 0 .000 0 .000 0 .003 0 . 000 0 .000 0 . 000 0 .008 0 .003 0.012 0 . 009 0 .007 0 .003 0 . 004 0 .006 0 .000 0 . 000 Fe 0 . 899 0 .883 0 . 939 0 . 921 0 .9 14 0 . 849 0 . 926 0 .901 0 . 883 0 . 846 0 .694 0 .816 0 . 639 0 . 505 0 . 820 0 . 540 0 . 842 0 . 508 0 .8 76 0 .856 Mn 0.044 0 .045 0.048 0 . 050 0 .045 0 .046 0 .053 0 . 045 0 .032 0 . 044 0 .031 0 . 043 0 .014 0 .0 13 0 .038 0 . 025 0 .044 0 .010 0 . 047 0 . 039 M9 1 .036 1 .024 0 . 990 0 . 972 0 . 995 1 .038 1 .008 1 . 023 1 . 076 1 .085 1 .2 12 1 .087 1 . 264 1 .405 1 .061 1 . 336 1 .090 1 . 401 1 .045 1 .082 ea 0 .033 0 .047 0 .040 0.044 0 .047 0 .031 0 .034 0 .042 0.048 0 . 031 0 .052 0 .041 0 .071 0 .085 0 .046 0 . 039 0 .039 0 .051 0 . 030 0 .034 Sum 4 .010 4 . 005 4 .014 3 . 998 4 .004 3 . 984 4 .0 15 4 .010 4 .024 4 . 006 4 . 007 4 .003 4 .014 4 .020 3 . 994 3 . 987 4 .0 12 4 .015 4 . 003 4 .01 1 En 53 . 5 53. 7 51 . 3 5 1 .4 52 . 1 55 .0 52 . 1 53 . 2 54 . 9 56 . 2 63.6 57 . 1 66 .4 73 .6 56 .4 7 1 . 2 56 . 4 73 .4 54 .4 5 5 . 8 IV -..J w APPENDIX 7 . 4 z Continued. Sample 89 89 89 89 89 89 89 10 10 10 10 10 10 10 10 10 10 10 10 10 s toz 5 1 . 50 50 .68 5 1 . 16 5 1 . 94 49.45 5 1 .44 5o .o7 50.43 50 .29 52 . 73 50 .45 50 .33 53.63 50 . 59 50 .83 50 . 45 50 . 70 50 . 54 50 .35 50 . 95 Alz03 1 .01 1 .07 0 . 4 1 0 . 54 0 . 34 0 . 35 1 .03 0 . 39 0 . 42 1 . 19 0 . 36 0 .65 1 . 34 0 .42 0 .47 0 . 45 0 . 32 0 . 73 0 . 51 0 .42 Tf02 0 . 24 0 . 20 0 . 00 0 . 00 0 . 00 0 . 00 0 . 32 0 . 1 5 0 . 18 0 . 24 0 . 10 0 . 2 1 0 . 21 0 . 1 2 0 . 14 0 . 16 0 . 16 0 . 22 0 .00 0 . 1 9 FeO 1 9 .63 24 . 94 27 . 5 7 2 7 . 03 30 .32 2 7 . 1 6 31 . 04 30 . 1 5 31 .05 1 7 . 42 30 . 45 30 . 02 1 8 . 25 30 . 02 29 . 59 30 . 10 30 . 06 29 .41 29 .86 30 . 5 1 MnO 0 . 55 1 . 1 5 1 . 24 1 . 1 4 1 . 63 1 . 23 0 .85 1 .67 1 .87 0 .43 1 .82 1 . 72 0 . 52 1 .68 1 .65 1 .80 1 .66 1 .62 1 � 73 1 . 67 MgO 23 . 78 1 9 . 27 1 8 . 33 1 8 . 23 1 5 . 37 18 .43 1 4 . 34 15 .07 1 4 . 36 24 . 98 1 4 . 95 1 5 .02 24 .9 1 1 4 . 92 1 5 . 54 1 4 .86 14 .87 1 5 . 58 14 .93 1 4 . 7 1 CaO 1 .42 1 . 16 0 . 70 0 . 98 0 .84 0 . 75 2 .00 1 . 24 1 . 35 1 . 46 1 . 24 1 . 42 1 . 55 1 . 25 1 . 24 1 . 25 1 . 2 1 1 . 35 1 . 31 1 . 29 Total 98.13 98.47 99.41 99.86 97.95 99.36 99.65 99.10 99.52 98.45 99.37 99.37 100.41 99.00 99.46 99.07 98.98 99.45 98.69 99.74 Cations on the bas i s of 6 oxygens S1 1 . 944 1 .957 1 . 978 1 . 990 1 . 977 1 . 984 1 .968 1 . 988 1 . 985 1 . 957 1 . 987 1 .979 1 . 957 1 . 994 1 .989 1 . 990 1 . 999 1 . 978 1 . 992 1 . 996 Al 0 . 045 0 . 049 0 . 019 0 . 024 0 . 016 0 .0 16 0 . 048 0 .018 0 . 020 0 . 052 0 .0 1 7 0 . 030 0 . 058 0 . 020 0 .022 0 .021 0 .0 15 0 . 034 0 .024 0 .0 19 T t 0 . 007 0 .006 0 . 000 0 . 000 0 .000 0 .000 0 . 009 0 . 004 0 . 005 0 . 007 0 . 003 0 .006 0 . 006 0 . 004 0 .004 0 . 005 0 .005 0 . 006 0 .000 0 .006 Fe 0 . 620 0 .806 0 . 891 0 . 866 1 .014 0 .876 1 .020 0 . 994 1 .025 0 . 54 1 1 .003 0 . 987 0 . 557 0 . 990 0 . 968 0 . 993 0 . 991 0 . 962 0 . 988 1 .000 Mn 0 . 018 0 . 038 0 . 041 0 .037 0 . 055 0 . 040 0 . 028 0 . 056 0 .063 0 .0 14 0 .061 0 . 057 0 .016 0 .056 0 .055 0 . 060 0 . 055 0 .054 0 . 058 0 . 055 Mg 1 . 337 1 . 109 1 .056 1 . 041 0 . 916 1 .060 0 .840 0 .885 0 .845 1 . 382 0 .878 0 .880 1 . 355 0 .877 0 . 906 0.874 0 .874 0 . 909 0 . 880 0 .859 ea 0 . 057 0 . 048 0 . 029 0 . 040 0 . 036 0 .031 0 .084 0 . 052 0 . 057 0 . 058 0 . 052 0 . 060 0 . 061 0 . 053 0 .052 0 . 053 0 .051 0 .057 0 . 056 0 . 054 Sum 4 . 027 4 .0 12 4 . 0 13 3 . 998 4 .015 4 . 008 3 . 998 3 . 998 4 . 000 4 . 010 4 .001 4 . 000 4 . 009 3 . 992 3 . 996 3 . 995 3 . 989 3 . 999 3 .997 3 . 989 En 68 . 3 5 7 . 9 54 . 2 54 . 6 4 7 . 5 54 . 7 45 .2 47 . 1 45 . 2 71 . 9 46 . 7 4 7 . 1 70 . 9 4 7 . 0 48 . 3 46 .8 46 . 9 48 .6 47 . 1 46 .2 N ...J � 2 7 5 Append ix 8 : Proporti on of the s i l t f ract i on removed from the Tokomaru s i l t l oam du r ing the a c i d d i s s o lut ion treatments . 5-2l.lm ---- -- 2 0- Sl.lm - -- - - - - ------ 6 3 - 2 � m ------ No . Res idue HC l H2S iF 6 R e s i du e HC l H 2 S iF 6 Res idue T l 2 7 . 2 7 . 1 53 . 7 3 9 . 2 2 . 8 4 7 . 5 5 0 . 0 T2 3 2 . 3 6 . 5 58 . 5 3 5 . 0 2 . 7 4 8 . 2 49 . 0 T 3 2 1 . 3 4 . 5 85 . 3 1 0 . 2 1 . 8 6 6 . 7 3 1 . 5 T4 1 8 . 8 5 . 7 7 3 . 3 2 1 . 1 2 . 7 52 . 5 44 . 8 T 5 2 6 . 2 7 . 3 60 . 1 3 2 . 6 2 . 8 5 0 . 1 47 . 1 T 6 2 7 . 0 7 . 0 57 . 6 3 5 . 4 2 . 6 4 8 . 5 49 . 0 T7 2 6 . 5 6 . 8 53 . 6 3 9 . 6 2 . 4 4 6 . 0 5 1 . 6 TB 2 8 . 5 6 . 6 55 . 9 3 7 . 6 2 . 2 4 5 . 0 52 . 8 T9 3 0 . 7 6 . 7 55 . 4 3 8 . 0 2 . 6 4 6 . 8 5 0 . 6 T 1 0 3 1 . 9 6 . 5 54 . 3 3 9 . 3 2 . 5 4 7 . 7 49 . 7 T l l 3 0 . 0 6 . 5 54 . 5 ) 3 8 . 9 2 . 3 4 5 . 6 52 . 2 T 1 2 3 1 . 2 6 . 4 55 . 9 3 7 . 7 2 . 2 4 9 . 3 52 . 5 T 1 3 3 0 . 3 6 . 0 53 . 1 4 0 . 9 2 . 3 4 6 . 9 5 0 . 8 T 1 4 3 1 . 0 6 . 0 5 1 . 3 4 2 . 8 2 . 3 4 5 . 1 52 . 6 T 1 5 3 0 . 8 6 . 5 5 0 . 8 4 2 . 7 2 . 1 4 5 . 3 52 . 5 T 1 6 3 3 . 4 6 . 2 52 . 4 4 1 . 4 2 . 3 4 1 . 5 5 6 . 3 T 1 7 2 8 . 6 6 . 6 53 . 4 4 0 . 5 2 . 2 4 4 . 3 53 . 4 T 1 8 2 8 . 4 6 . 4 53 . 8 3 9 . 8 2 . 3 4 7 . 8 49 . 9 T 1 9 3 2 . 5 5 . 0 53 . 0 4 2 . 1 1 . 7 4 4 . 6 53 . 8 T2 0 3 2 . 2 3 . 8 53 . 0 4 3 . 2 1 . 1 4 4 . 9 54 . 0 T 2 1 4 3 . 6 2 . 9 54 . 6 4 2 � 5 1 . 0 4 3 . 2 55 . 8 T 2 2 4 1 . 9 2 . 3 53 . 7 4 4 . 0 1 . 0 4 0 . 1 58 . 9 T 2 3 4 0 . 1 1 . 8 52 . 4 4 5 . 8 0 . 8 4 1 . 4 57 . 8 T 2 4 3 6 . 4 1 . 9 47 . 8 5 0 . 3 0 . 7 3 5 . 5 63 . 9 T 2 5 4 0 . 0 2 . 0 56 . 3 4 1 . 8 0 . 6 4 2 . 0 57 . 4 Appendix 9 : Key to sample depths ( m ) . Tokomaru s i l t loam T l T2 T3 T4 T5 T6 T7 T8 T9 T l O 2 . 4 2 - 2 . 5 0 2 . 3 4 - 2 . 4 2 2 . 2 4 - 2 . 3 4 2 . 1 4 - 2 . 2 4 2 . 0 0 - 2 . 1 4 1 . 9 0- 2 . 0 0 1 . 8 0 - 1 . 9 0 1 . 7 0- 1 . 8 0 1 . 6 0- 1 . 7 0 1 . 5 0- 1 . 6 0 T l l 1 . 4 0- 1 . 5 0 T l 2 1 . 3 0- 1 . 4 0 T l 3 1 . 2 0- 1 . 3 0 T l 4 T l 5 T l 6 T l 7 T l 8 T l 9 T2 0 T2 l T2 2 T2 3 T2 4 T2 5 1 . 1 0- 1 . 2 0 1 . 0 0 - 1 . 1 0 0 . 9 0- 1 . 00 0 . 8 0- 0 . 9 0 0 . 7 0 - 0 . 8 0 0 . 6 0 - 0 . 7 0 0 . 5 0 - 0 . 60 0 . 4 0 - 0 . 5 0 0 . 3 0- 0 . 4 0 0 . 2 0- 0 . 3 0 0 . 1 0- 0 . 2 0 0 . 0 0 - 0 . 1 0 Hamil ton c l ay loam Rl R2 R3 R4 R5 R6 R7 R8 R9 R l O 0 . 0 - 0 . 1 0 . 1 - 0 . 2 0 . 2 - 0 . 3 0 . 3 - 0 . 4 0 . 4 - 0 . 5 0 . 5 - 0 . 6 0 . 6- 0 . 7 0 . 7 - 0 . 8 0 . 8 - 0 . 9 0 . 9 - 1 . 0 Te K owha i s i lt loam TK 1 TK2 TK3 TK4 TK5 TK6 TK7 TK8 TK9 TK 1 0 0 . 0- 0 . 1 0 . 1 - 0 . 2 0 . 2 - 0 . 3 0 . 3 - 0 . 4 0 . 4 - 0 . 5 0 . 5 - 0 . 6 0 . 6- 0 . 7 0 . 7 - 0 . 8 0 . 8 - 0 . 9 0 . 9 - 1 . 0 Na ike cl ay N 1 N2 N3 N4 N5 N 6 N7 N8 N9 N 1 0 0 . 0- 0 . 1 0 . 1 - 0 . 2 0 . 2 - 0 . 3 0 . 3 - 0 . 4 0 . 4 - 0 . 5 0 . 5 - 0 . 6 0 . 6- 0 . 7 0 . 7 - 0 . 8 0 . 8 - 0 . 9 0 . 9 - 1 . 0 Waiareka c l ay W 1 W2 W3 W4 W5 W6 0. 0- 0 . 1 0 . 1 - 0 . 2 0 . 2 - 0 . 3 0 . 3- 0 . 4 0 . 4- 0 . 5 0 . 5- . 5 5 2 7 6 Append i x 1 0 : An a lyses of p hosphorus and carbon from se l ected dep t h s a nd s amp l e s i n the Tokomaru s i l t 1 oam . Depth ( cm ) JJ 919 p+ Samp l e %C* 0-5 562 T25 7 . 70 5- 1 0 446 T24 1 . 45 1 0- 1 5 390 T23 1 . 02 1 5 -20 306 T22 0 . 63 20-25 243 T2 1 0 . 5 1 25 -30 1 96 T20 0 . 48 30-35 1 50 T1 9 0 . 30 35 -40 1 08 T 18 0 . 1 5 40-45 60 T1 7 0 . 1 2 45 -50 40 T1 6 0 . 1 50-55 33 T1 5 0 . 1 55 -60 34 T 1 3 0 . 1 60-65 3 1 T 1 1 0 . 1 65 -70 55 T9 0. 1 70-75 1 24 TB 0 . 1 7 5 -80 3 1 3 T7 0 . 1 80 -90 34 1 T5 0 . 1 90 - 1 00 35 1 T3 0 . 1 1 00- 1 1 0 340 T1 0 . 1 + Wal ker and Adams ( 1 958 ) * A . West an a l yst 2 7 7 Append i x 1 1 : The percent heavy m i n era l s i n the f i ne and very f i ne s and fract i on s from the Hami l ton , Na i ke and Te Kowha i so i l s . S amp l e R 1 R 1 R3 R4 R 5 R6 R 7 R8 R9 R 1 0 S amp l e N 1 N2 N3 N4 N5 N6 N 7 N 8 N9 N 1 0 Samp l e TK1 TK2 TK3 TK4 TK5 TK6 TK7 TK8 TK9 TK 1 0 250- 1 25 llm 1 3 . 0 1 1 . 5 1 1 . 2 1 2 . 0 1 1 . 3 1 4 . 4 1 3 . 8 1 1 . 5 1 1 . 1 1 5 . 1 2 50- 1 25 llm 5 . 2 4 . 4 4 . 8 6 . 6 1 2 . 1 1 3 . 3 1 4 . 9 1 2 . 2 4 . 0 1 . 3 250- 1 25 llm 3 . 7 3 . 3 1 . 4 0 . 1 0 . 1 0 . 1 0 . 1 0 . 2 0 . 2 0 . 2 1 25 - 63 llm 1 6 . 4 1 6 . 1 1 7 . 5 24 . 2 25 . 8 28 . 7 25 . 9 24 . 3 22 . 2 29 . 6 1 25 -63 llm 1 0 . 6 8 . 4 1 1 . 1 1 6 . 6 2 1 . 0 24 . 8 2 7 . 7 2 1 . 0 9 . 3 2 . 7 1 25-63 llffi 3 . 1 2 . 5 0 . 4 0 . 3 0 . 2 0 . 5 0 . 3 0 . 5 0 . 5 0 . 3 2 7 8 Appendix 12 : E lectron mi croprobe analyses of s o i l minerals . Samp l e S i02 Al20 3 Ti02 FeO MnO M gO CaO Na2o K20 C l Total Samp le S i02 Al 20 3 Ti02 FeO MnO M gO CaO Na2o K20 C l Tota l Samp l e S i02 Al20 3 T i02 FeO MnO M gO CaO Na2o K20 C l Tota l 12 . 1 : Glasses . T l T l T 1 T l T l T l Tl T l 7 4 . 3 4 7 3 . 8 0 7 3 . 1 5 7 4 . 7 1 7 4 . 0 7 7 3 . 9 7 7 6 . 0 0 7 3 . 1 3 1 1 . 2 7 1 1 . 1 9 1 1 . 1 1 1 1 . 3 5 1 1 . 1 0 1 1 . 2 8 1 1 . 5 9 12 . 0 9 0 . 1 6 0 . 0 9 0 . 0 0 0 . 1 7 0 . 1 0 0 . 12 0 . 1 5 0 . 1 7 1 . 02 1 . 1 4 1 . 2 8 1 . 1 0 1 . 12 1 . 0 4 1 . 13 1 . 9 5 0 . 1 4 0 . 0 0 0 . 0 0 0 . 0 0 0 . 12 0 . 0 0 0 . 0 0 0 . 0 0 0 . 1 1 0 . 1 0 0 . 1 3 0 . 1 1 0 . 0 9 0 . 1 0 0 . 0 9 0 . 1 0 0 . 87 0 . 9 5 1 . 0 3 1 . 0 2 0 . 9 8 0 . 9 5 0 . 9 4 1 . 0 7 3 . 2 1 3 . 4 6 2 . 9 6 3 . 2 7 2 . 9 8 2 . 9 7 3 . 6 0 4 . 1 5 3 . 6 4 2 . 8 8 2 . 7 9 2 . 9 0 2 . 9 0 3 . 0 5 3 . 7 4 3 . 3 3 0 . 0 0 0 . 0 8 0 . 0 9 0 . 0 9 0 . 1 0 0 . 0 6 0 . 1 1 0 . 1 0 94 . 7 6 9 3 . 6 9 9 2 . 5 4 9 4 . 7 2 9 3 . 5 6 T 3 T3 T3 T 3 T 3 66 . 8 0 64 . 2 8 62 . 0 0 13 . 7 7 1 5 . 3 7 1 4 . 3 8 1 . 1 8 1 . 1 7 0 . 9 6 5 . 0 5 5 . 3 5 5 . 5 4 0 . 04 0 . 00 0 . 1 1 1 . 1 4 1 . 2 6 2 . 0 0 3 . 4 3 5 . 3 8 5 . 0 4 3 . 7 5 3 . 9 6 3 . 2 5 3 . 3 3 2 . 2 9 2 . 5 6 0 . 0 0 0 . 07 0 . 1 0 7 4 . 8 0 7 3 . 12 1 1 . 1 8 1 1 . 2 7 0 . 0 0 0 . 1 3 1 . 0 7 1 . 1 8 0 . 0 0 0 . 0 0 0 . 1 0 0 . 1 1 0 . 92 1 . 07 3 . 5 0 3 . 5 5 2 . 8 7 2 . 7 1 0 . 07 0 . 0 7 98 . 4 9 9 9 . 1 3 T5 T5 7 4 . 6 3 7 5 . 0 2 1 1 . 34 1 1 . 4 1 0 . 10 0 . 0 0 1 . 1 5 1 . 0 8 0 . 0 0 0 . 0 0 0 . 1 5 0 . 1 4 1 . 04 1 . 0 6 3 . 2 0 3 . 17 2 . 6 9 2 . 7 7 0 . 1 5 0 . 1 7 9 5 . 9 4 9 4 . 5 1 93 . 2 1 T 5 T 5 T5 7 3 . 7 5 6 7 . 9 7 6 8 . 52 1 1 . 2 9 1 3 . 0 4 13 . 1 4 0 . 1 4 0 . 8 0 0 . 7 7 0 . 9 4 3 . 1 8 3 . 8 7 0 . 0 0 0 . 1 3 0 . 1 5 0 . 0 9 0 . 8 7 0 . 83 0 . 6 8 3 . 5 0 2 . 9 0 2 . 4 9 3 . 5 3 3 . 2 7 4 . 5 1 3 . 3 3 3 . 3 9 0 . 18 0 . 12 0 . 00 9 3 . 5 4 9 7 . 3 5 9 6 . 0 9 T 3 T 3 T 3 7 4 . 5 0 7 5 . 1 9 7 3 . 7 7 1 1 . 3 2 1 1 . 4 4 1 1 . 1 5 0 . 1 2 0 . 1 1 0 . 1 3 1 . 0 0 1 . 2 1 1 . 0 7 0 . 0 0 0 . 0 0 0 . 0 0 0 . 1 3 0 . 12 0 . 1 0 0 . 9 7 1 . 0 7 0 . 8 3 3 . 5 4 3 . 4 3 3 . 5 3 3 . 1 4 2 . 7 6 2 . 8 6 0 . 1 0 0 . 0 9 0 . 1 0 9 4 . 82 9 5 . 4 2 9 3 . 5 4 T 5 T 5 T5 6 8 . 3 4 7 5 . 5 4 7 4 . 1 5 1 4 . 5 7 1 1 . 3 4 1 1 . 2 6 1 . 0 4 0 . 13 0 . 0 0 3 . 6 3 0 . 9 8 1 . 0 1 0 . 0 0 0 . 0 0 0 . 1 4 1 . 3 1 0 . 09 0 . 1 3 2 . 7 7 0 . 7 4 0 . 9 3 5 . 5 5 2 . 7 6 2 . 83 1 . 4 9 4 . 5 5 2 . 9 5 0 . 0 0 0 . 2 0 0 . 0 0 94 . 4 5 94 . 82 9 4 . 07 9 6 . 4 7 9 6 . 8 4 9 8 . 7 0 9 6 . 3 3 9 3 . 4 0 27 9 2 80 Appendix 12 . 1 : continued . Samp le T 6 T6 T6 T6 T6 T 6 T 6 S i02 7 5 . 1 1 62 . 4 4 7 4 . 5 6 7 4 . 8 3 7 4 . 14 7 4 . 7 2 7 4 . 37 Al2 0 3 1 1 . 3 8 1 5 . 8 7 1 1 . 4 0 1 1 . 2 8 1 1 . 3 0 1 1 . 3 2 1 1 . 3 3 T i02 0 . 08 0 . 5 6 0 . 1 3 0 . 1 1 0 . 1 5 0 . 1 1 0 . 0 0 FeO 1 . 0 3 3 . 1 2 1 . 0 7 1 . 0 9 0 . 9 7 1 . 0 1 1 . 1 5 MnO 0 . 0 0 0 . 1 6 0 . 0 0 0 . 0 0 0 . 0 0 0 . 0 0 0 . 0 0 M gO 0 . 1 1 l . 2 3 0 . 1 2 0 . 1 1 0 . 0 8 0 . 1 0 0 . 1 3 CaO 1 . 1 0 2 . 7 6 l . 0 4 l . 0 4 0 . 88 0 . 9 3 1 . 0 9 Na2o 2 . 9 6 4 . 10 2 . 9 0 2 . 8 4 2 . 5 9 2 . 9 0 2 . 82 K20 2 . 62 4 . 14 2 . 92 2 . 9 1 2 . 8 1 3 . 1 3 2 . 8 4 C l 0 . 0 8 0 . 1 1 0 . 0 0 0 . 1 0 0 . 1 0 0 . 1 1 0 . 0 8 ------ -------- ------------------------------ - - - Total 94 . 4 7 94 . 4 9 9 4 . 1 4 9 4 . 3 1 93 . 02 9 4 . 3 3 93 . 8 1 S amp le T6 T6 T 6 T6 Tl3 Tl3 T 1 4 S i02 7 4 . 9 1 7 5 . 17 7 5 . 0 7 7 4 . 4 2 7 3 . 02 7 2 . 9 8 7 3 . 5 6 Al 20 3 1 1 . 2 9 1 1 . 4 7 1 1 . 2 4 1 1 . 2 2 1 1 . 5 0 1 1 . 6 3 1 1 . 7 1 T i02 0 . 0 9 0 . 14 0 . 1 3 0 . 12 0 . 0 8 0 . 1 4 0 . 0 9 FeO 1 . 1 5 1 . 0 8 1 . 1 8 1 . 1 3 1 . 1 1 1 . 0 2 0 . 94 MnO 0 . 0 0 0 . 0 0 0 . 0 0 0 . 0 0 0 . 0 0 0 . 0 0 0 . 00 M gO 0 . 12 0 . 1 2 0 . 1 0 0 . 1 1 0 . 1 1 0 . 1 2 0 . 0 8 CaO 0 . 9 5 0 . 9 9 0 . 9 7 1 . o s 1 . 12 1 . 0 7 0 . 63 Na2o 2 . 9 3 3 . 19 2 . 7 9 2 . 52 3 . 1 6 2 . 6 1 3 . 4 1 K2 0 2 . 5 0 2 . 6 8 2 . 6 9 2 . 9 3 2 . 8 3 2 . 82 4 . 2 5 C l 0 . 0 9 0 . 10 0 . 0 9 0 . 0 7 0 . 1 1 0 . 0 8 0 . 1 3 ------- ---- --------- - - - ----- -------------------- Tota l 94 . 0 9 9 4 . 9 4 94 . 4 4 9 3 . 5 7 93 . 0 4 92 . 4 7 94 . 8 0 S amp le T14 Tl4 T l 6 T l 6 T 1 6 T 1 6 S i02 7 4 . 09 7 4 . 6 3 7 3 . 1 8 7 3 . 4 4 7 4 . 2 6 7 1 . 6 7 A l203 1 1 . 7 5 1 1 . 7 1 1 1 . 7 4 1 1 . 6 8 12 . 0 8 12 . 6 7 Ti02 0 . 1 1 0 . 1 1 0 . 0 9 0 . 0 0 0 . 14 0 . 2 6 FeO 1 . o s 1 . 3 5 1 . 1 5 1 . 08 1 . 04 1 . 7 6 M nO 0 . 00 0 . 00 0 . 0 0 0 . 00 0 . 0 0 0 . 00 M gO 0 . 07 0 . 04 0 . 1 3 0 . 16 0 . 08 0 . 2 3 CaO 0 . 67 0 . 5 9 1 . 0 4 1 . 05 0 . 9 8 1 . 4 0 Na2o 3 . 5 3 3 . 92 3 . 2 6 3 . 4 1 3 . 3 2 3 . 7 1 K20 4 . 0 3 3 . 7 6 2 . 8 5 2 . 7 6 3 . 82 2 . 6 4 C l 0 . 1 4 0 . 0 9 0 . 1 3 0 . 12 0 . 1 9 0 . 00 ---------------------------------------- Total 9 5 . 4 4 9 6 . 2 0 93 . 5 7 9 3 . 7 0 9 5 . 9 1 9 4 . 3 4 Appen dix 12 . 1 : Con t inued . Samp le S i02 Al 203 Ti02 FeO MnO M gO CaO Na2o K20 C l Tota l Samp le S i02 Al203 Ti02 FeO MnO M gO CaO Na2o K20 C l Tota l Samp le S i02 Al203 Ti02 FeO MnO M gO CaO Na2o K20 C l Total T2 4 T2 4 T2 4 T 2 4 T24 T 2 4 T2 4 T2 4 7 5 . 1 8 7 5 . 4 5 72 . 0 1 7 5 . 2 7 7 3 . 1 3 7 3 . 4 3 7 4 . 52 7 5 . 0 4 12 . 6 2 1 1 . 6 9 12 . 3 7 12 . 6 5 1 2 . 5 7 1 1 . 2 3 1 1 . 5 0 12 . 3 8 0 . 1 8 0 . 1 1 0 . 2 7 0 . 2 0 0 . 2 6 0 . 1 3 0 . 1 6 0 . 2 2 1 . 5 7 1 . 2 3 1 . 7 8 1 . 8 6 1 . 8 2 1 . 0 6 1 . 2 1 1 . 6 8 0 . 0 0 0 . 0 0 0 . 00 0 . 0 0 0 . 1 1 0 . 0 0 0 . 0 0 0 . 0 0 0 . 1 8 0 . 1 3 0 . 2 4 0 . 1 8 0 . 2 3 0 . 12 0 . 1 3 0 . 1 7 1 . 3 9 1 . 0 3 1 . 4 2 1 . 4 7 1 . 4 3 0 . 9 4 1 . 02 1 . 6 0 3 . 9 6 3 . 7 1 3 . 8 0 4 . 0 5 3 . 9 9 3 . 0 1 3 . 7 2 3 . 9 6 2 . 9 8 . 3 . 02 2 . 5 8 2 . 9 3 2 . 6 9 3 . 2 3 2 . 9 3 2 . 9 5 0 . 12 0 . 0 8 0 . 1 0 0 . 0 7 0 . 0 9 0 . 1 1 0 . 1 0 0 . 0 8 9 8 . 1 8 9 6 . 4 5 T2 4 T2 4 7 4 . 8 2 72 . 6 9 1 1 . 5 1 12 . 3 1 0 . 0 0 0 . 2 4 1 . 0 6 1 . 7 7 0 . 0 0 0 . 00 0 . 1 1 0 . 2 5 1 . 0 8 1 . 4 2 3 . 5 5 4 . 3 2 3 . 4 1 2 . 6 5 0 . 0 9 0 . 0 9 9 5 . 6 3 T 2 4 7 5 . 3 1 12 . s s 0 . 1 9 1 . 5 9 0 . 0 0 0 . 1 4 1 . 2 5 5 . 5 1 1 . 5 7 0 . 0 6 9 5 . 7 4 T 2 4 6 8 . 3 2 1 4 . 4 5 0 . 3 9 1 . 7 9 0 . 2 4 0 . 4 0 1 . 5 8 4 . 4 0 4 . 8 8 0� 1 0 94 . 5 7 9 8 . 6 8 9 6 . 3 2 9 3 . 2 6 T2 4 T 2 4 T2 4 T 2 4 7 6 . 3 6 7 6 . 4 0 7 6 . 8 4 7 7 . 2 3 1 1 . 9 2 1 1 . 7 3 1 1 . 7 8 1 1 . 7 8 0 . 1 6 0 . 1 1 0 . 1 0 0 . 12 1 . 2 7 1 . 2 5 1 . 1 7 1 . 0 5 0 . 0 0 0 . 0 0 0 . 00 0 . 0 0 0 . 1 4 0 . 12 0 . 1 0 0 . 1 4 1 . 1 5 0 . 9 3 1 . 0 8 0 . 9 8 3 . 6 4 3 . 8 0 3 . 6 9 3 . 9 6 3 . 3 4 3 . 2 9 3 . 2 5 3 . 3 5 0 . 1 1 0 . 1 0 0 . 0 5 0 . 1 0 9 8 . 0 9 T2 4 62 . 2 2 1 5 . 7 9 1 . os 6 . 1 1 0 . 0 0 2 . 0 5 5 . 5 7 3 . 9 8 2 . 2 8 0 . 04 9 7 . 7 3 9 8 . 0 6 9 8 . 7 1 T2 4 T2 4 T2 4 7 4 . 5 6 7 0 . 2 6 6 6 . 6 1 12 . 3 0 1 2 . 2 8 1 5 . 1 8 0 . 1 4 0 . 2 4 0 . 4 2 1 . 4 7 3 . 0 0 2 . 1 9 0 . 0 0 0 . 1 5 0 . 12 0 . 1 0 0 . 3 8 O . S l 1 . 1 5 1 . 7 3 2 . 0 1 3 . 8 4 3 . 17 4 . 2 0 3 . 8 9 2 . 3 3 4 . 4 8 0 . 0 8 0 . 1 1 0 . 1 8 95 . 2 9 T2 4 7 3 . 0 1 13 . 2 8 0 . 52 2 . 6 5 0 . 0 0 0 . 3 9 2 . 1 9 4 . 1 5 2 . 8 1 0 . 07 9 9 . 0 7 T2 4 62 . 5 0 1 4 . 9 7 1 . 0 2 5 . 8 9 0 . 0 0 2 . 1 5 5 . 1 7 3 . 9 6 2 . 4 3 0 . 06 9 8 . 0 8 T2 4 7 4 . 1 6 1 3 . 3 5 0 . 4 0 2 . 3 9 0 . 0 0 0 . 3 5 2 . 10 3 . 6 4 2 . 7 9 0 . 0 5 9 9 . 2 3 T2 4 7 4 . 3 2 1 1 . 4 1 0 . 0 0 1 . 0 7 0 . 0 0 0 . 1 0 1 . 02 2 . 9 8 2 . 7 6 0 . 09 9 8 . 1 7 9 6 . 5 5 9 9 . 0 9 9 7 . 5 3 9 3 . 6 5 9 5 . 9 0 9 8 . 1 5 9 3 . 7 5 281 App endix 12 . 1 : Con t inued . S amp le S i02 Al20 3 Ti02 FeO MnO M gO CaO Na2o K20 C l Total Samp le S i02 Al203 Ti02 FeO MnO M gO CaO Na20 K20 C l T2 5 T2 5 T2 5 T 2 5 67 . 6 4 6 7 . 3 6 6 3 . 6 7 7 7 . 5 2 1 1 . 2 5 14 . 6 9 1 5 . 8 6 12 . 0 8 0 . 6 5 0 . 3 1 0 . 6 1 0 . 0 9 5 . 8 5 1 . 9 1 3 . 1 0 1 . 2 4 0 . 1 3 0 . 0 0 0 . 00 0 . 1 0 3 . 9 6 0 . 3 3 0 . 9 3 0 . 1 5 2 . 2 7 1 . 7 2 2 . 6 5 0 . 9 4 2 . 3 4 3 . 3 9 4 . 4 5 3 . 8 0 3 . 0 9 4 . 2 7 4 . 19 3 . 12 0 . 1 1 0 . 1 4 0 . 1 5 0 . 1 0 T 2 5 T2 5 T2 5 7 4 . 6 3 7 5 . 0 6 7 5 . 2 0 1 1 . 7 3 1 1 . 3 7 1 1 . 1 8 0 . 0 0 0 . 1 6 0 . 1 0 0 . 9 4 1 . 0 0 0 . 9 6 0 . 0 0 0 . 0 0 0 . 0 0 0 . 12 0 . 1 1 0 . 0 8 0 . 8 1 0 . 92 0 . 7 4 2 . 9 7 2 . 8 7 2 . 8 8 2 . 8 8 2 . 6 9 2 . 8 8 0 . 1 0 0 . 0 9 0 . 0 9 97 . 2 9 9 4 . 1 2 9 5 . 6 1 9 8 . 1 4 94 . 1 8 94 . 2 7 94 . 1 1 T2 5 T2 5 T2 5 T2 5 T2 5 7 5 . 3 3 7 7 . 6 7 7 6 . 2 1 7 5 . 1 4 6 0 . 6 5 1 1 . 3 6 1 1 . 8 5 12 . 4 3 12 . 7 0 1 8 . 3 7 0 . 1 0 0 . 0 0 0 . 2 0 0 . 1 9 0 . 6 3 1 . 1 3 1 . 12 1 . 7 3 1 . 9 6 4 . 6 5 0 . 0 0 0 . 0 0 0 . 1 1 0 . 0 0 0 . 1 5 0 . 1 0 0 . 1 4 0 . 1 8 0 . 2 8 1 . 6 1 0 . 8 4 0 . 8 6 1 . 1 7 1 . 2 6 7 . 1 4 3 . 1 6 3 . 4 1 3 . 6 5 3 . 7 3 3 . 9 1 2 . 8 1 3 . 3 2 2 . 9 0 2 . 8 9 1 . 7 2 0 . 1 0 0 . 1 4 0 . 0 7 0 . 0 6 0 . 0 6 T2 5 T2 5 6 5 . 4 4 6 4 . 7 2 14 . 0 6 1 4 . 1 9 0 . 6 3 0 . 6 3 5 . 6 3 6 . 5 3 0 . 1 9 0 . 1 7 1 . 3 7 1 . 4 1 3 . 83 3 . 9 1 3 . 6 3 3 . 6 4 1 . 9 9 1 . 8 3 0 . 0 8 0 . 0 7 T2 5 7 5 . 9 9 12 . 8 3 0 . 1 5 1 . 6 3 0 . 0 0 0 . 1 8 1 . 2 4 3 . 6 8 2 . 9 8 0 . 1 1 9 8 . 7 9 T2 5 64 . 2 3 1 3 . 9 1 0 . 5 4 6 . 1 5 0 . 00 1 . 4 9 4 . 1 7 3 . 5 7 1 . 92 0 . 0 0 282 Total 94 . 9 3 9 8 . 5 1 98 . 6 5 9 8 . 2 1 9 8 . 89 9 6 . 8 5 97 . 1 0 9 5 . 9 8 Samp l e T2 5 T 2 5 S i02 59 . 8 5 62 . 2 6 Al2 03 19 . 5 0 1 6 . 3 1 T i02 0 . 5 3 0 . 7 6 FeO 4 . 2 8 5 . 9 3 MnO 0 . 0 0 0 . 1 6 MgO 1 . 7 3 2 . 2 7 CaO 7 . 9 5 6 . 2 2 Na2 0 3 . 8 6 3 . 87 K20 1 . 4 1 1 . 9 3 C l 0 . 00 0 . 0 0 T2 5 T2 5 7 0 . 9 7 64 . 3 7 14 . 8 0 14 . 7 6 0 . 3 4 0 . 7 8 1 . 7 0 6 . 5 8 0 . 1 5 0 . 0 0 0 . 2 9 1 . 32 1 . 5 1 4 . 7 2 5 . 1 5 4 . 6 4 4 . 1 7 1 . 9 3 0 . 1 8 0 . 0 9 T2 5 5 6 . 4 0 2 3 . 8 5 0 . 2 8 2 . 5 4 0 . 00 0 . 6 4 1 0 . 0 1 4 . 1 5 0 . 9 7 0 . 0 0 T2 5 7 5 . 7 0 13 . 6 8 0 . 2 3 0 . 4 4 0 . 0 0 0 . ·00 2 . 2 7 4 . 5 2 1 . 87 0 . 00 T2 5 7 0 . 2 1 1 3 . 8 5 0 . 8 8 1 . 4 1 0 . 0 0 0 . 1 1 1 . 3 9 3 . 2 2 5 . 9 6 0 . 0 0 T2 5 T2 5 6 4 . 2 2 67 . 7 8 1 3 . 7 2 1 7 . 5 3 0 . 5 3 0 . 5 7 5 . 3 3 1 . 8 3 0 . 1 7 0 . 0 0 3 . 1 1 0 . 1 1 4 � 5 0 5 . 4 9 3 . 9 9 5 . 0 9 1 . 02 0 . 4 1 0 . 0 8 0 . 0 0 Total 9 9 . 1 1 9 9 . 7 1 9 9 . 2 6 9 9 . 1 9 9 8 . 84 9 8 . 7 1 9 7 . 0 3 9 6 . 6 7 9 8 . 8 1 Appendix 12 . 2 : Amph iboles . Samp le T3 T3 S i02 4 7 . 3 2 4 7 . 5 8 Al 20 3 6 . 3 3 6 . 2 0 Ti02 1 . 3 0 1 . 3 0 FeO 1 6 . 3 9 1 5 . 9 1 MnO 0 . 3 7 0 . 4 4 MgO 12 . 7 2 12 . 8 3 CaO 1 0 . 4 8 1 0 . 4 9 Na 20 1 . 5 1 1 . 4 0 K20 0 . 3 1 0 . 2 7 Tota l Samp le S i02 Al20 3 Ti02 FeO MnO M gO CaO Na 2o K20 Tota l Samp le S i02 Al 20 3 Ti02 FeO MnO M gO CaO Na 2o K20 9 6 . 7 3 TS 4 2 . 8 9 1 1 . 0 3 3 . 8 3 1 0 . 9 0 0 . 3 2 1 4 . 2 5 1 1 . 4 6 2 . 6 4 0 . 9 4 9 6 . 4 2 TS 4 0 . 7 4 12 . 5 7 2 . 7 6 12 . 0 9 0 . 2 6 1 3 . 0 8 1 1 . 9 0 2 . 3 5 0 . 8 5 9 8 . 2 6 9 6 . 6 0 TS TS 4 0 . 0 6 42 . 9 4 1 0 . 8 3 1 1 . 4 2 3 . 5 7 3 . 3 1 1 1 . 8 1 1 1 . 1 3 0 . 3 6 0 . 2 8 1 3 . 6 1 14 . 4 5 1 1 . 1 9 1 1 . 5 4 2 . 4 8 2 . 5 3 0 . 8 9 0 . 82 T 3 4 7 . 1 7 6 . 3 7 1 . 5 3 1 5 . 32 0 . 3 6 13 . 2 9 10 . 7 5 1 . 5 5 0 . 3 2 9 6 . 6 6 T S 4 1 . 5 8 1 1 . 9 0 2 . 5 9 1 1 . 2 1 0 . 4 0 14 . 3 7 1 1 . 3 8 2 . 6 0 0 . 8 7 9 6 . 9 0 T S 3 9 . 7 8 14 . 4 9 2 . 4 2 1 1 . 2 8 0 . 0 0 13 . 6 2 12 . 2 6 2 . 32 1 . 0 6 T3 T3 T3 4 7 . 2 4 7 . 3 0 1 . 57 12 . 7 5 0 . 2 6 1 4 . 4 8 1 1 . 1 0 1 . 1 3 4 7 . 6 4 4 8 . 2 7 7 . 4 6 6 . 9 0 1 . 4 9 1 . 4 2 1 1 . 9 4 1 2 . 6 0 0 . 1 8 0 . 2 3 1 4 . 8 7 1 5 . 0 9 1 1 . 2 0 1 1 . 0 3 1 . 2 1 1 . 1 6 0 . 2 0 0 . 2 1 0 . 2 0 9 8 . 13 TS 42 . 3 7 1 0 . 9 6 3 . 5 9 1 1 . 17 0 . 3 4 14 . 3 6 1 1 . 3 9 2 . 5 4 0 . 8 3 9 6 . 2 0 TS 42 . 3 6 1 1 . 02 3 . 6 0 1 0 . 9 2 0 . 3 2 14 . 18 1 1 . 0 6 2 . 62 0 . 8 5 9 7 . 5 5 9 6 . 9 3 T S TS 3 9 . 9 4 3 9 . 9 9 1 3 . 4 2 1 3 . 6 0 2 . 4 6 2 . 6 8 1 1 . 4 6 1 1 . 7 7 0 . 1 4 0 . 17 1 3 . 4 4 1 3 . 4 6 12 . 3 0 12 . 0 6 2 . 3 9 2 . 4 5 0 . 9 0 0 . 9 5 9 6 . 9 0 T S 4 1 . 2 4 12 . 8 5 2 . 7 7 1 1 . 8 8 0 . 1 8 1 3 . 9 8 1 2 . 0 9 2 . 4 7 0 . 8 5 9 8 . 3 1 T S 4 1 . 9 4 1 1 . 6 6 3 . 5 4 12 . 4 3 0 . 3 4 1 3 . 0 6 1 1 . 3 6 2 . 4 7 0 . 9 2 283 TS 3 9 . 38 1 3 . 3 7 2 . 4 5 1 1 . 4 2 0 . 2 0 1 3 . 2 2 12 . 0 8 2 . 5 2 0 . 82 9 5 . 4 6 TS 3 8 . 89 1 3 . 5 5 2 . 7 3 1 1 . 7 0 0 . 14 1 3 . 0 8 12 . 0 2 2 . 4 3 0 . 82 9 5 . 3 6 TS 42 . 1 3 1 0 . 9 6 3 . 4 5 1 1 . 5 5 0 . 3 0 14 . 12 1 1 . 3 2 2 . 4 6 0 . 82 TS 4 1 . 9 0 1 1 . 8 4 3 . 1 1 12 . 5 3 0 . 2 9 12 . 9 2 1 1 . 6 0 2 . 5 6 0 . 92 9 7 . 6 7 T S 42 . 7 4 1 1 . 1 6 3 . 6 3 1 1 . 2 6 0 . 3 2 14 . o s 1 1 . 5 1 2 . 4 7 0 . 8 6 9 8 . 0 0 TS 3 9 . 82 1 3 . 80 2 . 3 6 1 1 . 3 4 0 . 1 8 13 . 6 3 12 . 2 5 2 . 4 8 0 . 9 2 To tal 9 4 . 8 0 98 . 4 2 97 . 2 3 9 6 . 4 5 9 7 . 1 3 9 7 . 7 2 9 7 . 1 1 9 6 . 7 8 284 App endix 12 . 2 : Continued . Samp l e T6 T 6 T 6 T 6 T 6 T6 T6 T 6 S i02 4 1 . 8 3 4 1 . 3 0 4 0 . 7 2 42 . 9 6 4 0 . 7 4 4 2 . 2 1 42 . 0 8 42 . 3 5 Al 2 03 1 1 . 6 0 1 3 . 0 7 1 3 . 4 6 1 1 . 0 5 1 3 . 1 0 1 1 . 0 6 12 . 0 7 1 0 . 8 6 Ti02 3 . 0 7 2 . 3 7 2 . 02 3 . 3 4 2 . 4 3 3 . 6 2 3 . 0 9 3 . 4 8 FeO 1 1 . 9 2 1 1 . 5 7 1 1 . 87 1 1 . 8 9 1 1 . 6 5 1 0 . 8 8 1 1 . 7 1 1 1 . 2 8 MnO 0 . 2 3 0 . 1 5 0 . 0 0 0 . 3 2 0 . 1 7 0 . 2 6 0 . 2 1 0 . 2 7 M gO 1 3 . 6 7 1 3 . 6 8 1 3 . 2 4 13 . 9 3 1 3 . 4 4 1 4 . 14 13 . 3 0 14 . 2 7 CaO 1 1 . 7 0 12 . 02 1 1 . 9 6 1 1 . 3 6 12 . 04 1 1 . 4 2 1 1 . 82 1 1 . 4 5 Na2 o 2 . 5 0 2 . 3 3 2 . 4 8 2 . 6 6 2 . 3 9 2 . 4 7 2 . 5 0 2 . 42 K 20 0 . 8 6 0 . 8 0 0 . 8 4 0 . 9 3 0 . 8 4 0 . 9 5 0 . 82 0 . 8 0 ------------- ----- -------- ---------------------- ------ Tot a l 9 6 . 9 3 9 7 . 2 9 9 6 . 5 9 98 . 4 4 9 6 . 8 0 9 7 . 0 1 97 . 6 0 9 7 . 1 8 Samp l e T6 T6 T6 T6 T 6 T 6 T6 T6 S i02 42 . 5 4 42 . 9 6 42 . 4 4 42 . 4 1 42 . 4 1 4 2 . 4 9 42 . 3 7 4 1 . 4 7 A l20 3 1 0 . 8 0 1 0 . 9 3 10 . 9 7 10 . 8 0 1 0 . 8 0 1 0 . 8 9 10 . 4 8 1 1 . 5 0 Ti02 3 . 3 9 3 . 5 1 3 . 6 9 3 . 1 5 3 . 1 5 3 . 5 1 3 . 4 9 3 . 2 6 FeO 1 1 . 6 0 1 1 . 1 8 1 1 . 8 4 12 . 2 7 12 . 2 7 1 1 . 1 3 12 . 07 12 . 0 8 MnO 0 . 3 3 0 . 2 6 0 . 3 1 0 . 2 8 0 . 2 8 0 . 2 6 0 . 2 9 0 . 2 8 M gO 1 3 . 9 5 1 4 . 0 7 1 3 . 8 5 1 3 . 7 3 1 3 . 7 3 1 4 . 0 8 13 . 68 1 3 . 2 1 CaO 1 1 . 3 1 1 1 . 4 6 1 1 . 4 2 1 1 . 2 0 1 1 . 2 0 1 1 . 3 2 1 1 . 12 1 1 . 3 9 Na2o 2 . 5 1 2 . 6 1 2 . 5 6 2 . 3 8 2 . 3 8 2 . 55 2 . 6 3 2 . 4 8 K20 0 . 8 5 0 . 8 1 0 . 8 8 0 . 87 0 . 8 7 0 . 89 0 . 9 6 0 . 9 8 --------- - -- ------------------ - - - - -- ------------------ Tota l 9 7 . 2 8 9 7 . 7 9 9 7 . 9 6 9 7 . 0 9 9 7 . 0 9 9 7 . 12 97 . 0 9 9 6 . 6 5 Samp l e T 6 T6 T 6 T 6 T 6 T 6 T6 S i02 4 0 . 4 0 4 0 . 7 7 4 2 . 1 6 42 . 5 3 4 1 . 6 9 4 2 . 7 7 42 . 5 3 Al203 12 . 10 12 . 0 8 1 0 . 92 1 1 . 0 7 1 1 . 7 5 1 0 . 92 1 1 . 1 4 Ti02 2 . 92 2 . 8 3 3 . 5 4 3 . 62 3 . 5 1 3 . 4 8 3 . 4 1 FeO 12 . 57 12 . 4 5 1 0 . 8 7 1 1 . 02 1 1 . 62 1 1 . 3 0 1 1 . 55 MnO 0 . 2 5 0 . 3 1 0 . 2 1 0 . 32 0 . 2 8 0 . 3 0 0 . 3 2 M gO 12 . 6 9 12 . 5 8 1 3 . 9 0 1 4 . 3 5 1 3 . 53 1 4 . 2 9 1 3 . 7 9 CaO 1 1 . 7 3 1 1 . 7 7 1 1 . 4 0 1 1 . 52 1 1 . 54 1 1 . 3 2 1 1 . 2 2 Na2o 2 . 4 7 2 . 3 5 2 . 6 1 2 . 52 2 . 5 7 2 . 6 3 2 . 5 4 K20 0 . 84 0 . 82 0 . 7 9 0 . 82 0 . 9 4 0 . 7 6 0 . 8 5 ---------- - - - - - -------------------------------- Tota l 9 5 . 97 9 5 . 9 6 9 6 . 4 0 9 7 . 7 7 9 7 . 4 3 9 7 . 7 7 9 7 . 3 5 285 Appendix 12 . 2 : Cont inued . Samp l e T2 4 T2 4 T2 4 T 2 4 T2 4 T 2 4 T2 4 T2 4 S i02 4 2 . 2 5 4 3 . 2 8 4 1 . 3 1 4 3 . 0 8 42 . 5 6 4 0 . 6 4 40 . 4 6 4 1 . 4 6 Al20 3 1 2 . 1 7 1 0 . 1 4 13 . 0 0 1 0 . 3 0 1 1 . 0 0 1 2 . 4 8 13 . 5 9 13 . 0 8 Ti02 2 . 7 8 3 . 3 1 2 . 1 1 3 . 1 7 3 . 1 6 2 . 8 0 2 . 3 4 2 . 9 1 FeO 1 3 . 6 1 1 1 . 4 3 9 . 6 0 12 . 2 3 1 1 . 8 4 12 . 7 9 1 1 . 5 8 12 . 2 4 MnO 0 . 3 0 0 . 4 2 0 . 0 0 0 . 3 6 0 . 2 9 0 . 3 0 0 . 1 8 0 . 0 0 M gO 1 1 . 9 1 13 . 7 7 14 . 9 2 1 3 . 4 7 13 . 5 5 1 2 . 5 0 13 . 5 5 13 . 6 8 cao 1 1 . 7 9 1 1 . 4 4 12 . 2 7 1 1 . 4 2 1 1 . 6 3 1 1 . 7 7 12 . 4 0 12 . 1 6 Na2o 2 . 2 9 2 . 3 3 2 . 3 7 2 . 3 5 2 . 5 0 2 . 54 2 . 2 9 2 . 5 3 K20 0 . 87 0 . 8 3 1 . 0 1 0 . 8 5 0 . 8 7 0 . 7 1 0 . 92 0 . 8 5 -------- --------------- ------- - - - -- - - --- -------------- Tota l 9 7 . 9 7 9 6 . 9 5 9 6 . 5 9 9 7 . 2 3 97 . 4 0 9 6 . 5 3 97 . 3 1 9 8 . 9 1 Samp l e T24 T2 4 T2 4 T 2 4 T 2 4 T 2 4 T2 4 T2 4 S i02 4 0 . 3 1 4 0 . 4 4 42 . 2 1 4 3 . 0 6 42 . 0 8 4 3 . 7 7 39 . 9 9 3 9 . 5 8 Al20 3 1 3 . 8 0 13 . 8 1 1 1 . 4 2 1 0 . 5 5 1 1 . 0 0 1 0 . 2 8 14 . 0 6 14 . 2 7 Ti02 2 . 3 0 2 . 3 6 2 . 8 9 3 . 3 0 3 . 6 4 2 . 6 8 1 . 44 2 . 4 9 FeO 1 1 . 16 1 1 . 2 1 14 . 19 12 . 3 4 1 1 . 1 7 12 . 4 7 12 . 14 12 . 0 7 MnO 0 . 0 0 0 . 0 0 0 . 4 4 0 . 3 3 0 . 3 3 0 . 4 7 0 . 1 6 0 . 0 0 M gO 1 3 . 6 0 13 . 6 4 1 1 . 8 7 1 3 . 5 8 14 . 19 1 3 . 2 4 12 . 8 6 12 . 9 0 CaO 12 . 2 1 12 . 2 6 1 1 . 5 8 1 1 . 2 7 1 1 . 3 6 1 1 . 5 6 12 . 1 1 12 . 0 1 Na2o 2 . 3 7 2 . 4 3 2 . 3 8 2 . 4 5 2 . 5 3 2 . 32 2 . 3 7 2 . 4 2 K20 0 . 9 5 1 . 0 0 0 . 9 0 0 . 87 0 . 89 0 . 92 0 . 9 7 0 . 9 3 ------------------ ---- ------------------------------- - Tot a l 9 6 . 7 0 9 7 . 1 5 9 7 . 8 8 9 7 . 7 5 97 . 19 9 7 . 7 1 9 6 . 10 9 6 . 6 7 Samp le T2 4 T2 4 T2 4 T2 4 T2 4 T2 4 T2 4 T 2 4 S i02 4 1 . 5 0 3 9 . 7 8 4 0 . 2 3 42 . 6 8 4 0 . 1 1 4 3 . 07 4 3 . 7 2 4 3 . 7 6 Al20 3 1 3 . 5 6 1 4 . 4 7 1 3 . 9 1 1 0 . 8 9 1 5 . 9 0 1 0 . 0 9 9 . 9 1 1 0 . 1 6 Ti02 2 . 8 6 2 . 3 2 2 . 87 2 . 7 8 2 . 1 1 3 . 1 9 3 . 0 5 3 . 0 0 FeO 1 1 . 18 1 1 . 7 3 1 1 . 0 5 12 . 3 3 10 . 7 1 1 1 . 5 1 12 . 3 3 1 1 . 4 3 MnO 0 . 00 0 . 1 3 0 . 0 0 0 . 3 5 0 . 0 0 0 . 4 5 0 . 4 3 0 . 3 7 M gO 1 4 . 3 0 1 3 . 1 8 1 3 . 8 6 1 3 . 3 1 1 3 . 6 3 1 3 . 7 6 1 4 . 02 1 3 . 7 2 CaO 1 1 . 8 0 12 . 12 12 . 0 5 1 1 . 7 5 12 . 83 1 1 . 5 0 1 1 . 5 0 1 1 . 5 9 Na2o 2 . 5 1 2 . 4 3 2 . 4 3 2 . 4 4 2 . 3 7 2 . 3 1 2 . 4 5 2 . 4 1 K20 0 . 87 0 . 9 2 0 . 8 6 0 . 8 3 0 . 6 4 0 . 82 0 . 8 7 0 . 8 3 ------------------------------------------- ----------- Tot a l 9 8 . 6 4 9 7 . 0 8 9 7 . 2 6 9 7 . 3 6 9 8 . 3 0 9 6 . 7 0 9 8 . 2 8 9 7 . 2 7 App endix 12 . 2 : Con t inued . Samp le S i02 Al 20 3 Ti02 FeO MnO M gO CaO Na2o K20 Tota l Samp le S i02 Al 20 3 Ti02 FeO MnO M gO CaO Na2o K20 Tota l Samp l e S i02 A l203 Ti02 FeO MnO M gO CaO Na2o K20 T2 5 T2 5 4 5 . 2 0 4 5 . 8 0 7 . 7 0 6 . 8 4 1 . 9 7 1 . 5 4 1 7 . 0 6 18 . 3 3 0 . 4 8 0 . 3 8 1 1 . 4 9 1 1 . 4 6 1 0 . 6 3 10 . 3 4 1 . 8 6 1 . 4 9 0 . 2 9 0 . 3 1 T2 5 T2 5 T2 5 4 0 . 9 5 4 1 . 8 1 4 1 . 7 6 1 1 . 9 8 1 3 . 5 3 10 . 9 5 2 . 8 8 1 . 6 8 3 . 5 0 12 . 4 8 1 0 . 2 4 12 . 87 0 . 2 4 0 . 1 3 0 . 3 0 1 3 . 0 1 1 4 . 5 3 13 . 03 1 1 . 8 3 12 . 1 6 1 0 . 79 2 . 4 5 2 . 4 0 2 . 3 8 0 . 8 7 0 . 3 3 1 . 1 4 T2 5 4 2 . 3 9 1 1 . 0 2 3 . 7 2 12 . 7 6 0 . 2 8 12 . 9 6 1 1 . 0 2 2 . 3 0 1 . 3 4 9 6 . 6 8 9 6 . 4 9 9 6 . 6 9 9 6 . 8 1 96 . 72 9 7 . 7 9 T2 5 T2 5 T2 5 T2 5 T2 5 T2 5 4 2 . 82 43 . 6 0 4 3 . 4 5 4 1 . 5 5 4 1 . 82 42 . 62 1 0 . 1 7 9 . 7 2 1 0 . 1 0 1 1 . 4 8 1 1 . 54 1 0 . 4 1 3 . 0 7 3 . 0 5 3 . 0 1 2 . 6 8 2 . 5 5 3 . 3 4 12 . 1 9 12 . 4 0 12 . 2 2 1 2 . 9 2 12 . 4 7 1 1 . 6 4 0 . 4 1 0 . 4 5 0 . 4 2 0 . 3 0 0 . 2 9 0 . 3 1 1 3 . 7 2 13 . 6 8 1 3 . 6 6 1 2 . 5 9 13 . 0 6 1 4 . 0 0 1 1 . 6 6 1 1 . 6 9 1 1 . 6 3 1 1 . 8 0 1 1 . 89 1 1 . 3 2 2 . 3 6 2 . 3 2 2 . 3 8 2 . 4 1 2 . 3 8 2 . 4 0 0 . 92 0 . 8 9 0 . 8 8 0 . 8 0 0 . 8 1 1 . 0 0 9 7 . 3 2 9 7 . 8 0 9 7 . 7 5 T2 5 T2 5 T2 5 4 2 . 3 8 42 . 4 7 4 2 . 7 3 1 0 . 4 6 1 0 . 2 0 1 0 . 12 3 . 4 0 3 . 2 9 3 . 1 6 12 . 0 4 12 . 1 1 12 . 1 1 0 . 3 7 0 . 3 1 0 . 3 8 1 3 . 5 1 1 3 . 62 1 3 . 7 6 1 1 . 9 0 1 1 . 5 4 1 1 . 5 6 2 . 3 5 2 . 3 8 2 . 3 9 0 . 9 2 0 . 9 5 0 . 9 1 9 6 . 5 3 T2 5 4 3 . 0 3 1 0 . 2 6 3 . 1 6 1 1 . 9 6 0 . 4 0 1 3 . 8 1 1 1 . 3 8 · 2 . 4 8 0 . 7 9 9 6 . 8 1 9 7 . 04 T2 5 T2 5 42 . 62 4 0 . 9 9 10 . 4 5 1 2 . 9 7 3 . 3 1 1 . 8 0 1 1 . 8 8 9 . 6 7 0 . 32 0 . 0 0 1 3 . 7 3 1 5 . 0 3 1 1 . 3 5 1 2 . 3 6 2 . 5 8 2 . 12 0 . 8 1 1 . 0 6 T 2 5 T2 5 4 0 . 4 9 4 1 . 0 7 13 . 4 4 13 . 62 2 . 6 0 2 . 4 5 10 . 6 9 10 . 8 9 0 . 00 0 . 0 0 14 . 1 6 14 . 2 0 12 . 0 1 12 . 1 8 2 . 5 1 2 . 4 8 0 . 9 1 0 . 9 7 286 T2 5 4 1 . 0 9 1 3 . 5 4 2 . 0 5 1 0 . 0 9 0 . 0 0 1 4 . 7 4 1 2 . 2 1 2 . 3 9 1 . 1 1 96 . 8 1 9 7 . 8 6 9 7 . 2 2 T2 5 T2 5 T2 5 42 . 1 1 42 . 8 6 4 0 . 9 0 1 1 . 12 10 . 3 4 1 3 . 5 6 2 . 7 7 3 . 2 5 2 . 4 9 13 . 3 3 1 1 . 3 9 1 0 . 8 7 0 . 3 3 0 . 2 9 0 . 0 0 12 . 83 1 3 . 7 7 1 3 . 7 6 1 1 . 8 8 1 1 . 4 9 12 . 1 8 2 . 3 0 2 . 4 7 2 . 2 6 0 . 8 9 0 . 9 1 1 . 0 4 97 . 5 6 T2 5 42 . 5 6 10 . 4 3 3 . 3 8 1 1 . 4 7 0 . 3 5 1 3 . 7 2 1 1 . 5 6 2 . 4 5 0 . 8 0 9 6 . 7 7 T2 5 42 . 1 5 10 . 9 6 3 . 6 6 1 1 . 2 0 0 . 2 7 1 4 . 2 6 1 1 . 3 0 2 . 5 3 0 . 7 8 9 7 . 0 6 T2 5 4 2 . 3 2 12 . 7 0 1 . 9 8 8 . 7 7 0 . 0 0 1 5 . 5 3 12 . 3 2 2 . 3 9 0 . 8 6 Tota l 9 7 . 3 3 9 6 . 87 9 7 . 12 9 7 . 2 7 9 7 . 0 5 9 6 . 0 0 9 6 . 7 3 9 7 . 1 1 9 6 . 8 7 287 Appendix 12 . 3 : C l i nopyrox ene . Sampl e T5 T5 T 5 T 5 T5 T 5 T 5 T 5 S i02 5 1 . 9 0 4 7 . 5 7 52 . 52 52 . 0 4 4 9 . 5 1 5 1 . 1 7 52 . 2 0 5 1 . 4 6 Al 20 3 2 . 2 9 6 . 7 8 2 . 8 0 1 . 8 0 5 . 2 3 2 . 1 1 2 . 0 7 2 . 45 Ti02 0 . 8 0 1 . 0 6 0 . 3 4 0 . 5 2 0 . 8 0 0 . 6 4 0 . 4 5 0 . 64 FeO 1 1 . 4 3 7 . 7 2 6 . 7 0 9 . 8 0 7 . 2 0 1 1 . 9 2 7 . 8 5 7 . 9 1 M nO 0 . 2 9 0 . 1 5 0 . 1 9 0 . 1 6 0 . 14 0 . 3 7 0 . 4 5 0 . 4 0 M gO 1 4 . 7 9 12 . 7 4 1 6 . 3 7 1 4 . 6 8 13 . 19 1 3 . 7 7 1 5 . 8 3 1 5 . 08 CaO 1 8 . 3 7 2 2 . 2 5 2 1 . 0 8 2 0 . 3 4 2 3 . 4 1 1 9 . 1 0 2 0 . 85 2 0 . 2 9 Na 2o 0 . 4 4 0 . 2 8 0 . 2 9 0 . 3 0 0 . 2 6 0 . 3 5 0 . 3 2 0 . 3 9 cr 2 o3 0 . 3 9 0 . 0 0 0 . 0 0 0 . 0 0 0 . 0 0 0 . 0 0 0 . 0 0 0 . 00 - - - - - -- - - - - - - - - - - - - - - - - -- ---------- - - - - - - - - - - - - - - - ----- Total 1 0 0 . 7 0 9 8 . 5 5 10 0 . 2 9 9 9 . 6 4 9 9 . 7 4 9 9 . 4 3 10 0 . 0 2 9 8 . 62 S ample T 5 T 5 T 5 T 5 T5 T5 T 5 T 5 S i0 2 5 1 . 1 3 5 0 . 7 5 5 0 . 1 0 5 0 . 3 3 49 . 7 4 5 1 . 8 3 5 1 . 2 9 4 9 . 92 Al 2 0 3 2 . 5 8 3 . 4 8 4 . 3 8 3 . 4 9 2 . 4 3 2 . 4 0 2 . 8 1 4 . 1 1 T i0 2 0 . 6 4 0 . 8 2 0 . 8 5 0 . 7 3 0 . 6 1 0 . 5 0 0 . 6 5 0 . 9 0 FeO 9 . 2 5 7 . 9 6 8 . 7 8 8 . 1 1 7 . 7 1 6 . 1 7 7 . 5 9 8 . 3 0 MnO 0 . 1 6 0 . 4 0 0 . 4 4 0 . 3 0 0 . 2 8 0 . 4 6 0 . 2 8 0 . 2 8 M gO 1 4 . 3 2 14 . 5 7 1 3 . 4 9 1 4 . 4 3 1 5 . 18 1 5 . 1 6 14 . 7 4 13 . 7 5 CaO 2 0 . 2 1 2 1 . 3 1 2 1 . 9 3 2 0 . 8 7 2 1 . 2 4 2 1 . 4 6 2 1 . 8 1 2 1 . 9 8 Na2 o 0 . 3 6 0 . 3 3 0 . 4 0 0 . 3 6 0 . 4 0 0 . 3 8 0 . 3 9 0 . 32 Cr 2 o 3 0 . 0 0 0 . 0 0 0 . 0 0 0 . 0 0 0 . 0 0 0 . 0 0 0 . 0 0 0 . 0 0 - - - - - - - - - - - - - - - - - - - - - - - - - ----------- - - - - - - - - - - - ------- Total 9 8 . 6 5 9 9 . 62 1 0 0 . 3 7 9 8 . 6 2 97 . 5 9 9 8 . 3 6 9 9 . 5 6 9 9 . 5 6 288 Appendix 12 . 3 Con t inued . Samp l e T2 4 T2 4 T 2 4 T 2 4 T24 T2 4 T 2 4 T2 4 S i02 52 . 5 6 5 0 . 2 8 52 . 4 3 4 9 . 7 9 52 . 12 49 . 7 4 5 0 . 6 0 52 . 3 5 A l20 3 1 . 5 8 3 . 9 1 1 . 6 3 3 . 7 2 3 . 0 3 4 . 54 2 . 8 0 1 . 4 0 Ti02 0 . 4 3 0 . 8 3 0 . 4 1 0 . 8 1 0 . 4 5 0 . 8 4 0 . 6 7 0 . 3 9 FeO 1 1 . 0 2 8 . 5 2 8 . 1 7 8 . 4 9 5 . 7 3 6 . 4 2 9 . 9 3 10 . 7 8 MnO 0 . 2 5 0 . 2 9 0 . 62 0 . 5 4 0 . 00 0 . 0 0 0 . 2 7 0 . 2 6 M gO 15 . 0 0 1 4 . 2 8 1 5 . 5 8 1 3 . 2 9 1 5 . 42 14 . 1 6 13 . 6 8 14 . 9 1 CaO 18 . 9 6 2 1 . 2 3 2 0 . 82 2 2 . 1 9 2 3 . 0 4 23 . 67 2 0 . 5 1 1 9 . 3 9 Na2 o 0 . 2 9 0 . 3 8 0 . 4 6 0 . 4 2 0 . 2 6 0 . 2 5 0 . 4 0 0 . 2 9 - ---- - - - - - --------------- ---------- ------ ------------- - To t a l 1 00 . 0 9 9 9 . 7 2 1 0 0 . 12 9 9 . 2 5 1 0 0 . 0 5 99 . 62 9 8 . 8 6 9 9 . 7 7 Samp l e T2 4 T 2 4 T2 4 T 2 4 T2 4 T24 T2 4 T2 4 S i02 5 1 . 2 9 5 1 . 8 4 4 8 . 0 3 5 1 . 2 3 5 1 . 00 5 1 . 87 53 . 60 52 . 1 0 Al20 3 3 . 07 2 . 2 7 6 . 0 4 2 . 6 7 2 . 3 7 2 . 4 0 1 . 2 0 1 . 54 Ti02 0 . 5 9 0 . 57 0 . 9 3 0 . 5 6 0 . 59 0 . 4 5 0 . 2 8 0 . 4 3 FeO 8 . 02 1 1 . 1 6 9 . 02 8 . 9 4 1 1 . 0 3 5 . 67 7 . 4 0 9 . 9 3 MnO 0 . 17 0 . 2 6 0 . 3 0 0 . 4 1 0 . 2 3 0 . 0 0 0 . 6 1 0 . 2 5 M gO 1 3 . 6 6 1 4 . 0 9 12 . 0 1 1 3 . 0 1 14 . 1 5 1 5 . 72 1 5 . 0 2 1 5 . 0 4 CaO 2 2 . 7 6 1 9 . 8 4 22 . 7 3 2 2 . 4 3 1 9 . 6 4 2 3 . 4 4 2 2 . 2 8 1 9 . 5 9 Na2o o . 2 5 0 . 2 9 0 . 4 7 0 . 3 3 0 . 3 1 0 . 2 3 0 . 3 9 0 . 2 8 ------------ ------------ ---------------- ------- ------- Tot a l 9 9 . 8 1 1 0 0 . 32 9 9 . 5 3 9 9 . 5 8 9 9 . 3 2 9 9 . 7 8 1 0 0 . 7 8 9 9 . 1 5 289 Appendix 12 . 3 : Con t i nued . Samp l e T2 5 T2 5 T2 5 T2 5 T2 5 T2 5 T2 5 T 2 5 S i02 5 1 . 6 7 5 0 . 8 5 5 1 . 6 3 5 0 . 2 5 5 0 . 3 0 4 8 . 8 6 5 1 . 4 2 52 . 0 9 A l203 2 . 6 0 3 . 1 0 2 . 5 4 3 . 6 6 3 . 62 5 . 1 3 2 . 1 4 3 . 6 6 Ti02 0 . 4 3 0 . 5 1 0 . 4 6 0 . 6 3 0 . 5 5 0 . 7 4 0 . 3 2 0 . 3 0 FeO 8 . 4 3 7 . 4 1 7 . 6 2 8 . 4 8 8 . 6 8 7 . 02 9 . 0 6 6 . 4 8 MNO 0 . 3 9 0 . 2 9 0 . 5 1 0 . 3 5 0 . 3 5 0 . 07 0 . 2 4 0 . 1 6 M gO 1 4 . 3 5 1 4 . 1 4 14 . 9 7 13 . 0 3 1 3 . 3 4 1 3 . 82 14 . 3 5 1 5 . 3 1 CaO 2 1 . 5 4 2 2 . 7 0 2 1 . 6 0 2 2 . 2 6 2 2 . 2 8 2 3 . 0 3 2 0 . 6 7 2 1 . 6 4 Na2o 0 . 3 3 0 . 3 0 0 . 3 9 0 . 52 0 . 4 9 0 . 3 1 0 . 3 3 0 . 3 7 ------------ - - - - - ------- - - - - - - - ----------------------- Total 9 9 . 7 4 9 9 . 3 6 9 9 . 7 2 9 9 . 1 8 9 9 . 6 1 9 8 . 9 8 98 . 5 3 1 0 0 . 0 1 Samp le T2 5 T2 5 T2 5 T2 5 T 2 5 T2 5 T2 5 T2 5 S i02 5 3 . 2 6 52 . 1 4 5 1 . 12 52 . 8 0 5 1 . 2 5 5 0 . 8 7 5 1 . 1 7 5 1 . 1 1 A l203 1 . 7 2 3 . 2 9 2 . 5 8 1 . 0 6 2 . 4 8 2 . 6 7 2 . 8 1 2 . 5 2 T i02 0 . 1 9 0 . 4 2 0 . 3 5 0 . 2 2 0 . 4 3 0 . 4 6 0 . 4 7 0 . 4 0 FeO 4 . 4 9 5 . 1 1 8 . 3 1 7 . 2 6 8 . 0 5 1 1 . 2 2 9 . 0 3 8 . 9 1 MNO 0 . 1 3 0 . 1 4 0 . 2 8 0 . 6 5 0 . 4 0 0 . 3 1 0 . 2 2 0 . 1 5 M gO 1 6 . 4 4 1 5 . 3 1 1 3 . 5 2 14 . 8 3 1 3 . 6 5 1 3 . 8 3 14 . 4 6 1 4 . 7 8 CaO 2 2 . 5 0 2 3 . 4 3 2 2 . 8 0 22 . 0 4 2 2 . 6 8 1 9 . 6 9 2 0 . 7 4 2 0 . 3 5 Na2o 0 . 2 4 0 . 3 3 0 . 3 6 0 . 3 6 0 . 3 5 0 . 3 5 0 . 1 6 0 . 3 8 -- -- - - - - - ---- ---------------- ------------------ ------- Tota l 9 8 . 9 7 1 0 0 . 1 7 9 9 . 3 2 9 9 . 2 2 9 9 . 2 9 9 9 . 4 0 99 . 0 6 9 8 . 6 0 S amp le T2 5 T2 5 T 2 5 T2 5 T 2 5 T2 5 T2 5 T2 5 S i02 52 . 2 6 52 . 2 5 5 0 . 3 7 50 . 4 7 4 8 . 3 1 4 8 . 3 1 5 1 . 9 9 5 1 . 6 2 A l20 3 2 . 02 2 . 62 4 . 02 3 . 5 4 5 . 82 5 . 6 5 2 . 4 4 3 . 2 6 T i02 0 . 4 4 0 . 3 9 0 . 4 2 0 . 4 0 0 . 6 9 0 . 7 0 0 . 4 4 0 . 3 9 FeO 8 . 3 8 8 . 5 2 7 . 2 7 7 . 1 7 8 . 8 7 8 . 3 0 9 . 9 5 6 . 0 6 MNO 0 . 2 0 0 . 1 7 0 . 2 2 0 . 2 1 0 . 1 3 0 . 1 5 0 . 2 5 0 . 0 0 M gO 1 5 . 5 1 1 5 . 0 9 1 3 . 4 2 13 . 8 4 12 . 3 5 12 . 3 2 14 . 6 8 1 4 . 8 3 CaO 2 0 . 0 3 2 0 . 6 1 2 3 . 2 8 2 3 . 0 5 2 2 . 8 9 2 2 . 8 0 1 9 . 7 2 2 3 . 6 5 Na2o 0 . 3 5 0 . 3 3 0 . 3 1 0 . 3 1 0 . 3 6 0 . 4 2 0 . 4 5 0 . 2 5 ----------- - - - ----- ----------------------------------- Tota l 9 9 . 1 9 9 9 . 9 8 9 9 . 3 1 9 8 . 9 9 9 9 . 4 2 9 8 . 65 99 . 92 1 0 0 . 0 6 290 Appendix 12 . 4 : Or thopyroxenes . S amp l e T3 T3 T3 T3 T3 T3 T3 T 3 S i02 5 1 . 4 6 5 1 . 3 4 5 4 . 2 2 53 . 5 3 5 1 . 1 4 5 4 . 2 5 53 . 7 5 5 3 . 5 5 A l 20 3 0 . 3 5 0 . 3 8 1 . 4 1 1 . 4 9 0 . 2 8 2 . 4 8 1 . 6 6 2 . 54 T i 02 0 . 1 0 0 . 1 2 0 . 14 0 . 1 4 0 . 0 0 0 . 1 0 0 . 1 6 0 . 12 FeO 2 8 . 6 0 2 9 . 4 1 1 6 . 2 3 15 . 3 4 2 9 . 7 0 1 1 . 7 2 14 . 9 6 1 1 . 8 6 MnO 1 . 3 3 1 . 5 9 0 . 2 9 0 . 3 3 1 . 4 4 0 . 2 1 0 . 3 3 0 . 22 M gO 1 6 . 9 9 1 6 . 1 8 2 5 . 7 9 2 6 . 0 8 1 5 . 6 0 2 9 . 4 5 27 . 12 2 8 . 7 4 CaO 0 . 80 0 . 8 9 1 . 4 5 1 . 1 9 0 . 83 1 . 42 1 . 54 1 . 47 --------- ------------------------------- --- -------- --- Tot a l 9 9 . 6 3 9 9 . 9 1 9 9 . 5 3 9 8 . 1 0 9 8 . 9 9 9 9 . 7 9 99 . 5 2 9 8 . 5 0 S amp l e T 3 T 3 T 3 T3 T3 T 3 T 3 T 3 S i0 2 54 . 1 3 5 1 . 6 3 5 1 . 8 6 5 0 . 8 7 5 1 . 4 5 5 1 . 3 1 5 1 . 5 9 5 3 . 4 7 A l20 3 2 . 4 8 0 . 3 4 0 . 3 0 0 . 3 5 0 . 4 2 0 . 3 3 0 . 4 2 0 . 7 9 Ti02 0 . 12 0 . 0 5 0 . 0 9 0 . 0 6 0 . 12 0 . 0 8 0 . 0 0 0 . 1 1 FeO 1 1 . 67 2 8 . 1 5 2 6 . 6 8 2 8 . 3 5 2 6 . 7 0 2 8 . 5 6 2 7 . 3 5 2 0 . 4 2 MnO 0 . 2 2 1 . 4 4 1 . 3 5 1 . 32 1 . 1 9 1 . 3 4 1 . 1 8 0 . 7 0 M gO 2 8 . 9 6 17 . 3 9 1 8 . 2 0 1 6 . 7 3 1 7 . 9 5 1 6 . 3 7 17 . 52 2 3 . 4 5 CaO 1 . 4 7 0 . 8 3 0 . 7 9 0 . 8 3 1 . 2 7 0 . 8 6 1 . 3 0 0 . 7 9 ------------ ---- -------------------------------------- Tot a l 9 9 . 0 5 9 9 . 83 9 9 . 2 7 9 8 . 5 1 9 9 . 1 0 9 8 . 8 5 9 9 . 3 6 9 9 . 7 3 Samp l e T3 T3 T 3 S i02 53 . 4 6 52 . 9 8 5 3 . 5 4 A l20 3 0 . 6 8 1 . 82 1 . 4 3 Ti02 0 . 0 0 0 . 1 3 0 . 2 5 FeO 19 . 89 17 . 5 1 1 6 . 9 8 M nO 0 . 7 2 0 . 2 8 0 . 32 M gO 2 3 . 5 7 2 4 . 92 2 4 . 9 5 CaO 0 . 89 1 . 5 1 1 . 9 5 ------------------- Tot a l 99 . 2 1 9 9 . 1 5 9 9 . 4 2 291 App endix 12 . 4 : Cont inued . S amp le T2 4 T2 4 T2 4 T 2 4 T2 4 T 2 4 T2 4 T2 4 S i02 5 0 . 6 8 52 . 3 8 5 3 . 3 9 5 1 . 1 2 5 1 . 2 6 52 . 5 1 52 . 8 5 52 . 9 2 Al 20 3 1 . 1 6 1 . 52 1 . 3 6 0 . 3 7 0 . 4 0 1 . 7 9 1 . 07 3 . 6 4 T i02 0 . 2 3 0 . 3 1 0 . 2 7 0 . 1 3 0 . 1 9 0 . 2 0 0 . 2 5 0 . 0 0 FeO 2 8 . 2 0 1 9 . 7 0 1 8 . 0 2 3 0 . 62 3 0 . 7 3 1 9 . 2 7 2 0 . 1 2 1 4 . 0 9 MnO 1 . 3 9 0 . 4 7 0 . 4 6 1 . 7 1 1 . 7 7 0 . 4 6 0 . 3 7 0 . 2 6 M gO 1 6 . 2 7 22 . 9 8 2 4 . 1 6 14 . 4 5 14 . 4 1 2 3 . 5 0 22 . 4 7 2 7 . 0 4 CaO 1 . 9 1 1 . 2 8 1 . 3 2 1 . 1 8 1 . 2 5 1 . 3 3 1 . 7 7 1 . 3 5 ---- ---------------------------- ------ ---------------- Total 9 9 . 8 4 9 8 . 6 4 9 8 . 9 8 9 9 . 5 8 1 0 0 . 0 1 9 9 . 0 6 9 8 . 9 0 9 9 . 3 0 S amp l e T 2 4 T2 4 T2 4 T24 T2'4 T2 4 T2 4 T2 4 S i02 5 4 . 4 0 52 . 3 8 52 . 8 2 5 1 . 5 6 5 0 . 6 3 52 . 1 4 52 . 0 6 54 . 1 5 A l20 3 2 . 2 6 1 . 2 0 0 . 7 4 0 . 6 8 0 . 4 4 0 . 6 9 0 . 82 0 . 8 8 T i02 0 . 1 7 0 . 3 1 0 . 2 1 0 . 18 0 . 1 3 0 . 2 3 0 . 2 6 0 . 2 0 FeO 1 3 . 7 8 2 0 . 9 6 1 8 . 84 2 4 . 2 7 2 8 . 4 2 2 4 . 4 1 2 4 . 1 5 1 8 . 5 5 MnO 0 . 2 6 0 . 5 2 0 . 5 8 0 . 8 4 1 . 5 7 0 . 5 0 0 . 7 2 0 . 3 9 M gO 2 7 . 5 2 2 1 . 7 3 2 4 . 0 5 1 9 . 7 9 15 . 7 8 1 9 . 3 3 19 . 4 0 2 3 . 8 5 CaO 1 . 1 3 1 . 5 3 1 . 5 8 1 . 3 3 1 . 2 9 1 . 32 1 . 6 1 1 . 8 5 --- - -------- --------- -------- -------- ----------------- T o t a l 9 9 . 52 9 8 . 6 3 9 8 . 82 9 8 . 6 5 9 8 . 2 6 9 8 . 6 2 9 9 . 02 9 9 . 8 7 S amp l e T2 4 T2 4 T2 4 T24 T2 4 T2 4 T2 4 T2 4 S i02 5 1 . 0 1 5 1 . 7 8 53 . 4 5 5 1 . 6 2 52 . 2 4 5 2 . 5 3 53 . 6 1 53 . 3 9 A l 20 3 0 . 5 2 0 . 4 3 0 . 8 8 0 . 5 1 3 . 4 6 1 . 2 5 1 . 9 9 1 . 2 3 T i 02 0 . 1 7 0 . 1 9 0 . 2 2 0 . 1 8 0 . 2 2 0 . 00 0 . 2 3 0 . 3 5 FeO 2 8 . 0 5 2 6 . 7 4 2 0 . 5 9 2 7 . 9 8 1 8 . 7 3 2 1 . 5 7 1 7 . 4 0 1 9 . 5 4 MnO 1 . 5 4 1 . 5 7 0 . 5 9 1 . 54 0 . 3 7 0 . 5 2 0 . 2 5 0 . 3 6 M gO 1 6 . 5 0 1 7 . 6 1 2 2 . 7 1 1 6 . 7 4 2 3 . 6 4 2 1 . 7 5 2 4 . 9 8 2 2 . 8 3 CaO 1 . 32 1 . 2 6 1 . 6 7 1 . 2 0 1 . 2 1 1 . 5 6 1 . 4 3 2 . 1 4 --------------- --------------------------------------- T o t a l 9 9 . 1 1 99 . 5 8 1 0 0 . 1 1 9 9 . 7 7 9 9 . 8 7 9 9 . 1 8 9 9 . 8 9 9 9 . 8 4 292 Appen dix 12 . 4 : Cont inued . Samp l e T2 5 T2 5 T2 5 T 2 5 T2 5 T 2 5 T 2 5 T2 5 S i02 5 1 . 4 8 5 1 . 0 6 52 . 7 8 5 3 . 0 9 53 . 9 5 52 . 8 3 52 . 9 4 5 3 . 7 9 Al203 0 . 4 3 0 . 4 2 1 . 3 5 1 . 0 6 1 . 0 6 1 . 4 9 1 . 2 3 1 . 3 1 T i02 0 . 1 3 0 . 1 1 0 . 2 9 0 . 3 1 0 . 2 0 0 . 2 4 0 . 2 3 0 . 0 0 FeO 2 8 . 6 4 2 8 . 5 8 2 0 . 4 3 2 0 . 9 7 1 8 . 9 9 1 9 . 5 9 2 0 . 4 0 17 . 3 6 MnO 1 . 5 8 1 . 6 9 0 . 5 0 0 . 4 0 0 . 3 9 0 . 6 2 0 . 4 7 0 . 3 9 M gO 1 6 . 2 9 1 6 . 4 2 22 . 5 7 2 2 . 3 5 2 3 . 9 6 2 3 . 0 2 22 . 9 7 2 4 . 9 2 CaO 1 . 2 1 1 . 2 4 1 . 4 4 1 . 5 5 1 . 34 1 . 5 1 1 . 5 6 1 . 4 8 - - - - --------------- ----- --------------- --------------- Total 9 9 . 7 6 9 9 . 5 2 99 . 3 6 9 9 . 7 3 9 9 . 8 9 9 9 . 3 0 99 . 8 0 9 9 . 2 5 Samp l e T2 5 T2 5 T2 5 T2·5 T2 5 T2 5 T2 5 T2 5 S i02 5 3 . 3 9 52 . 5 6 52 . 4 4 52 . 7 6 5 3 . 2 0 52 . 9 5 52 . 5 6 52 . 4 8 A l203 1 . 0 3 3 . 9 7 4 . 0 7 1 . 4 3 3 . 1 5 1 . 12 1 . 2 1 1 . 0 0 Ti02 0 . 2 1 0 . 14 0 . 17 0 . 2 2 0 . 17 0 . 1 9 0 . 2 6 0 . 2 6 FeO 2 0 . 0 1 14 . 7 0 1 5 . 14 1 9 . 7 5 1 3 . 5 0 1 9 . 5 5 18 . 7 7 2 0 . 3 4 MnO 0 . 4 6 0 . 2 5 0 . 3 1 0 . 6 0 0 . 3 1 0 . 6 1 0 . 4 1 0 . 4 7 M gO 2 3 . 5 4 2 5 . 9 3 2 6 . 0 2 2 3 . 0 5 2 7 . 2 8 2 2 . 87 2 3 . 55 2 2 . 6 9 CaO 1 . 6 7 1 . 0 9 1 . 1 0 1 . 5 5 1 . 3 3 1 . 5 2 1 . 6 6 1 . 7 1 - - - - - ------------------------------------ -------------- Total 1 0 0 . 3 1 9 8 . 6 4 9 9 . 2 5 9 9 . 3 6 9 8 . 9 4 9 8 . 8 1 98 . 4 2 9 8 . 9 5 Samp l e T2 5 T2 5 T2 5 T2 5 T2 5 T2 5 T2 5 T2 5 S i02 5 2 . 6 9 52 . 5 8 5 3 . 1 1 52 . 9 6 5 3 . 7 9 52 . 9 7 53 . 62 5 1 . 8 9 Al203 0 . 9 9 1 . 3 5 1 . 1 9 0 . 7 9 0 . 9 6 1 . 00 1 . 30 0 . 4 2 Ti02 0 . 2 1 0 . 2 4 0 . 2 5 0 . 1 6 0 . 1 7 0 . 2 3 0 . 12 0 . 0 0 FeO 1 9 . 7 5 2 0 . 2 8 1 9 . 2 3 2 3 . 3 6 1 8 . 6 7 1 7 . 6 9 18 . 14 2 7 . 9 5 MnO 0 . 4 1 0 . 4 2 0 . 5 2 0 . 62 0 . 4 6 0 . 4 2 0 . 4 5 1 . 7 5 M gO 2 2 . 9 1 2 2 . 7 0 2 3 . 5 2 1 9 . 9 5 2 3 . 5 6 2 4 . 3 6 2 4 . 3 5 1 6 . 9 5 CaO 1 . 7 0 1 . 7 0 1 . 6 4 2 . 0 1 1 . 82 2 . 12 1 . 52 1 . 1 2 - - - - --------- ------------------------ - - - -------------- Total 9 8 . 6 6 9 9 . 2 7 9 9 . 4 6 9 9 . 8 5 9 9 . 4 3 9 8 . 7 9 9 9 . 50 1 0 0 . 0 8 BIBLIOGRAPHY Ager, T . A . 1 9 8 3 : Glacial and floral changes in southern Argentina since 1 4 0 0 0 years ago . National geographic research report 1 5 : 457-47 9 . 2 9 3 Alaily, F . 1 9 8 6 : Cracks in sandy soils of the ext reme arid part o f the Sahara . Abstracts of the 13th Congress of the International Society of Soil Science, 1 98 6, Hamburg III : l 023-1024 . Anderson, R . B . ; Hallet , B . 1 98 6 : Sediment transport by wind : towards a general model . Geological society of America bulletin 9 7 : 523-535 . Anderton, P . W . 1 9 8 1 : Structure and evolution of the south Wanganui Basin . New Zealand journal of geology and geophysics 24 : 3 9- 63 . Andrews , J . T . 1 9 82 : On tne reconstruct ion of the Pleistocene ice sheets : a review . Quaternary sciences review 1 : 1-31 . Anonymous 1 9 8 1 : Post-conference tour, North Island . in Pollok, J . A . ; Parfitt, R . L . ; Furket , R . J . eds . Guide book 4 . Soils with Variable Charge Conference, 1 981, Palmerston North . Anthony, J . C . 1 9 8 4 : The stratigraphy and mineralogy of a Late P leistocene loess sequence in southern Manawatu . Unpublished B . Sc . ( Hons . ) dissertation held in the Department of Soil Science , Massey University . Aoyagi , K . ; Kazama , T . 1 9 8 0 : Transformat ional changes of clay minerals , zeolites and silica minerals during diagenesis . Sedimentology 27 : 1 7 8-188 . Applernan, D . E . ; Nis sen, H . U . ; Stewart , D . B . ; Clark, J . R . ; Dowty, E . ; Huebner , J . S . 1 971 : Studies of Lunar plagioclases , tridymite and cristobalite . Proceedings of the Second Lunar Conference 1 : 1 1 - 133 . Arrhenius, G . O . 1 952 : Sediment cores from the east Pacific . Chapter 5 . In Pettersson, H . ed. Reports of the Swedish Deep-sea Expedit ion . 227pp . Backett , W . 1 9 8 5 : Geology and petrology of Ruapehu Volcano and related vents . Unpublished Ph . D . thesis held in the Library, Victoria University of Wellington . Bagnold, R . A . 1 9 7 3 : The physics of blown sand and desert dunes . New York, Methuen . 2 65p . Bailey, J . M . 1 97 1 : Extraction and radiocarbon dating of dispersed organic material from loess in the South Island of New Zealand . New Zealand journal of science 1 4 : 4 9 0-5 03 . 2 9 4 Baker, G . 1 959 : Opal phytoliths in some Victorian soils and "Red Rain" residues . Australian journal of botany 7 : 64-8 7 . Baker, G . 1 9 6 0 : Hook-shaped opal phytoliths in the epidermal cells of oats . Australian journal of botany 8 : 6 9 -7 4 . Balsam, W . 1 9 81 : Late Quaternary sedimentation in the western north At lantic : stratigraphy and palaeoecology . Palaeogeography, palaeoclimatology, palaeoecology 35 : 2 15-240 . Barnett , R . 1 9 8 4 : Upper Quaternary stratigraphy in the Otaki district . Unpublished B : Sc . (Hons ) thesis , held in the Library, Victoria University of Wellington . Barratt , B . C . 1 98 1 : Micromorphology of a yellow-grey earth to yellow­ brown earth soil sequence on loess in Canterbury, Otago and Southland, New Zealand . New Zealand Soil Bureau scientific report 45 . Barratt , B . C . 1 9 8 4 : Micromorphology of yellow-grey earths . Pp 59- 6 4 . In Bruce , J . G . ( ed . ) . Soil Groups of New Zealand. Part 7 . Yellow­ grey earths . Lower Hutt , New Zealand Society of Soil Science . Barron , E . J . ; Washington, W .M . 1 982 : Atmospheric circulat ion during warm geologic periods : Is the equator-to-pole surface-temperature gradient the controlling factor . Geology 1 0 : 633-63 6 . Bartoli, F . 1 9 8 5 : Crystallochemistry and surface properties of biogenic opal . Journal of soil science 3 6 : 3 35-350 . Bartoli , F . ; Guillet , B . 1977 : Etude compareie des phytilithiques et polliniques d ' un podzol des vosges Greseuses . Acadimie des Science Comptes Rendus 284D : 3 53-35 6 . Bartoli , F . ; Wilding, L . P . 1 9 80 : Dissolution of biogenic opal as a function of its physical and chemical prope rties . Journal of the Soil Science Society of America 44 : 8 73-87 8 . Beavers , A . H . ; Stephen, I . 1958 : S ome features of the distribution of p lant-opal in Illinois soils . Soil science 8 6 : 1-5 . Beget , J . E . 1 9 8 3 : Radiocarbon-dated evidence of world wide early Holocene climatic change . Geology 1 1 : 38 9-3 93 . Benny, L . A . 1 982 : A mineralogical and textural study of the central North Island tephra, Okareka Ash and its overlying tephric loess deposit . Unpublished M . Sc . thesis, held in the Library, Massey University . 2 9 5 Bernard, A . ; Guern , F . 1 9 8 6 : Condensation o f volatile elements in high temperature gases of Mount St . Helens . Journal of volcanology and geothermal research 28 : 91-1 05 . Birrell , K . S . 1 9 5 6 : Soil conditions in relat ion to engineering in New Zealand . Proceedings of the 2nd Australia-New Zealand Conference on Soil Mechanics and Foundation Engineering, 1 95 6, Christchurch . Pp 17-19 . Birrell , K . S . 1 972 : The physical properties of loess s oils and the influence of cultivat ion . In Watt , J . P . C . ed . Loess Soils and Land use on the Downlands of the South Island of New Zealand, with particular reference to the North Otago area . Otago Catchment Board Publication 4 : 2 9-44 . Birrell , K . S . ; Packard, R . Q . 1 953 : Some Phys ical properties of New Zealand "loes s" . New Zealand journal of science and technology B35 : 30-35 . Birrell, K . S . ; Pullar , W . A . 1 97 3 : Weathering of paleosols in Holocene and Late Pleistocene tephras in central North Island, New Zealand . New Zealand journal of geology and geophysics 1 6 : 687- 7 02 . Bishop, D . G . ; Lindqvist , J . K . ; Ritchie , D . D . ; Turnbull , I . M . 1 9 8 4 : Modern sedimentat ion at Falls Dam, upper Manuherikia River, Central Otago, New Zealand . New Zealand journal of geology and geophysics 2 7 : 30 5 -312 . Blakemore , L . C . 1 9 5 8 : Chemistry of the yellow-grey earths in the North Island, New Zealand . New Zealand soil news 6 : 2 1 8-2 2 5 . B lakemore , L . C . 1 9 8 4 : Survey chemistry of yellow-grey earths . Pp . 66- 7 0 . In Bruce, J . G . ed. Soil Groups of New Zea land . Part 7 , Yellow-grey earths . New Zealand Society of Soil Science , Lower Hutt , New Zealand . Blattner, P . ; Bird, G . W . 1 974 : Oxygen isotope fractionation between quartz and K-feldspar at 6 0 0°C . Earth and planetary science letters 23 : 21-2 7 . 2 9 6 Sleeker , P . ; Parfitt , R . L . 1 974 : Volcanic ash and its clay mineralogy at Cape Hoskins , New Brittain, Papua New Guinea . Geoderma 1 1 : 123- 135 . Bloom, A . L . 1 97 1 : Glacial eustatic and isostatic cont rols of sea level s ince the last glaciat ion . Pp 355-3 7 9 . In Turekian, K . K . ed . Late Cenozoic glacial ages . New Haven, Yale University P ress . Bloom, A . L . 1 9 8 3 : Sea level movements during the last interglacial hemicycle . International geological correlation program report No . 11 . Bloom, A . L . ; Broecker, W . S . ; Chappel , J . M . A . ; Mathews , R . K . ; Mesolella, K . J . 1 97 4 : Quaternary sea level fluctuat ions on a · tectonic coast : New 230Th/234u dates from Huon Peninsula , New Guinea . Quaternary research 4 : 1 8 5-2 0 5 . Bott inga , Y . ; Javoy, M . 1 97 3 : Comments on oxygen isotope geothermometry . Earth and planetary science letters 2 0 : 250-2 65 . Bra z ier , J . D . ; Franklin, G . L . 1 9 6 1 : Identification of hardwoods ; a microscopic key . Forest Products research bulletin 4 6 . Brindley, G . W . 1 957 : Fullers earth from near Dry Branch, Georgia - a montmorillonite-cristobalite clay . Clay mineralogy bulletin 3 : 1 67-1 6 9 . Bronger , A . 1 9 8 6 : Argillic horizons in modern loess soils in an ustic soil moisture regime in the temperate climatic zone . Abstracts of the 13th International Soil Science Society Congress, 1 986, Hamburg III : 1 0 68-10 6 9 . Brooks , R . R . 1 9 65 : The distribution of elements in gleyed and concretionary material in a New Zealand yellow-grey earth . New Zealand journal of science 8 : 8 8 -92 . Brown, G . 1 9 8 0 : Associated Minerals . Pp 3 61-411 . In Brindley, G . W . ; B rown, G . eds . Crystal structures of clay minerals and their X­ ray identificat ion . London, Mineralogical Society . Bruce , J . G . 1 972 : Loess soils in the South Island . In Watt , J . P . C . ed. Loess Soils and Land use on the Downlands of the South Island of New Zealand, with particular reference to the North Otago area . Otago Catchment Board Publication 4 : 1-2 8 . Bruce, J . G . 1 9 7 3a : A time-stratigraphic sequence of loess deposits on near coasta l surfaces in the Balclutha district . New Zealand journal of geology and geophysics 1 6: 5 4 9-55 6 . Bruce , J . G . 1973b : Loessial deposit s in southern South Island, with a def init ion of Stewarts Claim Format ion . New Zealand journal of geology and geophysics 1 6 : 533-548 . Bruce , J . G . 1978a : Loess content of soils in South Island, New Zealand; scale 1 : 1 , 0 0 0 , 0 0 0 . Map to accompany Watt, J . P . C . ed . Loess Soils and Land use on the Downlands of the South Is land of New Zealand, with part icular reference to the North Otago area . Otago Catchment Board Publication 4 . 2 9 7 Bruce , J . G . 1 978b : Soils o f part o f Raglan county, South Auckland, New Zealand . New Zealand Soil Bureau bulletin 41 . Bruce , J . G . 1 9 8 3 : Effect of climate on morphological features of soils f rom loess in the southern part of South Island, New Zealand . Australian journal of soil science 21 : 3 5 9-37 1 . Bruce, J . G . 1 9 84a : Yellow-grey earths of Southland and West Otago . Pp 4 6- 5 1 . In Bruce , J . G . ed . Soil Groups of New Zealand Part 7 . Yel low-grey earths . Lower Hutt, New Zealand Society of Soil Science . Bruce , J . G . ed. 1 9 8 4b : Soil Groups of New Zealand . Part 7 . Yel low-grey earths . Lower Hutt , New Zealand Society of Soil Science . Bruce , J . G . ; Ives , P . W . ; Leamy, M . L . 1 97 3 : Maps and sections showing the distribution and stratigraphy of South Island loess deposits, New Zealand 1 : 1 , 0 0 0 , 0 0 0 . New Zealand soil survey report 7 . Buerger , M . J . 1954 : The stuffed derivatives o f the silica st ructure . American mineralogist 39 : 6 00-614 . Bul l , P . A . ; Bridges , E .M . 1 97 8 : Micromorphological and genetic properties of a gleyic brown podzolic soil from South Wales , United Kingdom . Abstracts of the 1 1 th International Society of Soil Science Congress, 1 9 78, Edmonton . P 3 4 . Burns , R . E . ; Andrews , J . E , et al 1 97 3 : Initial report of the deep sea drilling project , 2 1 . Washington, United States Government P rint ing Office . Butzer, K . W . 1 983 : Global sea level stratigraphy . Quaternary science review 2 : 1-17 . Buurman, P . 1 972 : Mineralisation of fossil wood . Scripta geologica 12 : 1- 4 3 . Calvert, S . E . 1 971a :. Composition and origin o f North Atlantic deep sea cherts . Contributions to mineralogy and petrology 33 : 27 3 -2 8 8 . 2 9 8 Calvert , S . E . 1 9 7 1b : Nature of silica phases in deep sea chert s o f the North Atlantic . Nature, physical sciences 234 : 33-34 . Campbell, I . B . 1 97 9 : Occurrence of Kawakawa Tephra near Nelson - Note . New Zealand journal of science 22 : 1 33-1 3 6 . Carpente r , M . A . ; Wennemer, M . 1 9 8 5 : Characterisation of synthetic t ridymite by t ransmission electron microscopy . American ndneralogist 7 0 : 517-52 8 . Carter, L . 1 980 : I ronsands in cont inental shelf sediments off western New Zealand - a synopsis . New Zealand journal of geology and geophysics 23 : 455-468 . Champnes s , P . E . ; Durham, A . C . ; Gibb, F . G . F . ; Giles, H . N . ; MacKenzie, W . S . ; Stumpfl, E . F . ; Zussman, J . 1 97 1 : Mineralogy and pet rology o f s ome Apollo 12 Lunar samples . Proceedings of the Second Lunar Conference 1 : 35 9-37 6 . Chapman, S . L . ; Syers , J . K . ; Jackson , M . L . 1 9 6 9 : Quantitative det ermination of quart z in soils, sediments and rocks by pyrosulfate fusion and hydrofluorosilicic acid t reatment . Soil s cience 1 0 7 : 3 4 8-355 . Childs , C . W . 1973 : Patterns of total element concentration in Quaternary loess columns . Abstracts of the 9th INQUA Conference 1 973, Christchurch . P 6 1 . Childs , C . W . ; Leslie , D . M . 1 9 7 7 : Interelement relationships in Fe-Mn concretions from a catenary of yellow-grey earth soils in loess . Soil science 123 : 3 6 9-37 6 . Childs , C . W . ; Searle , P . L . 1 97 5 : Element distributions in loess columns at Claremont , Table Flat , and Stewarts Claim, New Zealand . New Zealand Soil Bureau Scientific Report 20 . Christie , J . M . ; Lally, J . S . ; Heuer, A . H . ; Fisher, R .M . ; Griggs , D . T . ; Radcliffe , S .V . 1 97 1 : Comparative electron petrography of Apollo 1 1 , Apollo 12 and terrestrial rocks . Proceedings of the Second Lunar Science Conference 1 : 69-8 9 . Claridge, G . G . C . ; Weatherhead, A . V . 1 978 : Mineralogy of the silt f raction of New Zealand soils . New Zealand journal of science 21 : 4 13-42 3 . Clayton, L . ; Moran, S . R . 1 982 : Chronology of Late Wisconsin glaciation in middle North America . Quaternary science review 1 : 55-82 . Clayton, R . N . ; Epstein, S . 1 9 5 8 : The relationship between o18 : o1 6 ratios in coexistng quart z , carbonate, and iron oxides from various geological deposits . Journal of geology 66: 352-3 7 3 . Clayton, R . N . ; Mayeda , T . 1 9 6 3 : The use of bromine pentafluoride in the extraction of oxygen from oxides and silicate minerals for isotopic analysis . Geochimica et cosmochimica acta 2 7 : 43-52 . Clayton, R . N . ; O ' Neil, J . R . ; Mayeda , T . K . 1972 : Oxygen isotope exchange between quartz and water . Journal of geophysical research 7 7 : 3057-3 0 6 3 . CLIMAP Project Members , 1 97 6 : The surface of the ice-age Earth . Science 1 91 : 1 1 31-1137 . 2 9 9 Cole , J . W . 1 97 0 : Description and correlation o f Holocene volcanic formations in the Tarawera-Rerewhakaaitu region . Transactions of the Royal Society of New Zealand, earth science 8 : 93-107 . Cole , J . W . 1 97 9 : St ructure , petrology and genesis of Cenozoic volcanism, Taupo Volcanic Zone , New Zealand - a review . New Zealand journal of geology and geophysics 22 : 631- 657 . Cophen, T . B . ; Kendall, C . ; Hopple , J . 1 9 8 3 : Comparison of stable isotope reference samples . Nature 302 : 235-2 3 8 . Cornish, R . 1 98 3 : Glacial erosion in an ice divide zone . Nature 301 : 413-4 1 5 . Cortez , A . ; Franzmeier, D . P . 1 9 72 : Weathering of primary minerals in volcanic ash-derived soils of the cent ral cordillera of Columbia . Geoderma 9 : 1 65-17 6 . Cotton, C . A . 1 9 1 7 : The geomorphology of the coasta l district of south western Wel lington . Transactions and proceedings of the New Zealand Institute 50 : 2 12-222 . Cowie , J . D . 1 9 63 : Dune-building phases in the Manawatu District , New Zealand . New Zealand journal of geology and geophysics 6 : 2 6 8 -2 8 0 . Cowie, J . D . 1 9 6 4a : Aokautere Ash in the Manawatu district . New Zealand journal of geology and geophysics 7 : 67-77 . Cowie , J . D . 1 9 6 4b : Loess in the Manawatu district , New Zealand . New Zealand journal of geology and geophysics 7 : 3 8 9-3 9 6 . Cowie , J . D . 1 97 3 : P retoria Road Site section (p 8 3 ) In IX INQUA Congress Guidebook for Excursion A2, Central North Island, New Zealand . Cowie , J . D . 1 97 8 : Soils and agriculture of Kairanga County . New Zealand Soil Bureau bulletin 33 . Cowie , J . D . 1 9 8 4 : Yellow-grey earths - definit ion and classificat ion . Pp . 7 - 1 0 . In Bruce , J . G . ed . Soil Groups of New Zealand . Part 7 , Yellow-grey earths . New Zealand Society of Soil Science , Lower Hutt, New Zealand . Cowie , J . D . ; Milne , J . D . G . 1 97 3 : Maps and sections showing the distribution and strat igraphy of North Island loess and associated deposit s , New Zealand . 1 : 1 , 00 0 , 0 0 0 . New Zealand soil survey report 6 . Cowie, J . D . ; Wellman, H . W . 1 9 62 : Age of Ohakean Terrace , Rangit ikei River . New Zealand journal of geology and geophysics 5 : 6 1 7- 6 1 9 . Cox, J . E . ; Vucetich , C . G . ; Mead, C . B . , Owers, W . R . ; Daly, B . 1 97 3 : 3 0 0 Loess fallout measurements near Barrhill, Canterbury, New Zealand 1 959- 64 . Abstracts of the 9th INQUA Conference 1 9 73, Christchurch . Pp 7 0 -7 1 . Craig, H . 1 9 6 1 : Standard for reporting concentrat ions of deuterium and oxygen-1 8 in natural waters . Science 1 33 : 1 833 . Crawford, J . C . 1 8 6 9 : On the geology of the province of Wellington . Transactions of the New Zealand Institute 2 : 3 43-360 . Crawford, J . C . 1 8 8 6 : Geology of the North Island, New Zealand . Transactions of the New Zealand Institute 1 : 3 0 5-32 8 . Croney, D . ; Coleman, J . D . 1 95 3 : Soil moisture suction propert ies and their bearing on the moisture distribution in soils . Proceedings of the 3rd International Conference on Soil Mechanics and Foundation Engineering 1 : 13-18 . Croney, D . ; Jacobs , J . C . 1 9 67 : The frost susceptibility of soils and road materials . Road Research Laboratory, Report LR 90 . 68 p . Cronin, T .M . 1 9 82 : Rapid sea level and climatic changes : evidence from continental and island margins . Quaternary science review 1 : 17 7 - 215 . Cui , B . ; Kromar , P . D . ; Baba , J . 1 9 8 3 : Settling velocit ies of natural sand grains in air . Journal of sedimentary petrology 53 : 12 05- 12 1 1 . Cullen, D . J . 1 9 6 7 : S�marine evidence from New Zealand of a rapid rise in sea level at 1 1 , 0 0 0 years B . P . Palaeogeography, palaeoclimatol ogy and palaeoecology 3 : 2 8 9-2 98 . 30 1 Darragh, P . T . ; Gaskin, A . J . ; Terrell, B . C , ; Sanders, J . V . 1 9 6 6 : Origin o f precious opal . Nature 209 : 13-1 6 . Davis , J . C . 1 97 0 : Pet rology of Cretaceous Mowry Shale of Wyoming . American association of petroleum geologists 54 : 4 8 7 -502 . Davoren, A . 197 6 : A pedological study of the Kauroa Ash Formation . Unpublished M . Sc . thesis, held in the Library, Univers ity of Waikato . De Angelis, M . ; Barkov, N . I . ; Pet rov, V . N . 1 9 8 6 : Aerosol concentrat ions over the last climate cycle ( 1 60 kyr ) from an Antarctic ice core . Nature 325 : 3 1 8 -32 1 . Deer, W . A . ; Howie, R . A . ; Zussman, J . 1 9 67 : Rock-forming minerals , V . 4 F ramework silicates . London , Longmans . De Kimp, C . 197 0 : Chemical, physical and mineralogical properties of a podzol soil with fragipan derived from glacial till in the province of Quebec . Canadian journal of soil science 5 0 : 317-330 . De Kimp , C . R . 1 97 6 : Influence of parent material and moisture regime on soils genesis in the Appalachian Highlands , Quebec . Canadian journal of soil science 56 : 2 7 1 -2 8 3 . Denton , G . H . ; P rentice , M . L . ; Kellogg, D . E . ; Kellogg, T . B . 1 9 8 4 : Late Tertiary history of the At lantic ice sheet : evidence from the Dry Valleys . Geology 12 : 2 63-2 67 . Derbyshire , E . 1 9 8 3 : The loess at Jiuzhoutai, Lanzhour, People ' s Republic of China . Loess Letter 9 : 1 0 -13 . Dethier , D . P . ; Pevear, D . R . ; Frank, D . 1 9 8 1 : The 1 9 8 0 erupt ions of Mount St Helens Washington : Alteration of new volcanic deposits . United States Geological Survey professional paper 1250 : 649-665 . Duce , R . A . ; Unui, C . K . ; Ray, B . J . ; Prospero, J . M . ; Merrill, J . T . 1 9 8 0 : Long range atmospheric transport of soil dust from Asia to t ropical North Pacific : temporal variability . Science 209 : 1522- 1 52 4 . Dunbar , C . O . ; Rodgers , J . 1 958 : Principles of Stratigraphy . John Wiley and Sons , London . Duples sey, J . C . ; Arnold, M . ; Maurice , P . ; Bord, E . ; Duprat , J . ; Moyes , J . 1 9 8 6 : Direct dating of the oxygen isotope record of the last glaciation by 14c accelerator mass spectrometry . Nature 320 : 350- 352 . 3 0 2 Dutch, M . E . ; Miller , R . B . 1 965 : Rate of breakdown of Beech litter . New Zealand soil news 13 : 130-131 . Egun j obi, J . K . 1 9 6 9 : Primary productivity and nutrient cycling in terrestrial ecosystems . Tuatara 1 7 : 4 9 - 6 7 . Ehrenberg, C . G . 1 8 47 : Passatstaub und Blut regen . Deutsche Academie Wissenschafte , Berlin Abhandlungen : 2 6 9-460 . Eitel, W . 1 954 : The phys ical chemistry of the silicates . Chicago , University of Chicago Press . Elder, N . L . 1 9 6 5 : Vegetation of the Ruahine Range : An int roduction . Transactions of the Royal Society of New Zealand, botany 3 : 13- 66 . Emery, K . O . 1 9 6 9 : The continental shelves . Scientific american 221 : 1 0 6-128 . Emery, K . O . ; Kuhn , G . G . 1 982 : Sea cliffs : Their processe s , profiles and classification . Geological Society of America bulletin 93 : 6 4 4-654 . Emiliani , C . 1 9 6 6 : P aleotemperature analys is of Caribbean cores P 6304- 8 and P6304-9 and a generalised temperature curve for the past 42 5 , 0 0 0 years . Journal of geology 75 : 1 0 9 - 12 6 . Engel , A . E . J . ; Clayton, R . N . ; Epstein, S . 1 9 5 8 : Variat ions in isotopic composition of oxygen and carbon in Leadville limestone (Mississippian , Colorado) and its hyrothermal and metamorphic phases . Journal of geology, 66 : 37 4 -3 9 3 . Epstein, S . ; Buchsbaum, R . ; Lowenstam, H . A . ; Urey, H . C . 1 9 5 3 : Revised carbonate-water i sotopic temperature scale . Geological society of America bulletin 64 : 1315-132 6 . Epstein, S . ; Taylor , H . P . (Jr . ) 1 9 67 : Variat ion of 1 8o : 1 6o in minerals and rocks . Pp 2 9- 6 2 . In Abelson, P . H . ed. Researches in geochemistry I I . New York . E rnst , W . G . ; Calvert , S . E . 1 9 6 9 : An experimental study of the recrystallisation of porcelanite and its bearing on the origin of some cherts . American journal of science 2 67A : 114-133 . Ewart , A . 1 9 6 5 : Mineralogy and petrogenesis of the Whakamaru ignimbrite in the Maraeti area of t he Taupo Volcanic Zone , New Zealand . New Zealand journal of geology and geophysics 8 : 611-677 . Ewart , A . 1 9 7 1 : Chemical changes accompanying spherulitic c rystallisation in rhyolitic lava , central volcanic region , New Zealand . Mineralogical magazine 38 : 424-434 . Ewart , A . 1 9 6 8 : The petrography of the central North Island lava s . Part 2 . Regional petrography including notes on associated ash-flow pumice deposits . New Zealand journal of geology and geophysics 1 1 : 4 78-54 5 . Fairbridge , R . W . 1 9 8 2 : The Pleistocene-Holocene boundary . Quaternary science review 1 : 2 1 5-24 4 . Fenner , C . N . 1913 : Stability relations of the silica minerals . American journal of science 36 : 331-3 8 4 . Fielde s , M . 1 952 : Abnormal behaviour of a lpha-quartz from some New Zealand soils . Nature 1 70 : 3 6 6-367 . Fielde s , M . 1958 : Clay mineralogy of yel low-grey earths . New Zealand soil news 6 : 225-227 . Fielde s , M . 1 9 6 6 : The nature of allophane in soils . Part 1 : 3 0 3 Significance of st ructural randomnes s in pedogenesis . New Zealand journal of science 9 : 5 99-607 . Fie lde s , M . ; Furkert , R . J . 1 9 6 6 : The nature of allophane in soil s , Part 2 . Differences i n composition . New Zealand journal of science 9 : 6 0 8-622 . Fielde s , M . ; Swindale , L . D . 1 954 : Chemical weathering of silicates in soil formation . New Zealand journal of science and technology B36 : 1 4 0-154 . Fielde s , M . ; Walker, I . K . ; Williams , P . P . 1 95 6 : Clay mineralogy of New Zealand soils : Part 3- Infrared abso rption spectra of soil clays . New Zealand journal of science and technology B38 : 31-43 . Fielde s , M . ; Weatherhead, A . V . 1 9 6 6 : Mineralogy of sand fract ions of New Zealand Soils . New Zealand journal of science 9 : 1 0 0 6-102 1 . Fielde s , M . ; Weatherhead, A . V . 196 8 : Mineralogy of the sand fract ion . Pp 8-2 1 . In New Zealand Soil Bureau . 1 9 6 8 : Soils of New Zealand . New Zealand Soil Bureau bulletin 2 6 ( 2 ) . Fielde s , M . ; Williamson, K . I . 1 955 : Clay mineralogy of New Zealand soils : Part 1 - Elect ron microscopy . New Zealand journal of science and technology B37 : 314-335 . Fife , C . V . 1 945 : Study of a yellow-grey loam in the Manawatu . New Zealand journal of science and technology A26 : 281-293 . Fit zpatrick , E . A . 1 95 6 : An indurated soil horizon formed by permafrost . Journal of soil science 7 : 2 48 -254 . Fit zpatrick, E .A . 1 97 6 : Cryons and isons . Proceedings of the North England soils discussion group (1 974) 1 1 : 3 1-43 . F leming, C .A . 1 97 0 : Radiocarbon dating and pollen analyses from Otiran periglacial fans in western Wellington . Transactions of the Royal Society of New Zealand, earth science 7 : 1 97-2 0 8 . Flerning, C . A . 1 97 9 : The geological history of New Zealand . Auckland University Press . 1 4 1p . Florke , O . W . 1 955 : Zur frage des "hoch"-cristobalite in opalel , bentoniten und glasern . Neues Jahrbuch fur Mineralogie 1 955 : 2 1 7- 2 2 3 . Florke , O . W . ; Hollmann, R . ; von Rad, U . ; Rosch, H . 1 97 6 : Intergrowth and twinning in opal -CT lepispheres . Contributions to mineralogy and petrology 58 : 235-2 42 . Florke , O . W . ; Jones, J . B . ; Segnit, E . R . 1 9 7 5 : Opal-CT crystals . Neues Jahrbuch fur Mineral ogie Mh . H8 : 3 6 9-37 7 . Folk, R . L . 1 97 4 : Petrology of Sedimentary Rocks . Hemphill, Austin, Texa s . 1 82p . Frank s , A . M . 1 9 8 4 : Soils of Eltham County and the tephrachronology of Cent ral Taranaki . Unpublished Ph .D . thesis held in the Library, Mas sey University . Froggat t , P . C . 1 9 82 : A study of some aspects of the volcanic history of the Lake Taupe Area , North Island, New Zealand . Unpublished Ph . D . thesis held at the Library, Victoria University of Wellington . Froggatt , P . C . 1 9 8 3 : Towards a comprehensive Upper Quaternary tephra and ignirnbrite stratigraphy in New Zealand using electron microprobe analys is of glass shards . Quaternary Research 1 9 : 1 8 8 - 2 0 0 . 3 0 4 Froggatt , P . C . ; Solloway, G . J . 1 98 6 : Correlation of Papanetu Tephra to Karapiti Tephra , central North Island, New Zealand . New Zealand j ournal of geology and geophysics 2 9 : 3 0 3-313 . Fronde l , C . 1 9 62 : Dana' s system of mineralogy . Volume III . Silica minerals . John Wiley and Sons , New York . Froude , D . O . 1 9 8 5 : Petrography, mineralogy and chemistry of Titiraupenga Volcano, · North I sland, New Zealand . New Zealand journal of geology 28 : 4 8 7- 4 9 6 . Fruchter , J . S . ; Robertson, D . E . ; Evans, J . C . et al . 1 9 8 0 : Mount St . Helens ash from the 1 8 May 1 9 8 0 erupt ion - chemical , physica l , mineralogical and biological properties . Science 209 : 11 1 6 - 1 12 5 . Gage , D . R . ; Jernegan, M . F . ; Farwell, S . O . 1 98 1 : Characteristics and quantification of inhalable particulate volcanic ash from Mt St Helens . Mt St Helens : One Year Later Conference, Washington, May 1981 . 3 0 5 Gage , M . 1 9 57 : The geology of Waitaki Division . New Zealand Geological Survey bulletin 55 . Gagosian, R . B . ; Pelt zer, E . T . ; Merril , J . T . 1 9 8 7 : Long-range transport of terrest rially derived lipids in aerosols from the South Pacific . Nature 325 : 8 0 0 - 8 0 3 . Galehouse , J . S . 1 9 6 9 : Count ing grain mounts : number percentages versus number frequency . Sedimentary petrology 39 : 8 12 - 8 1 5 . Garlick, G . D . ; Epstein, S . 1 9 67 : Oxygen isotope rat ios in coexistng minerals of regionally metamorphosed rocks . Geochimica et cosmochimica acta 31 : 1 8 1 -2 1 4 . Gibb, J . G . 1 97 9 : Late Quaternary shoreline movements in New Zealand . Unpublished Ph . D . thesis , held in the Library, Victoria University of Wellington . Gibb, J . G . 1 9 83 : Sea levels during the past 1 0 , 0 0 0 years B . P . from the New Zealand region - South Pacific Ocean . Pp 28-31 . Abstracts of the International Symposium of Coastal Evolution in the Holocene, Tokyo . Japanese Society for the Promotion of Science . Gibb, J . G . 1 98 6 : A New Zealand regional Holocene eustatic sea level curve and its applicat ion to determination of vertical tectonic movement s . Royal Society of New Zealand bulletin 24 : 377-397 . Gibbs , H . S . 1 9 64 : Some reflect ions on soil formation and loess . New Zealand soil news 1 2 : 222-22 5 . Gibbs, H . S . 1 9 8 0 : New Zealand soils . Wellington, Oxford University P res s . Ginzburg, I . I . ; Kabanova , E . S . 1 9 6 0 : Silica content and its form in natural waters . Kora Vyvetrivaniya , Akad . Nauk SSSR, Inst . Geol . Gudnykh Mestorozhden . , Pet rog . , Mineral . i Geokhim . 3 : 313 . Goh, K .M . ; Tonkin, P . J . ; Rafter , T . A . 1 978 : Implications of improved radiocarbon dates of Timaru peats on Quaternary loess s tratigraphy . ·New Zealand journal of geology and geophysics 2 1 : 4 6 3 -4 6 6 . Gradwell M . W . 1 97 4 : The available-water capacities of some southern and central zonal soils of New Zealand . New Zealand journal of agricultural research 1 7 : 4 6 5 - 47 8 . Gradwell , M . W . 1 97 8a : Pore size distributions of some New Zealand soil groups . New Zealand journal of agricultural research 21 : 603-61 4 . Gradwell , M . W . 1 9 7 8b : Subsoil hydraulic conductivit ies of ma jor New Zealand soil groups at water content near field capacity . New Zealand journal of agricultural research 22 : 60 3 - 6 1 4 . Graham, I . V . 1 9 8 5 : Petrochemical and Sr isotopic studies of lavas and xenoliths from Tongariro Volcanic Centre - Implicat ions for crustal contamination of calc-alkaline magmas . Unpublished Ph . D . thesis held in the Library, Victoria University, Wellington . Grange , L . I . 1 9 45 : Farming in New Zealand . North Island Soils . New Zealand journal of agriculture 70 : 3 87-397 . Grange , L . I . 1 94 6 : Farming in New Zealand . South Island soils . New Zealand journal of agriculture 72 : 5 83-5 9 1 . 3 0 6 Green , J . D . ; Lowe , D . J . 1 9 8 5 : St ratigraphy and development of c . 17 , 0 0 0 year old Lake Maratoto, North Island, New Zealand, with some inferences about postglacial climatic change . New Zealand journal of geology and geophysics 28 : 675-7 0 1 . Greenwood, R . 1 9 73 : Cristobalite : its relationship to chert format ion in selected samples from t he deep sea drilling proj ect . Journal of sedimentary petrology 43 : 7 0 0 -808 . Greig, J . W . 1932 : The existence of the high-temperature form of cristobalite at room temperature and the crystallinity of opal . Journal of the American chemical society 54 : 2 8 4 6-2 8 4 9 . Griggs , G . B . ; Carter, L . ; Kennett , J . P . ; Carter, R . V . 1 9 8 3 : Late Quaternary marine stratigraphy southeast of New Zealand . Geological Society of America bulletin 94 : 7 9 1-797 . Grossman, R . B . ; Carlisle , F . J . 1 9 6 9 : Fragipan soils of the eastern United States . Advances in agronomy 21 : 237-27 6 . Guven, N . ; Grim, R . E . 1 972 : X-ray diffraction and electron optical studies on smectite and alpha-cristobalite associations . Clays and clay minerals 20 : 8 9-92 . Hall, R . D . ; Canepa, A . P . ; Ruhe, R . V . 1 97 3 : Paleosols of southwestern Indiana . Abstracts of the 9th INQUA Congress, 1 9 73, Christchurch . Pp 133-13 4 . Hallmark, C . T . ; Smeck, N . E . 1 97 9 : The effect of extractable aluminium, iron and silicon on strength and bonding of fragipans of northeastern Ohio . Journal of the Soil Science Society of America 43 : 1 45-150 . * Hackett , w . 1 9 85 : Geology and pet rology of Ruapehu volcano and re lated vents . Unpublished Ph . D . thesis held in the Library, Victoria University . 3 0 7 Hampton, C . M . ; Bailey, D . K . 1 9 8 5 : Sublimates obtained during fus ion of volcanic glas s . Journal of volcanology and geothermal research 25 : 145-155 . Hardjosoesastro , R . R . 1 956 : Preliminary note on cristobalite in clay fractions of volcanic glas s . Journal of soil science 7 : 1 85-188 . Harlan, P . W . ; Franzmeier , D . P . ; Roth, C . B . 1 9 77 : Soil formation on loess in southwestern Indiana . I . Loess stratigraphy and soil morphology . Journal of the Soil Science Society of America 41 : 93- 9 8 . Harland, W . B . 1 9 8 1 : Chronology of Earths glacial and tectonic record . Journal of the geological society of London 138 : 1 97 -2 0 3 . Harris , D . M . ; Rose, W . I . ; Roe , R . ; Thompson, M . R : 1 9 8 1 : The 1 9 8 0 eruptions o f Mt . St . Helens , Washington : radar observat ions of ash eruptions . United States Geological Survey professional paper 125 0 : 323-333 . Harris , W . F . 1 9 6 3 : Paleoecological evidence from pollens and spores . New Zealand Ecological Society proceedings 1 0 : 3 8 -55 . Harvey, C . C . 1 9 8 0 : A study of the alteration products of acid volcanic rocks from Northland, New Zealand . Unpublished Ph . D . thesis . Indiana University . Healy, J . 19 82 : Central Volcanic Region . In Soons, J .M . ; Sleby, M . J . eds . Landforms o f New Zealand . Longman-Paul, Auckland . Heath, G . R . ; Moberly, R . 1 97 1 : Cherts from the western Pacific , Leg 7 , deep sea drilling project . Pp 9 91-1007 . In Winterer e t al . ( eds . ) Init ial reports of the deep sea drilling pro ject VI I . Washington , United States Government Printing Office . Hein, J . R . 1 9 8 1 : Siliceous deposits of the Pacific region . International geological correlation program report 1 0 : 3 8-39 . Hein , J . R . ; Scholl, D . W . ; Baron, J . A . ; Jones, M . G . ; Miller, J . 1978 : · Diagenesis of late Cenozoic diatomaceous depos it s and formation of the bottom s imulating reflector in the southern Bering Sea . Sedimentology 25 : 155-181 . Hein, J . R . ; Yeh , H . 1 9 8 1 : Oxygen isotope composit ion of chert from the mid Pacific Mountains and Hes se Rise, Deep Sea Drilling Project , Leg 62 . Initial reports of the deep sea drilling project , Leg 62 . Washington D . C . , United States Government P rinting Office . 3 0 8 Hemley, J . J . ; Meyer , C . ; Richter, D . H . 1 9 6 1 : Some alteration react ions in the system Na2o-Al2o3-sio2 -H2 o . United States Geological Survey professional paper 424D : 3 8 8-340 . Henderson , J . H . ; Clayton, R . N . ; Jackson , M . L . ; Syers, J . K . ; Rex, R . W . ; Brown , J . L . ; Sachs , I . B . 1 972 : Cristobalite and quartz isolation from soils and s ediments by hydrofluorosilicic acid treatment and heavy liquid separat ion . Soil Science Society of America proceedings 3 6 : 8 3 0-835 . Henderson, J . H . ; Jackson, M . L . ; Syers , J . K . ; Clayton , R . N . ; Rex, R .W , 1 97 1 : Cristobalite authigenic origin in relation to montmorillonite and quartz origin in bentonites . Clays and clay minerals 1 9 : 22 9 -2 3 8 . Henmi , T . ; Parfitt , R . L . 1 9 80 : Laminar opaline silica from volcanic ash soils in New Zealand . Clays and clay minerals 28 : 57-60 . Hesp, P .A . ; Shepherd, M . J . 1978 : Some a spects of the late Quaternary geomorphology of the lower Manawatu valley, New Zealand . New Zealand journal of geology and geophyics 21 : 403-412 . Heusser, C . J . ; Rabassa , J . 1987 : Cold climate episode of younger Dryas age in Tierra del Fuego . Nature 328 : 6 0 9-611 . Heydemann, A . 1 9 64 : Untersuchunge uber die bildungsbedingungen van quart z im temperaturbereich zwaschen 1 0 0°C und 250°C . Beitrage vur mineralogie und petrographie 1 0 : 2 42 -2 5 9 . Hill, V . G . ; Roy, R . 1 9 5 8 a : Silica structure studies : V . the variable inversion of cristobalite . Journal of the American ceramic society 41 : 5 32-537 . Hill, V . G . ; Roy, R . 1 95 8b : Silica st ructure studies . VI on tridymite . Transactions of the British ceramic society 5 7 : 4 9 6-5 1 0 . Hodder , A . P . W . 1 9 7 8 : Refractive index and hydration of rhyolitic glass from Holocene tephras , North Island, New Zealand . New Zealand journal of geology and geophysics 21 : 155-1 6 6 . Hogg, A . G . 1 97 9 : Identification and corre lation of thinly bedded Late Quaternary t ephras of the Coromandel Peninsula , New Zealand . Unpublished D . Phil . thesis , held in the Library, University of Waikato . Hogg, A . G . ; McCraw, J . D . 1983 : Late Quaternary tephras of Coromandel Peninsular, New Zealand : a mixed peralkaline and calcalkaline tephra sequence . New Zealand journal of geology and geophysics 2 6 : 163-187 . Holmquist , S . B . 1 9 6 1 : Conversion of quart z to t ridymite . Journal of the American Ceramic Society 4 4 : 82-8 6 . Howorth , R . 1 97 6 : Late P leistocene tephras of the Taupo and Bay of P lenty regions . Unpublished Ph . D . thesis held at the Library, Victoria University of Wellington . Hubbard, C . B . ; Neal l , V . E . 1 98 0 : A reconst ruction of Late Quaternary e ros ional event s in the West Tamiki River catchment , Southern Ruahine Range , North Island, New Zealand . New Zealand journal of geology and geophysics 23 : 587-593 . Hudson , A . W . ; Fife , C . V . 1 9 40 : Mole drainage investigations in New Zealand . New Zealand journal of science and technology A22 : 1 97- 2 0 8 . 3 0 9 Hume , T .M . ; Nelson C . S . 1 9 8 6 : Distribut ion and origin o f clay minerals in surficial shelf sediments , western North Island, New Zealand . Marine geology 69 : 2 8 9-308 . Hume , T . M . ; Sherwood, A . M . ; Nelson, C . S . 1 97 5 : Alluvial sedimentology of the Upper Pleistocene Hinuera Formation, Hamilton bas in, New Zealand . Journal of the Royal Society of New Zealand 5 : 42 1-462 . Huut C . B . ; Robinson T . W . ; Bowles W . A . ; Washburn A . L . 1 9 6 6 : Hydrolic Basin Death Valley California . United States geological survey professional paper 4 9 4 -B . I i j ima , A . ; Matsumoto , R . ; Tada , R . 1 98 0a : Zeolite and silica diagenesis and s andstone petrography at s ites 438 and 4 3 9 off Sanriku, northwest Pacific . Pp 1 143-115 8 . In Lee , M . ; Stout , L . N . ed . Initial reports o f the deep sea drilling project , leg 57 . Washington, United States Government P rint ing Office � I i j ima , A . ; Matsumoto , R . ; Tada , R . 1 9 8 0b : Zeolite and silica diagenesis and s andstone petrography at s ites 438 and 4 3 9 off Sanriku , northwest Pacific . Pp 56-57 . In Lee , M . ; Stout , L . N . ed . Initial reports of the deep sea drilling project, leg 57 . Washington, United States Government Printing Office . I i j ima , A . ; Tada , R . 1 9 8 1 : Silica diagenesis of neogene diatomaceous and volcaniclast ic sediment in northern Japan . Sedimentology 2 8 : 1 8 5-2 0 0 . I s aacs , C . M . 1982 : Influence of rock composition on kinetics of silica phase changes in the Monterey Formation, Santa Barbara area, California . Geology 1 0 : 3 04-30 8 . Ives , D . 1 97 3 : Nature and distribut ion of 1oess in Canterbury, New Zea land . New Zealand journal of geology and geophysics 1 6 : 5 8 7- 610 . Ives , D . ; Stevenson, E . 1 97 3 : Recent loess sedimentation on the Canterbury Plains and its implications in terms of Late Quaternary loess deposit s . Abstracts of the 9th INQUA Congress, 1 9 73, Christchurch . Pp 1 8 6-1 8 9 . Jackson, M . L . 1 9 5 6 : Soil chemical analys is - advanced course . Department of Soil Science , University of Wisconsin, Madison, Wisconsin . Jacks on , M . L . ; Clayton, R . N . ; Fuj ii , N . ; Henderson, J . H . 1 9 7 7 : Cristobalite morphology and oxygen isotope compos ition variation under hydrothermal alteration . Clays and clay minerals 25 : 31-38 . 3 1 0 Jackson , M . L . ; Gillette, D . A . ; Danielson , E . F . ; Blifford, I . H . ; Byron , R . A . ; Syers, J . K . 1 97 3 : Global dust fall during the Quaternary as related to environment s . Soil science 1 1 6 : 135-145 . Jackson, M . L . ; Levett , W . M . ; Syers, J . K . ; Rex , R . W . ; Clayton, R . N . ; Sherman , G . D . ; Uehara , G . 1 9 7 1 : Geomorphological relationships of t ropospherically derived quartz in the soils of the Hawaiian I slands . Soil Science Society of America Proceedings 35 : 5 15-525 . Jane , D . S . 1 9 8 0 : Slope morphology, soils and erosion of a terrace s carp at the Fitzherbert site, Palmerston North . Dip . Ag . Sc . dis sertation held in the Department of Soil Science , Massey University . JCPDS . 1 9 7 4 : Selected powder diffraction data for minerals . Joint Committee on Powder Diffraction Standards . Pennsylvania . Jeans , C . V . 1 97 8 : Silicificat ions and associated clay assemblages in the Cretaceous marine sediments of southern England . Clay ndneralogy 1 3 : 10 1-125 . Jes sen, M . R . 1 977 : Horotiu and Waihou silt loams , a comparative study . Unpublished M . Sc . thesi s , held in the Library, University of Waikato . Joe , E . N . (Compiler ) 1 98 6 : Soil water characterisation studies of 6 soils in the Waikato district New Zealand . New Zealand Soil Bureau SWAMP data sheets 1 984 : 1-6 . JOIDES 1 9 67 : American association of petroleum geologists bulletin 51 . Jone s , J . B . ; Biddle , J . ; Segnit , E . R . 1 9 6 6 : Opal genesis . Nature 21 0 : 1353-1354 . Jone s , J . B . ; Sanders, J . V . ; Segn it , E . R . 1 9 64 : Structure of opal . Nat ure 204 : 9 9 0-991 . Jone s , J . B . ; Segnit , E . R . 1 9 6 9 : Water in sphere-type opal . Mineralogical magazine 3 7 : 357-3 6 1 . Jone s , J . B . ; Segnit , E . R . 1 9 7 1 : The nature of opal : I . Nomenclature and const ituent phases . Journal of the geological society of Australia 1 8 : 57-68 . Jones , J . B . ; Segnit , E . R . 1 97 5 : Nomenclature and the structure of natural disordered ( opaline ) silica . Contributions to mineralogy and petrology 51.: 231-2 3 4 . Jones , J . B . ; Segnit , E . R . ; Nickson, N . M . 1963 : Differential thermal and X-ray analysis of opal . Nature 1 98 : 1 1 91 . Jone s , L . H . P . ; Handreck, K . A . 1 9 67 : Silica in soils, plants and animals . Advances in Agronomy 1 9 : 107-1 49 . 3 1 1 Jones , L . H . P . ; Milne , A . A . ; Wadham, S .M . 19 63 : Studies o f silica in t he oat plant . II . Distribution of silica in the plant . Plant and soil 1 8 : 358-371 . Jones , R . C . ; Uehara, G . 1 97 3 : Amorphous coatings on mineral surfaces . Soil Science Society of America proceedings 3 7 : 7 92 -7 9 8 . Jone s , R . L . ; Beavers , A .H . 1 9 63 : Some mineralogical and chemical p roperties of plant opal . Soil science 9 6 : 375-7 9 . Jones , R . L . ; Beavers , A . H . 1 9 6 4 : Aspects of catenary and depth dist ribut ion of opal phytoliths in Illinois soils . Soil Science Society of American proceedings 28 : 4 13-41 6 . Jones , R . L . ; Hay, w .w . 197 5 : Bioliths . Pp . 4 8 1-4 9 6 . In Gieseking, J . E . ed . Soil Components : Volume 2 , Inorganic Components . New York, Springer-Verlag . Kadko, D . ; Blueford, J . R . ; Burckle, L . H . ; Barren, J . 1 9 8 3 : Selective dissolution of siliceous microfossils observed in a box core f rom the north east equatorial Pacific . Nature 302 : 139-141 . Kamatani , A . 1 97 1 : Physical and chemical characteristics of biogenous silica . Marine biology 8 : 8 9-95 . Kastner , M . ; Keene , J . B . ; Gieskes , J .M . 1 977 : Diagenesis of siliceous oozes - 1 . Chemical control on the rate of opal-A to opal-CT t ransit ion - an experimental study . Geochimica et cosmochimica acta 41 : 1041-1059 . 3 1 2 Kawabe I . 1 9 7 8 : Calculation o f oxygen isotope fractionation i n quart z­ water system with special reference to the low temperature fractionation . Geochimica et cosmochimica acta 42 : 613-62 1 . Kei l , K . ; Prinz , M . 1 97 1 : Mineralogy, petrology and chemistry of some Apollo 12 samples . Proceedings of the Second Lunar Conference 1 : 319-34 1 . Keller, M .A . ; Isaacs , C . M . 1 9 85 : An evaluat ion of temperature scales for silica diagenesis in diatomaceous sequences in the Miocene Monterey Formation, California . Geo�marine letters 5 : 31-35 . Kennedy, N . M . 1 9 8 0 : Field recognition of tephric loess (c . 42 , 0 0 0 - c . 15 , 0 0 0 years B . P . ) in cent ral North I sland . New Zealand soil news 28 : 55-58 . Kennedy, N . M . 1 9 82 : Tephric loess in the Rotorua-Bay of Plenty region , North Island, New Zealand . Pp 11 9-122 . In Was son, R . J . ed . Quaternary dust mantles of China , New Zealand and Australia . Canberra , Australia National University . Kennedy, N .M . ; Pullar, W . A . 1977 : Loess on the Mamaku Plateau . New Zealand soil news 25 : 9 1 . Kennett , J . P . ; Hout z , R . E . et al 1 975 : Initial reports of the deep sea drilling program 2 9 . Washington, United States Government Print ing Office . Kennett , J . P . ; van der Borch, C . C . et al 19 8 5 : Initial reports of the deep sea drilling program 90 . Washington , U . S . Government P rinting Office . Khangarat , A . S . ; Wilding, L . P . ; Hall , G . F . 1 9 7 1 : Composition and weathering of loess mantled Wiscons in and Illinoian-age terraces in central Ohio . Soil Science Society of America proceedings 35 : 621-62 6 . Kihara , K . 1 97 8 : Thermal change in unit-cell dimensions , and a hexagonal structure of t ridymite . Zeitschrift fur kristallographie 1 4 8 : 237 -253 . Kihara , K . 1 9 8 0 : On the split-atom model for hexagonal tridymite . Zeitschrift fur kristallographie 1 52 : 95-1 0 1 . Kingma , J . T . 1 9 62 : Geological map of New Zealand . 1 : 2 50 , 0 0 0 Sheet 1 1 - Dannevirke . Department of Scientific and Industrial Research, Wellington . 3 1 3 Kingma , J . T . 1 9 67 : Geological map of New Zealand . 1 : 2 5 0 , 0 0 0 . Sheet 12- Wellington . Department of Scientific and Industrial Research, Wellington . Kirkman, J . H . 1 97 1 a : Amorphous inorganic materials in three soils formed from loess . 1 . Application of select ive dissolution t echniques . New Zealand journal of science 1 6 : 7 9-93 . Kirkman , J . H . 1 9 7 1b : Amorphous inorganic materials in three soils formed from loess . 2 . Amounts and distribution . New Zealand journal of science 1 6 : 95-10 0 . Kirkman , J . H . 1 97 3 : Amorphous inorganic materials in the soils formed from loess . 2 . Amounts and distribution . New Zealand journal of science 1 6 : 95-10 0 . Kita I . ; Taguchi S . ; Matsubaga 0 . 1 9 85 : Oxygen isotope fract ionat ion between amorphous silica and water at 34-93°C . Nature 31 4 : 8 3-84 . Klein , C , ; Drake, J . C . ; Frondel, C . 1 97 1 : Mineralogical , pet rological and chemical features of four Apollo 12 Lunar microgabbros . Proceedings of the second Lunar conference 1 : 2 65-2 8 4 . Klein , C . ; Hurlbut , C . S . 1 98 5 : Manual of mineralogy . New York, John Wiley & Sons . Kleis s , H . J . 1973 : Loess distribution along the Illinois soil­ development sequence . Soil science 1 1 5 : 1 94-198 . Knauth, L . P . ; Epstein, S . 1 97 5 : Hyrogen and oxygen isotope ratios in s ilica from the JOIDES deep sea drilling project . Earth and planetary science letters 25 : 1-10 . Knauth , L . P . ; Epstein, S . 1 97 6 : Hydrogen and oxygen isotope rat ios in nodular and bedded chert s . Geochimica et cosmochimica acta 4 0 : 1 0 95-11 0 8 . Knauth , L . P . ; Epstein, S . 1 9 8 2 : The nature of water in hydrous s ilica . American mineralogist 6 7 : 510-52 0 . Kocurek , G . ; Hunter, R . E . 1 9 8 6 : Origin of polygonal fractures in sand, uppermost Nava j o and Page sandstones , Page , Arizona . Journal of sedimentary petrology 5 6 : 8 95-9 0 4 . Kohn, B . P . 1 97 0 : Identification of New Zealand tephras by emmission spectrograph analysis of their t itanomagnetites . Lithos 3 : 3 6 1- 3 6 8 . Kohn, B . P . ; Neall, V . E . 1 97 3 : Identification of Late Quaternary tephras for dating Taranaki lahar deposit s . New Zealand journal of geology and geophysics 1 6 (3) : 7 81-7 92 . Kolbe , R . W . 1 957 : Fresh water diatoms from At lantic deep-sea sediment s . Science 126 : 1 0 53-1 056 . Krauskopf , K . B . 1 9 67 : Int roduction to geochemistry . McGraw-Hill Book Co . , New York . Kuno , H . 1 93 3 : On silica minerals occurring in the groundrnass of common Japanese volcanic rocks . Earthquake Research Institute bulletin 1 1 : 382-3 9 0 . Kunt z, M . A . ; Rowley, P . D . , MacLeod, N . S . ; Reynolds , R . L . ; McBroome , 3 14 L . A . ; Kaplan, A . M . ; Lidke , D . J . 1 9 8 1 : The 1 9 8 0 e ruptions of Mount St Helens , Washington : Petrography and part icle-size distribut ion of pyroclastic-flow, ash-cloud, and surge deposits . United States Geological Survey professional paper 1250 : 525-63 9 . Labeyie , L . D . ; Pichon, J . J . ; Labracherie , M . ; Ippolito , P . ; Duprat , J . ; Duplessey, J . 1 98 6 : Melting history of Antarctica during the past 6 0 , 0 0 0 years . Nat ure 322 : 7 0 1-7 0 6 . Laffan, M . D . 1 97 9 : Slope stability in the Charleston-Punakaiki region, South Island, New Zealand . 2 . Soil disturbance by windthrow and podocarp logging on steepland soils formed from micaceous silty sandstone . New Zealand journal of science 22 : 193-20 1 . Lanering, F . C . ; Pannaiya , B . W . N . ; Crurnption, C . F . 1 958 : The chemical nature of silica in plant s . Plant physiology 33 : 339-343 . Langer, K . ; Florke, o . w . 1 97 4 : Near infrared adsorption spectra ( 4 0 0 0 -9 0 0 0cm-1 ) of opals and the role of "water" in these Sio2 . nH2o minerals . Fortschritte der mineral ogie 52 : 17-51 . Langohr, R . 1 98 7 : Consolidated horizons ( fragipans ? ) in loess soils of western Europe : their characteristics , impact on root penet rat ion and water percolation . and their use as paleoenvironrnental markers . Abstracts for International Symposium on Loess, 1 9 8 7, New Zealand . p15 . Latter, J . H . 1 9 8 5 : Frequency of eruptions at New Zealand volcanoes . Bulletin of the New Zealand national society for earthquake engineering 1 8 : 55-11 0 . 3 1 5 Latter, J . H . ; Houghton , B . F . ; Hackett , W . R . 1 9 8 1 : Volcanic risk assessment at Ruapehu volcano . Chapter 4 . in Houghton, B . F . ; Smith, I . E . M . ed . Volcanologic Workshop, 1 98 1 . Proceedings of the New Zealand volcanologic workshop, 1 981, Turangi . Leamy, M . L . 1 97 3 : Paleosol ident ification and soil strat igraphy in South Island, New Zealand . Abstracts of the 9th INQUA Congress, 1 9 73, Christchurch . Pp 2 0 4-2 0 5 . Leamy, M . L . ; Burke , A . S . 1973 : Identification and significance of paleosols in cover deposits in Central Otago . New Zealand journal of geology and geophysics 1 6 (3) : 623-635 . Leamy, M . L . ; Clayden, B . ; Hewitt , A . E . 1 9 83 : Soil classification in the New Zealand Soil Bureau . New Zealand soil news 31 : 1 83-185 . Leamy, M . L . ; Milne , J . D . G . ; Pullar, W . A . ; Bruce , J . G . 1 97 3 : Paleopedology and soil sratigraphy in the New Zealand Quaternary succession . New Zealand journal of geology and geophysics 1 6 : 723- 7 4 4 . Lee , K . E . 1 9 5 9 : The earthworm fauna of New Zealand . New Zealand Department of Scientific and Industrial Research bulletin 130 . Lee , K . E . 1 9 6 8 : A preliminary study of soil animals and their relationship to some New Zealand soils . New Zealand Soil Bureau bulletin 2 6 : 1 6 8-1 83 . Lee , R . ; Bailey, J . M . ; Northey, R . D . ; Blake , P . R . ; Gibson, E . J . 1 9 75 : Variations in some chemical and physical propert ies of three related soil types : Dannevirke silt loam, Kiwitea silt loam and Marten silt loam . New Zealand journal of agricultural research 1 8 : 2 9-3 6 . Lees, C . M . 1 9 8 1 : Some Aranuian (Postglacial) organic deposits in the south eastern Ruahine Range , North Island, New Zealand, invest igated by palynological methods . Unpublished M . Sc . thesis , held in the Library, Mas sey University . Lees, C .M . 1 9 8 6 : Late Quaternary palynology of the southern Ruahine Range, North I sland, New Zealand . New Zealand journal of botany 2 4 : 3 15-32 9 . Lewis , K . B . 1 97 9 : A storm-dominated inner shelf, western Cook Strait , New Zealand . Marine geology 31 : 31-43 . Lewis , K . B . ; Eade , J . V . 1 97 4 : Sedimentation in the vicinity of the Maui gas field . New Zealand Oceanographic Institute oceanography summary 6 . 3 1 6 Lewis , K . B . ; Mildenhall, D . C . ; Clowes , C . D . 1 9 8 5 : The Late Quaternary seismic , sedimentary and palynological st ratigraphy beneath Evans Bay, Wellington Harbour . New Zealand journal of geology and geophysics 2 8 : 12 9-152 . Lipman, P . W . ; Norton, D . R . ; Taggart , J . E . ; Brandt , E . L . ; Engleman , E . E . 1 9 8 1 : The 1 9 8 0 erupt ion of Mount St . Helens , Washington : Composit ional variations in 1 9 8 0 magmatic deposit s . United States Geological Survey professional paper 1250 : 63 1- 6 4 0 . Lithgow, N . A . 1 9 8 6 : A textural and mineralogical study of the beach sands a long the southwest coast of the North Island . Unpublished M . Sc . thesis , held in the Library, Massey University . Lofgrens, J . 1 9 8 1 : Analysis of volcanic ash from Mt . St . Helens by x­ ray diffraction . Mt St Helens : One Year Later Conference, Washington, May 1 981 . Lorius , C . ; Merlivat , L . ; Jouzel , J . ; Pourchet , M . 1 97 9 : A 3 0 , 0 00 year isotope climatic record from Antarctic ice . Nature 280 : 644-64 8 . Lovering, T . S . 1 9 5 9 : Significance of accumulator plants in rock weathering . Geological Society of America bulletin 70 : 7 81-800 . Lowe , D . J . 1 9 8 0 : Tephric Loess . New Zealand soil news 28 : 2 17-22 0 . Lowe , D . J . 1 9 8 1 : Origin and composite nature of Late Quaternary a irfall deposits , Hamilton Basin . Unpublished M . Sc . thesis, held in the Library, University of Waikato . Lowe , D . J . 1 9 8 6 : Controls on the rates of weathering and clay mineral genesis in airfall tephras : a review and New Zealand case study . Pp 2 65-330 . In Coleman, S . ; Dethier, D . ed . Rates of chemical weathering of rocks and minerals . New York, Academic P ress . Lowe , D . J . 198 7 : Studies on Late Quaternary tephras in th� Waikato and other regions in the northern North Island, New Zealand . Based on distal deposit s in lake sediments and peats . Unpulished Ph . D . thesis , held in the Library, Waikato University . Lowe , J . P . ; Lowe, D . J . ; Hodder, A . P . W . ; Wilson, A . T . 1 9 8 4 : A tritium­ exchange method for obsidian hydration shell measurements . Isotope geoscience 2 : 351-3 6 3 . McCraw, J . D . 1 9 67 : The surface features and soil patte rn of the Hamilton Bas in . Earth science journal 1 : 59-7 4 . 3 1 7 McCraw, J . D . 1 9 7 5 : Quaternary airfall deposits of New Zealand . Pp . 35- 4 4 . In Suggate, R . P . ; Cresswell, M . M . eds . Quaternary Studies . The Royal Society of New Zealand, Wellington . McGlone , M . S . 1 9 8 0 : The history of New Zealand Lowland forest since t he glaciation . Proceedings of the Symposium on Lowland Forest in New Zealand, 1 980, Hamilton . Pp 1 - 1 8 . McGlone , M . S . 1 9 8 5 : Biostratigraphy of the last interglacial-glacial cycle , southern North Island, New Zealand . Proceedings of the 2nd CLIMANZ conference, 1 985, Harihari, New Zealand . Pp 17 -32 . McGlone , M . S . ; Howarth, R . ; Pullar , W .A . 1 9 8 4 : Late Pleistocene stratigraphy, vegetat ion and climate of Bay of P lenty and Gisborne regions , New Zealand . New Zealand journal of geology and geophysics 2 7 : 327-350 . McGlone , M . S . ; Nelson, C . S . ; Hume , T . M . 1 97 8 : Palynology, age and environmental significance of some peat beds in Upper P leistocene H inuera Formation, south Auckland, New Zealand . Journal of the Royal Society of New Zealand 8 : 3 8 5- 3 9 3 . McGlone , M . S . ; Topping, W . W . 1 97 3 : Late Otiran/early Aranuian vegetation in the Tongariro area , central North Island, New Zealand . New Zealand journal of botany 1 1 : 2 83-2 9 0 . McGlone , M . S . ; Topping, W . W . 1 9 7 7 : Aranuian (Postglacial ) pollen diagrams from the Tongariro region , North Island, New Zealand . New Zealand journal of botany 1 5 : 7 4 9-7 60 McGlone , M . S . ; Topping, W . W . 1 98 3 : Late Quaternary vegetation, T ongariro region, central North I sland, New Zealand . New Zealand j ournal of botany 21 : 53-7 6 . Mcintyre , B .M . 1 97 5 : Upper Quaternary loess stratigraphy at two e xposures in southern Manawatu . Unpublished B � Sc . ( Hons . ) dissertation held in the Geography Department , Mas sey University . Mcintyre, D . J . 1 9 6 3 : Pollen analyses of a peat in Koputaroa dune s ands . New Zealand journal of geology and geophysics 6 : 2 7 8-2 8 0 . Mcintyre , D . J . 1 9 7 0 : Pollen analyses f rom the Lindale sect ion, Paraparaumu . Transactions of the Royal Society of New Zealand, earth science 7 : 203-2 0 6 . McKeague, J . A . and Cline , M . G . 1 9 6 3 : Sil ica in soils . Advances in Agronomy 1 5 : 3 3 9-3 9 6 . McKee , E . D . 1 9 83 : Eolian sand bodies of the world . Pp . 1-2 5 . In Brookfield, M . E . et al . eds . Eolian Sediments and Processes . Elsevier, Amsterdam . 3 1 8 McMillan, P . F . ; Remmele , R . L . 1 98 6 : Hydroxyl sites in Sio2 glass : a note on infrared and raman spectra . American mineralogist 71 : 772- 7 7 8 . McQueen , D . J . 1 97 5 : A study of the Horotiu - Te Kowhai soil complex . Unpublished M . Sc . thesis , held in the Library, University of Waikato . Mahood, G . A . ; Gilbert , C .M . ; Carrnichael, I . S . E . 1985 : Peralkaline and metalurninous mixed liquid ignirnbrites of the Guadala j ara Region, Mexico . Journal of volcanology and geothermal research 25 : 25 9- 2 7 1 . Marden, M . 1 9 84 : Geo logy and it s relationship to erosion in the southern Ruahine Range , North I sland, New Zealand . Unpublished Ph . D . thesis, held in the Library, Mas sey University . Marden, M . ; Paintin, I . K . ; Lees , C . M . ; Neall, V . E . 1 98 6 : Woodville neotectonics and Quaternary stratigraphy fieldtrip . Geological Society of New Zealand miscellaneous publication 35B : B3 . 1 -B3 . 2 0 . Marshal!, P . ; Kidson, E . 1 92 8 : The duststorrn of October , 1 92 8 . New Zealand journal of science and technology 1 0 : 2 9 1-2 9 9 . Marshal! , P . ; Murdoch, R . 1 92 0 : Tertiary rocks near Wanganui . Transactions of the New Zealand Instit ute 52 : 115-12 8 . Mason, B . 1 95 5 : Notes on some New Zealand minerals . New Zealand journal of science and technology B36 : 557 . Mason, B . 1 9 6 6 : P rinciples of geochemistry . New York . John Wiley & Sons . Mathews , B . 1 97 6 : S oils with discont inuous induration in the Penrith a rea of Cumbria . Proceedings of the North of England Soils Discussion Group (1 9 74) 1 1 : 11-1 9 . Mew, G . ; Hunt , J . L . ; Froggatt , P . C . ; Eden, D .N . ; Jackson, R . J . 1 9 8 6 : An occurrence o f Kawakawa tephra f rom the Grey River valley, S outh I sland, New Zealand . New Zea�and journal of geology and geophysics 28 : 3 15-323 . Mildenhall, D . C . 1 97 9 : Holocene pollen diagrams from Pauatahanui Inlet, Porirua, New Zealand . New Zealand journal of geology and geophysics 22 : 585-5 9 1 . 3 1 9 Mildenhall, D . C . ; Moore , P . R . 1 9 83 : A late Holocene pollen sequence at Turakirae Head, and climat ic and vegetational changes in the Wellington area in the last 1 0 , 0 0 0 years . New Zealand journal of science 26 : 447-4 5 9 . Mi ller , R . B . 1 9 6 1 : The chemical composition of rainwater at Taita, New Zealand, 1 956-58 . New Zealand journal of science 4 : 8 4 4- 8 5 3 . Miller , R . B . 1 9 63a : Plant nutrients in hard beech . I . The immobilisation of nut rient s . New Zealand journal of science 6 : 3 65-377 . Mil le r , R . B . 1 9 63b : Plant nutrients in hard beech . I I . Seasonal variation in leaf composit ion . New Zealand journal of science 6 : 378-387 . Miller , R . B . 1 9 63c : Plant nutrients in hard beech . I I I . The cycle of nutrients . New Zealand journal of science 6 : 388-413 . Mille r , R . B . 1 9 65 : Cycles of energy, minerals , water and organic matter in an ecosystem with hard beech . New Zealand soil news 1 3 : 113-119 . Mil le r , R . B . 1 978 : Soil Taxonomy . New Zealand soil news 2 6 : 1 7 6 -7 9 . Milne , J . D . G . 1 973a : Maps and sections of river terraces in the Rangitikei basin, North Island, New Zealand . New Zealand soil s urvey report 4 . Milne , J . D . G . 1 973b : Upper Quaternary geology o f the Rangitikei drainage basin, North Island, New Zealand . Unpublished Ph . D . t hesis , held in the Library, Victoria University o f Wel lington . Milne , J .D . G . 1 973c : Mount Curl Tephra , A 2 3 0 , 0 0 0 -year-old marker bed i n New Zealand, and its implication for Quaternary chronology . New Zealand journal of geology and geophysics 1 6 : 5 1 9-532 . Miln e , J . D . G . 1 97 6 : Upper Quate rnary geology of the Rangitikei val ley . Pp 60-62 . Excursion guide no . 55A and 5 6C. 25th International Geological Congress, 1 9 7 6, Sydney. Christchurch, P rogress P ress . Milne, J . D . G . 1 981 : Yellow-grey earths and yellow-brown earths formed f rom loess with tephra additions . Pp . 1 4-18 . In Soils with Variable Charge Conference Guidebook for Tour 4 . Government P rinter, Wellington . 32 0 Milne , J . D . G . ; Smalley, I . J . 1 97 9 : Loess depos its in the southern part of the North Island of New Zealand . An outline strat igraphy . Acta Geological Academiae Scientiarum Hungari cae, Tomus 22 (1-4) : 1 9 7- 2 0 4 . Mitchell , B . D . 1 97 5 : Oxides and hydrous oxide s of silicon . Pp 3 9 5-432 . In Gieseking, J . E . ed . Soil component s , Volume 2 . Inorganic components . New York, Springer-Verlag . Mitchell , R . S . 1 9 67 : Tridyrnite pseudomorphs a fter wood in Virginian Lower Cretaceous sediments . Science 1 5 8 : 9 0 95-91 0 6 . Mitchell , R . S . ; Tuft , S . 1 9 7 3 : Wood opal - A t ridyrnite-like mineral . American mineralogist 58 : 7 17-720 . Miyauchi, N . ; Aomine , S . 1 9 6 4 : Does "allophane B" exist in Japanese s oils? Soil Science and plant nutrients 1 0 : 1 9 9-2 03 . Mizota , C . 1 97 6 : Relat ionship between the primary mineral and the clay mineral compositions of s ome recent andosols . Soil science and plant nutrients 22 : 2 5 7 -2 6 8 . Mizot a , C . ; Aomine , S . 1 9 75 : Clay mineralogy of some volcanic ash s oils in which cristobalite predominates . Soil science and plant n utrition 21 : 327-335 . Mizot a , C . ; Toh, N . ; Matsuhia, Y . 1987 : Origin of cristobalite in s oils derived from volcanic ash in temperate and tropical regions . Geoderma 39 : 323-330 . Mizutani, S . 1 97 7 : P rogressive ordering of cristobalitic silica in the e arly stages of diagenesis . Contributions t o mineralogy and petrology 61 : 129-140 . Moar , N . T . 1 9 6 1 : Contributions to the Quaternary history of the New Zealand flora . 4 : Pollen diagrams from the western Ruahine Range . New Zealand journal of science 4 : 350-35 9 . Moar , N . T . 1 967 : Contributions to the Quaternary history of the New Zealand flora . 5 : Pollen diagrams from No Man' s Land bog, northern Ruahine Range . New Zealand journal of botany 5 : 3 9 4-399 . Moar, N . T . 1973 : A pollen diagram from a buried peat in loess at T irnaru, South Island, New Zealand . Abstracts of the 9th INQUA Congress, 1 9 73, Christchurch . Pp 245-2 4 6 . Moar , N . T . 1 98 0 : Late Otiran and early Aranuian grassland in central S outh Island . New Zealand journal of ecology 3 : 4-12 . Mokma , D . L . ; Syers , J . K . ; Jackson , M . L . ; Clayton, R . N . ; Rex, R . W . 1 972 : Eolian additions t o soils and sediments in the South Pacifica area . Journal of soil science, 23 : 1 4 7 -162 . Molina-Cru z , A . 1 9 7 7 : The relation of the southern trade wind to the upwel ling processes during the last 7 5 , 0 0 0 yea rs . Quaternary research 8 : 324-338 . Molloy, B . P . J . ; Cox, J . E . 1 9 65 : The role of Beech forest in the development of the yel low-brown earth to podzol sequence of eastern South Island . New Zealand soil news 1 3 : 95-103 . 3 2 1 Molloy, L . F . ; Speir, T . W . 1 97 7 : Studies on the clirnosequence of soils in tussock grassland . 1 2 . Constituents of the soil light fraction . New Zealand journal of science 20 : 1 67-17 7 . Moncure , G . K . ; Surdam, R . C . ; McKaque, H . L . 1 9 8 1 : Zeolite diagenesis below Pahute Mesa, Nevada test site . Clays and clay minerals 2 9 : 3 8 5 -3 9 6 . Moore , T . C . ; Hatson, W . H . ; Kipp, N . ; Hays , J . D . ; P rell , W . ; Thompson , ; Boden, G . 1 9 8 1 : The biological record of the ice age ocean . Palaeogeography, palaeoclimatology, palaeoecology 35 : 357-37 0 . Mullineaux, D . R . ; Crandell, D . R . 1 9 62 : Recent lahars from Mount St . Helens , Washington . Geological Society of America bulletin 73 : 8 55-87 0 . Mullins , C . E . ; Panayiotopoulas, K . 1 9 8 0 : Why are compact horizons unusua l . North of England soils discussion group (1 9 79) proceedings 1 6 : 127-130 . Murata, K . J . ; Friedman, I . ; Gleason, J . D . 1 977 : Oxygen isotope relations between diagenetic silica minerals in Monterey shale , Ternblar Range , California . American journal of science 277 : 2 5 9- 272 . Murata, K . J . ; Larson, R . R . 1 97 5 : Diagenesis of Miocene siliceous shales , Ternblar Range , California . Journal of research of the United States Geological Survey 3 : 553-5 6 6 . Murata, K . J . ; Nakata , J . K . 1 97 4 : Cristobalitic stage in the diagenesis of diatornaceous shale . Science 184 : 567-56 8 . Murray, H . H . ; Harvey, C . ; Smith , J .M . 1 977 : Mineralogy and geology of the Maungaporerua halloysite deposit in New Zealand . Clays and clay minerals 25 : 1-5 . 3 2 2 Neal J . T . ; Langer A . M . ; Kerr P . F . 1 97 9 : Giant des iccation polygons o f Great Bas in P layas . Geological society of America bulletin 79 : 6 9- 9 0 . . Neall, V . E . 1 97 2 : Tephrachronology and tephrastrat igraphy of western Taranaki . New Zealand Journal of Geology and Geophysics 15 (4 ) : 507-557 . Neall, V . E . 1 9 8 2 : Yellow-brown learns of Taranaki . Pp . 34-36 . In Neall , V . E . ed . Soil Groups of New Zealand . Part 6 , Yellow-brown learns . New Zealand Society of Soil Science , Wellington, New Zealand . Neall , V . E . ; Stewart , R . B . ; Smith, I . E . M . 1 9 8 6 : History and pet rology of the Taranaki volcanoes . Pp 2 5 1 -263 . In Smith, I . E . M . ed . Late Cenozoic Volcanism in New Zealand . Royal Society of New Zealand bulletin 23 . Neall , V . E . ; Stewart , R . B . ; Wallace , R . C . ; Mew, G . 19 8 3 : The origin of quartz and associated soil mineralogy in relation to terrace ages at Kumara , Westland, New Zealand . Abstracts, Pacific Science Association 1 5th Congress, Dunedin, New Zealand. Volume 1 : 17 4 . Nelson, C . S . 1 9 8 5 : Lithostratigraphy of DSDP leg 9 0 drill sites in the southwest P acific : An overview . Pp . 1 4 7 1-14 9 1 . In Kennett, J . P . ; van der Borch , C . C . et al . ed . Initial Report s of the DSDP , vol . XC . Washington, United States Government P rinting Office . Nelson, C . S . ; F roggatt , P . C . ; Gosson , G . J . 1 98 5 : Nature , chemistry, and origin of Late Cenozoic megascopic tephras in leg 90 cores from the s outhwest Pacific . Pp . 1 1 6 1-117 3 . In Kennett , J . P . ; van der Borch, C . C . et al . eds . Initial Reports of the DSDP , vol . XC . Washington, United States Government Printing Office . Nelson, C . S . ; Hendy, C . H . ; Cuthbertson, A . M . ; Jarrett , G . R . 1 9 85 : Late Quaternary carbonate and isotope stratigraphy, subantarctic site 5 9 4 , southwest Pacific . Pp . 1 425-1435 . In Kennett , J . P . ; van der Borch, C . C ; et al . ed . Initial Reports of the DSDP , vol . XC . Washington , United States Government Print ing Office . Nelson, C . S . ; Hendy, C . H . ; Jarrett , G . R . ; Cuthbertson, A . M . 1 985 : Near-synch roneity of New Zealand alpine glaciat ion and northern hemisphere continental glaciations during the past 75 0 kyr . Nature 3 1 8 : 3 6 1 -363 . Netolitsky, F . 1 92 9 : Die Kieselkorpen . Linsbauers Handb. der Pflanzenanatomie Berlin . 3 /1a : 1-8 0 . New Zealand Soil Bureau, 1 954 : General survey of the soils of North Island, New Zealand . New Zealand Soil Bureau bulletin 5 . New Zealand Soil Bureau, 1 9 6 8 : Soils of New Zealand . New Zealand Soil Bureau bulletin 26 : 3 volumes . Nikiforoff, C . C . 1 955 : Hardpan soils of the coastal plain of southern Maryland . United States Geological Survey Professional Paper 267B . 3 2 3 Norris , R . M . 1 972 : Shell and gravel layers , western cont inental shelf, New Zealand . New Zealand journal of geology and geophysics 1 5 : 572-58 9 . Norton, L . D . ; Bigham, J . M . ; Hall, G . F . ; Smeck, N . E . 1 9 8 3 : Etched thin sections for coupled optical and e lectron microscopy and microanalysis . Geoderma 30 : 55-64 . Oehler, J . H . 1 97 3 : Tridymite like c rystals in cristobalite "chert" . Nature, physical sciences 241 : 6 4-65 . Oliver, R . L . 1 9 48 : The Otaki sandstone and its geological history . Department of Scientific and Industrial Research geological memoir 7 . O ' Neil, J . R . ; Epstein, S . 1 9 6 6 : Oxygen isotope fractionation in the system dolomite-calcite-carbon dioxide . Science 1 52 : 1 9 8-200 . O ' Neil , J . R . ; Taylor , H . P . 1 967 : The oxygen isotope and cation exchange chemistry of feldspars . American mineralogist 52 : 1 414- 1437 . Packard, R . 1 9 5 8 : Physical properties of the yellow-grey earths . New Zealand soil news 6 : 227-2 30 . Pain, C . F . 1 97 5 : Some tephra depos its in the south-west Waikato area , North Island, New Zealand . New Zealand journal of geology and geophysics 1 8 : 5 4 1-550 . Palmer , A . S . : The stratigraphy and selected properties of loess in Wairarapa , New Zealand . Unpublished Ph . D . thesis held in the Library, Victo ria University of Wellington . Papike , J . J . ; Hedges , F . N . ; Bence , A . E . ; Cameron, M . ; Rhodes , J .M . 1 97 6 : Mare basalts : crystal chemistry, mineralogy and petrology . Reviews of geophysics and space physics 1 4 : 475-5 4 0 . Parfit t , R . L . 1 9 7 5 : Clay minerals in recent volcanic soils from Papua New Guinea . Pp 2 4 1 -2 4 5 . In Suggate, R . P . ; Cresswell , M .M . eds . Quaternary studies . Wellington, Royal Society of New Zealand . Parfitt , R . L . ; Milne , J . D . G . 1 9 8 4 : An hypothes is on the formation of yellow-grey earths . p . 65 . In Bruce , J . G . ed . Soil Groups of New Zealand . Part 7 , Yellow-grey earths . New Zealand Soceity of Soil Science , Lower Hutt, New Zealand . 3 2 4 Parfitt , R . L . ; Rus sell , M . ; Orbell, G . E . 1 9 8 3 : Weathering sequences of soils from volcanic ash involving allophane and halloysite , New Zealand . Geoderma 2 9 : 4 1-57 . Parfitt , R . L . ; Saigusa, M . ; Eden D . N . 1 9 8 4 : Soil development processes in an aqualf-ochrept sequence from loess with admixtures of tephra, New Zea land . Journal of soil science 35 : 62 5 - 6 4 0 . Park, J . 1 910 : The geology of New Zealand . Whitcombe & Tombs Ltd . Dunedin . Patel , R . N . 1 9 8 6 : Wood anatomy of the dicotyledons indigenous to New Zealand . 1 5 . Fagaceae . New Zealand journal of botany 2 4 : 1 8 9 -2 0 3 . Pau l , M . A . 1 9 8 0 : The compaction of soil : a geological and geotechnical analysis . Proceedings of the North of England soils discussion group 1 6 : 6 3-82 . Pede rsen, T . F . 1 98 3 : Increased productivity in the eastern equatorial Pacific during the last glacial maximum ( 1 9 , 0 00 to 1 4 , 0 0 0 years B . P . ) . Geology 1 1 : 1 6 - 1 9 . Peterson, M . N .A . ; von der Borch, C . C . 1 9 65 : Chert : modern inorganic deposition in a carbonate precipitat ing locality . Science 1 4 9 : 1501-15 0 3 . Pet it , J . R . ; Duval , P . ; Lorius, C . 1 9 8 7 : Long-term climatic changes indicated by c rystal growth in polar ice . Nature 325 : 62-64 . Pett i j ohn, F . J . ; Potter , P . E . ; Siever, R . 1 972 : Sands and sandstones . New York, Spring-Verlag . 618 p . Pewe , T . L . 1 9 8 1 : Desert dust : origin, characteristics and effects on Man . Geological Society of America special paper 1 8 6 . Pillans , B . J . 1 9 8 5 : Southwest North Island paleoenvironment s 1 50 , 0 0 0 years B . P . to present . P p 37-43 . In P illans , B . J . ed . The second symposium of results and discussions concerned with Late Quaternary climatic history of Aust ralia New Zealand and surrounding seas . Geology Department , Victoria Univerity of Wel lington Publication 3 1 . Pillans , B . J . 1 98 6 : A Late Quaternary uplift map for North Island, New Zealand . Royal Society of New Zealand bulletin 24 : 40 9- 4 17 . 3 2 5 P isciotto , K . A . 1 9 7 8 : Basinal sedimentary facies and diagenic aspects of the Monterey Shale , California . Unpublished Ph . D . thes is , held at the Univers ity of California , Santa Cruz . 450 p . Pisciotto , K . A . 1 9 8 1 : Diagenetic trends in the siliceous facies of the Monterey Shale in the Santa Maria region, California . Sedimentology 28 : 547-57 1 . Pohlen , I . J . ; Harris , C . S . ; Gibbs , H . S . ; Raeside , J . D . 1 9 4 7 : Soils and s ome related agricultural aspects of mid Hawke ' s Bay . New Zealand Department of Scientific and Industrial Research Bulletin 94 . 1 7 6 p . Pollok, J . A . 1975 : A comparative study of certain New Zealand and German soils formed from loess . Published Ph . D . thesis , Institue fur Badenkunde , Rheinischen Friedrich-Wilhelrns-Univeritat , Bonn . Pollok, J . A . 1 98 1 : Changes in pedogenic processes and soil propert ies of the junction between the fragipan and horizons above in a sequence of four New Zealand yellow-grey earths ( fragiochrepts to fragiaqualfs ) . Abstracts of the Soils With Variable Charge Conference, 1 981 , Palmerston North . p 1 9 0 . Pollok , J . A . 1 9 8 4 : Development of variable charge properties in T okornaru silt loam . Pp 7 6-7 9 . In Bruce, J . G . ed . Soil groups of New Zealand . Part 7 yellow-grey earths . Lower Hutt , New Zealand S ociety of Soil Science . Pollok , J . P . 1 97 6 : Towards a definitive account of the Tokomaru silt loam, (Summary) . New Zealand soil news 24 : 135-13 6 . Press , F . ; Siever , R . 1 97 4 : Earth . W . H . Freeman and Co . San Francisco . Pullar , W . A . 1 9 67 : Volcanic ash beds in the Waikato district . Earth science journal 1 : 17 -3 0 . Pullar , W . A . 1 9 8 0 : Tephra and loess cover deposits of Kaiangaroa P lateau including detailed lithology of upper Taupo Pumice . New Zealand Soil Bureau scientific report 44 . Pullar , W . A . ; Birrell , K . S . 1 97 3a : Age and distribution of late Quaternary pyroclastic and associated cover deposits of the Rotorua and Taupo area , North Island, New Zealand . New Zealand soil survey reports 1 . Pullar , W . A . ; Birrell , K . S . 1 9 7 3b : Age and distribution of late Quaternary pyroclastic and associated cover deposits of the Rotorua and Taupo area , North Island, New Zealand . New Zealand soil survey reports 2 . Pullar, W . A . ; Birrell, K . S . ; Heine , J . C . 1 97 3 : Named tephras and tephra format ions occurring in the central North Island, with notes on derived soils and buried paleosols . New Zealand journal of geology and geophysics 1 6 : 4 97-518 . Pullar, W . A . ; Pollok , J . A . 1 9 73 : Palaeosols and tephric loess associated with the Okareka and Te Rere Tephra formations . New Zealand soil news 21 : 1 8 6-188 . Pye , K . 1 9 8 4 : Some perspect ives on loess accumulation . Loess letter 1 1 : 5-10 . Pye , K . ; Sperling, C . H . B . 1 98 3 : Experimental invest igat ion of silt formation by static breakage proces ses : the effect of temperature , moisture and ·salt on quart z dune sand and granite regoliths . Sedimentology 30 : 49-63 . 3 2 6 Raeside , J . D . 1 956 : Yellow-grey earths of South I sland, New Zealand an example of polygenesis in soil development . Rapports 6e Congress International de la Science du Sol, 1 9 65, Paris . Pp 6 65-672 . Raes ide , J . D . 1958 : The yellow-grey earths of the South Island . New Zealand soil news 6 : 2 0 6-2 0 8 . Raeside , J . D . 1 9 64a : Loess deposits of the South Island, New Zealand, and soils formed on them . New Zealand journal of geology and geophysics 7 : 8 1 1-838 . Raeside , J . D . 1 9 64b : Loess and soil formation . New Zealand soil news 12 : 9 9-1 02 . Raeside , J . D . 1 9 6 4c : Further comment on loess and yellow-grey earths . New Zealand soil news 1 2 : 22 6-228 . Raeside , J . D . 1 97 0 : Some New Zealand plant opa l . New Zealand journal of science 13 : 122-132 . Raisbeck, G . M . ; Yiou F . ; Bourles , D . et al . 1 9 8 7 : Evidence for two intervals of enhanced 1 0Be deposition in Antarct ic ice during the last glacial period . Nature 326: 273-277 . Rankin , P . C . 1 97 3 : Correlation of volcanic glasses in tephras and soils using micro-element compositions . New Zealand journal of geology and geophysics 1 6 (3) : 637-6 4 1 . Reed, J . J . 1957 : Petrology o f the lower Mesozoic rocks of the Wellington district . New Zealand geological survey bulletin 5 7 . 6 0 p . Reid, J . S . 1 9 4 7 : Silica in Beech timbers . New Zealand journal of forestry 4 : 330-331 . 3 2 7 Reid, J . S . 1 9 5 5 : Beech t imbers . New Zealand Forest Service information series 1 7 . Reid, S . J . 1 9 82 : Surface wind frequencies in the southwest Pacific estimated from radar-wind data . New Zealand journal of science 25 : 3 03-3 1 1 . Reid, S . J . ; Penny, A . C . 1 9 8 2 : Upper-level wind f requencies and mean speeds for New Zealand and Pacific island station . New Zealand meteorological service miscellaneous publication 1 74 . Rex, R . W . 1 9 6 9 : X-ray mineralogical studies . pp 354-3 6 8 . In Ewing et . al . 1 9 6 9 : Initial reports of the deep sea drilling pro ject leg 1 , 672pp . Rex, R . W . ; Goldberg, E . D . 1 9 62 : Insolubles . In Hill, M . N . ed . The Sea . Interscience , London 1 : 2 95-304 . Reynolds , W . R . 1970 : Mineralogy and st ratigraphy of Lower Tertiary clays and claystones of Alabama . Journal of sedimentary petrology 40 : 82 9- 8 4 0 . Rich , C . C . 1 95 8 : Occurrence of sterrasters of the Geodiidae (Demospongea, Choristida ) in late Cenozoic strata of western Wellington province , New Zealand . New Zealand journal of geology and geophysics 1 : 6 41- 64 6 . Rich , C . C . 1 9 5 9 : Late Cenozoic geology of the lower Manawatu valley, New Zealand . Unpublished Ph . D . thesis, Harvard University . Richmond, G . M . 1 9 62 : Quaternary stratigraphy of the La Sal Mountains , Utah . United States Geological Survey professional paper 32 : 135 p. Riezebos , P . A . ; Lustenhouwer , W . J . 1983 : Characteristics and significance of composite particles derived from a Columbian andosol profile . Geoderma 30 : 1 95-217 . Rockett , T . J . ; Foster, W . R . 1 9 67 : The thermal stability of purified tridyrnite . American ndneralogist 52 : 1233-12 4 0 . Rogers , A . F . 1 92 8 . Natural history of the silica minerals . American mineralogist 1 3 : 7 3-90 . Romans , J . C . C . 1 97 6 : Indurated layers . Proceedings of the North of England soils discussion group (1 974) 11 : 2 0-30 . Roser, B . P . 1 9 8 3 : Comparat ive studies of copper and manganese minera lisat ion in Torlesse , Waipapa and Haast Schist terrains , New Zealand . Unpublished Ph . D . thesis, held in the Library, Victoria University of Wel lington . Ross , D . J . 1 9 8 4 : Some biochemical properties of two southern yellow­ grey earths under tussock grassland . Pp 1 0 4-1 0 7 . In Bruce , J . G . ed . Soil Groups of New Zealand Part 7 Yellow-grey earths . Lower Hutt, New Zealand Soil Science Society . Rovner , I . 1 97 1 : Potential of opal phytoliths for use in paleoecological reconstruct ions . Quaternary research 1 : 343-359 . Rowe , G . H . 1 9 8 0 : Applied geology of Wellington rocks for aggregates and concrete � Unpublished Ph . D . thesis held at the Library, Victoria University of Wellington . Roy, D . M . ; Roy, R . 1 9 6 4 : Tridymite-cristobalite relations and stable s olid solution . American mineralogist 4 9 : 953- 9 62 . Ruddiman, W . F . ; Duplessey, J . C . 1 9 85 : Conference on the last deglaciation : t iming and mechanism . Quaternary research 23 : 1-17 . 3 2 8 Ruddiman, W . F . ; Mcintyre , A . 1 9 8 1 : The North Atlantic Ocean during the last glaciation . Palaeogeography, palaeoclimatol ogy, palaeoecology 35 : 145-2 1 4 . Ruddiman, W . F . ; Mcintyre , A . 1 9 82 : Severity and speed of Northern Hemisphere glaciation pulses : the limiting case . Geological Society of America bulletin 93 : 1273-127 9 . Ruhe , R . V . 1 9 6 9 : Application of pedology to Quaternary research pp 1- 2 3 . In Pawluk, S . ed. Pedology and Quaternary Research . National Research Council of Canada and University of Albe rta . Ruhe , R . V . ; Miller, G . A . ; Vreeken, W . J . 1 97 1 : Paleosols , loess sedimentation and soil stratigraphy . Pp 4 1-60 . In Yaalon, D . H . ed . Paleopedology - Origin, natue and dating o f paleosols . Jerusalem, International Society of Soil Science and Israel University Press . Runge , E . C . A . ; Goh, K . M . ; Rafter 1 97 3 : 1 4c chronology and problems in their interpretation for Quaternary loess deposits - Timaru, New Zealand . Soil Science Society of America proceedings 3 7 : 7 42-64 6 . Runge, E . C . A . ; Walker , T . W . ; Howorth, D . T . 1 97 4 : A study of the Late P le istocene loess deposits, South Canterbury, New Zealand. Part l : Forms and amounts of phosphorus compared with other techniques for identifying paleosols . Quaternary research 4 : 7 6-84 . 3 2 9 Ruprecht , I . 1 8 6 6 : Geobotanical invest igat ions on Chernozem . St . Petersburg Imperiale Academie des Sciences . Rut ledge , E . M . ; Wilding, L . P . ; Ha ll , G . F . ; Holowaychuk , N . 1 975 : Loess in Ohio in relation to several poss ible source areas : II element and mineralogical composit ions . Soil Science Society of America proceedings 39 : 1133-1139 . Salinger , M . J . et al . 1985 : Modelling the Last Glacial/ Interglacial t ransition : Implications for New Zealand climate ( note ) . P roceedings of the Second CLIMANZ Conference , 1 9 8 5 , Westland, New Zealand . Geology Department , Victoria Univeristy of Wellington publication 31 . Sande r s , J : V . 1 9 6 8 : Diffraction of light by opals . Acta cyrstallographic A24 : 427-43 4 . Sarna-Wojcicki , A . M . ; Shipley, S . ; Waitt , R . B . ; Dzurisin, D . ; Word, S . H . 1 9 8 1 : The 1 9 8 0 erupt ions of Mount St . Helens , Washington : a rea distribut ion, thickness , mass , volume and grain size of a irfall ash from the six ma jor eruption of 1 9 8 0 . United States Geological Survey professi onal paper 1250 : 57 7-60 0 . Sato , M . 1 9 63a : X-ray studies of tridymite ( 1 ) on tridymite-M and t ridymite-S . Mineralogical journal 4 : 115-130 Sato , M . 1 963b : X-ray studies of tridymite (2 ) structure of low t ridymite , type M . Mineral ogical journal 4 : 131-1 4 6 . Sato , M . 1 9 63c : X-ray studies of t ridymite ( 3 ) unit cell dimensions and phase transitions of t ridymite , type S . Mineralogical journal 4 : 2 15-225 . Savin , S .M . ; Epstein, S . 1 9 7 0 : The oxygen isotopic composit ions of coarse grained sedimentary rocks and minerals . Geochimica et cosmochimica acta 34 : 323-32 9 . Schofield, J . C . 1 9 65 : The Hinuera Formation and associated Quaternary events . New Zealand journal of geology and geophysi cs 8 : 772-7 9 1 . Scotte r , D . R . ; Clothier , B . E . ; Corker , R . B . 1 97 9 : Soil water in a fragiaqualf . Australian journal of soil research 1 7 : 4 43-453 . Scurfie ld, G . ; Segnit , E . R . 1 9 8 4 . Petrification of wood by silica minerals . Sedimentary geology 3 9 : 1 4 9-167 . Segnit, E . R . ; Anderson, C . A . Jone s , J . B 1 9 7 0 : A scanning electron microscope study of the morphology of opal . Search 1 : 3 4 9-35 1 . Selby, M . J . 197 6 : Loess . New Zealand journal of geography 61 : 1- 1 8 . Sel f , S . 1 9 8 3 : Large-scale phreatomagmat ic silicic volcanism : a case study from New Zealand . Journal of volcanology and geothermal research 1 7 : 4 33-4 6 9 . 3 3 0 Self , S . Healy, J . 1 9 8 7 : Wairakei Format ion, New Zealand : Stratigraphy and correlation . New Zealand journal of geology and geophysics 3 0 : 7 3-8 6 . Senkayi , A . L . ; Dixon , J . B . ; Hossner, L . R . ; Yerima , B . P . K . ; Wilding, L . P . 1 9 85 : Replacement of quart z by opaline silica during weathering of pet rified wood . Clays and clay minerals 33 : 52 5-53 1 . Shackleton, N . J . ; Opdyke , N . D . 1973 : Oxygen isotope and paleomagnet ic s trat igraphy of equatorial Pacific core V2 8-238 : oxygen isotope t emperatures and ice volumes on a 1 0 4 year scale . Quaternary research 3 : 3 9-55 . Shepherd, G . T . 1 9 8 4 : A pedological study of the Hamilton Ash Group at ' Welches Road, Mangawara , north Waikato . Unpublished M . Sc . thesis, held in the Library, Waikato University . Sho j i , S . ; Saigusa, M . 197 8 : Occurrence of laminar opaline s ilica in some Oregon andosols . Soil science and plant nutrition 24 : 157- 1 6 0 . Sho j i , S . ; Takahashi, T . ; Saigusa, M . ; Yamada , I . ; Ugolini , F . C . 1 9 8 6 : Climo- and biosequences of tephra derived soils in Towada Dist rict , Northeastern Japan - chemical and mineralogical properties . Abstracts of the 13th International Soil Science Society Congress, 1 986, Hamburg III : 1274-1275 . Siever , H . C . ; Stein, C . L . 1 97 6 : Model s for the t ransformation of biogenic silica to chert . Transactions of the America Geophysical Union, EOS 5 7 : 2 5 6 . Sippel , R . F . 1 9 7 1 : Luminescence petrography of the Apollo 12 rocks and comparitive features of terrest rial rocks and meteorites . Proceedings of the second lunar conference 1 : 247-263 . S jarif , S . ; Gilkes , R . J . 1 9 8 6 : Some propert ies of Indonesian andosols and their sorption of phosphorus . New Zealand soil news 34 : 1 8 0 . Skinner , H . C . 1 9 63 : Precipitation of calcium dolomite and magnesium calcite in the southeast of South Australia . American journal of science 2 61 : 4 4 9-472 . Smal ley, I . J . 197 8 : The New Zealand loess and the ma jor categories of loess classificat ion . Search 9 : 2 8 1-282 . 3 3 1 Smal ley, I . J . 1 9 8 1a : Format ion o f a fragipan in a loess soil : An assumption, a speculation and a simple mathematical model (Pt 1 ) . New Zealand soil news 29 : 1 67-1 6 9 . Smalley, I . J . 1 9 8 1b : Format ion of a fragipan in a loess soil : An assumption, a speculat ion and a simple mathematical model (Pt 2 ) . New Zealand soil news 29 : 1 92-195 . Smalley, I . J . 1 982a : Format ion of a fragipan in a loess soil : An assumption, a speculat ion and a simple mathematical model (Pt 3 ) . New Zealand soil news 30 : 27 -2 9 . Sma lley, I . J . 1 982b : The New Zealand loess in a world setting . Pp 9 9- 1 0 9 . In Wasson, R . J . ed. Quaternary dust mant les of China, New Zealand and Aust ralia . Canberra , Australia National University . Smalley, I . J . ; Davin, J . E . 1 9 82 : Fragipan horizons in soils : a bibliographic study and review of some of the hard layers in loess and other materials . New Zealand Soil Bureau Bibliographic Report 30 . 122p . Smalley, I . J . ; Krinsley, D . H . 1 9 8 1 : The Urloss concept , and changing ideas on loess formation . New Zealand soil news 29 : 57 -5 9 . Smith , G . D . ; Ayra, L . M . ; Stark, J . 1 9 75 : The dens ipan, a diagnost ic horizon of Densiaqualfs for Soil Taxonomy . Soil Science Society of America Proceedings 3 9 : 3 6 9-37 0 . Smith , R . M . ; Twiss , P . C . ; Kraus , R . K . ; Brown , M . J . 1 9 7 0 : ·oust deposition in relation to site , season and climatic variations . Soil Science Society of America proceedings 34 : 112-117 . Soil Survey Staff, 1 9 5 4 : General survey of the soils of the North Island, New Zealand . New Zealand Soil Bureau bulletin 5 . Soil Survey Staff, 1 9 7 5 : Soil Taxonomy; A basic system of soil classification for making and interpreting soil surveys . United States Department of Agriculture, Soil Conservation Service, Agriculture Handbook 436 . 7 5 4p . Soons , J .M . 1 97 6 : Late Quaternary environments in the South Island of New Zealand . Abstract of the 25th International Geological Congress 2 : 51 1 . Sosman, R . B . 1932 : The inversion of cristobalite . Journal of the American chemical society 54 : 3 0 15-3 0 1 6 . Souster , W . E . ; Arnaud, R . J . St . ; Huang, P . M . 1 9 8 5 : Mineral sorting through aeolian processes . Loess letter 1 3 : 5-10 . 3 3 2 Sparl ing G . P . ; Milne J . D . G . ; Vincent , K . W . 1 98 6 : Effect o f soil moisture regime on the microbial contribution to Olsen P values . In Abst ract s , New Zealand Society of Soil S cience Conference . New Zealand soil news 34 : 1 8 0 . Splettstoesser J . F . ; Jirsa M . A . 1 985 : Columnar j ointed sandstone in Beacon supergroup, Britannia Range , Antarct ica . New Zealand journal of geology and geophysics 28 : 7 6 1 -7 6 4 . Sridhar , K . ; Jackson , M . L . ; Clayton, R . N . 1 97 5 : Quartz oxygen isotope stability in relation to isolat ion from sediments and divers ity of source . Soil Science Society of America proceedings 3 9 : 12 0 9- 1 2 1 3 . Stein , C . L . 1 982 : Silica recrystallisation in petrified wood . Journal of sedimentary petrology 52 : 1277-1282 . Stein, C . L . ; Kirkpat rick, R . J . 1 97 6 : Experimental porcelanite recrystallisation kinetics : A nucleat ion and growth model . Journal of sedimentary petrology 4 6 : 4 3 0-435 . Steinhaedt , G . C . ; Fransmeier 1 97 9 : Chemical and mineralogical properties of the fragipan of the Cincinnati catena . Journal of the Soil Science Society of America 43 : 1 0 0 8-1013 . Stevens , K . F . ; Vucetich, C . G . 1 9 8 4 : Pedogenic weathering of Upper Quaternary tephras in New Zealand 1 . Isovolumetric geochemical evidence of cation movement . Chemical geology 4 7 : 2 85-302 . Stevens , K . F . ; Vucetich , C . G . 1 9 85 : Weathering of Upper Quaternary tephras in New Zealand . Clay minerals and their climatic interpretation . Chemical geology 53 : 2 37-2 47 . Stewart M . K . ; Taylor C . B . 1 98 1 : Environmental isotopes in New Zealand hydrology . I . Introduction : The role of oxygen-1 8 , deuterium, and t ritium in hydrology . New Zealand journal of sedimentology 2 4 : 2 95-31 1 . Stewart , R . B . 1 9 82 : Origin of selected soil parent materials and s ediments in North Isla�d, New Zealand . Unpublished Ph . D . thes is , held in the Library, Massey University . Stewart , R . B . ; Neall, V . E . 1 98 4 : Chronology of palaeoclimatic changes at the end of the last glaciation . Nature 311 : 47-48 . Stewart , R . B . ; Neall, V . E . ; Pollok, J . A . ; Syers , J . K . 1 9 7 7 : Parent material st ratigraphy of an Egmont loam profile , Taranaki , New Zealand . Australian journal of soil research 1 5 : 1 7 7 - 1 9 0 . Stewa rt , R . B . ; Neall, V . E . ; Syers , J . K . 1 9 8 6a : Accumulation of aerosolic quart z in an andept chronosequence , North Is land, New Zealand . Geoderma 3 7 : 331-34 0 . Stewart , R . B . ; Neall, V . E . ; Syers , J . K . 1 9 8 6b : Origin of quartz in selected soils and sedirnents , North Is land, New Zealand . New Zealand journal of geology and geophysics 2 9 : 1 47-1 52 . Struve , G . A . 1 8 35 : De silica in plantis nounullis . Diss Berlin . Suggate, R . P . 1 9 8 5 : The glacial / interglacial sequence of north Westland, New Zealand . New Zealand Geological Survey record 7 . 3 3 3 Suggate , R . P . ; Moar, N . T . 1 9 7 0 : Revision of the chronology of the late Otira Glacial . New Zealand journal of geology and geophysics 1 3 : 7 42-7 4 6 . Suggate, R . P . ; Stevens , G . R . ; Te Punga , M . T . ed . 1 9 7 8 : Geology of New Zealand . Wellington, Government Printer . Swindale, L . D . ; Jackson, M . L . 1 9 6 0 : A mineralogical study of soil format ion in four rhyolit ic derived soils from New Zealand . New Zealand journal of geology and geophysics 3 : 1 4 1 - 1 8 3 . Syers , J . K . ; Jackson, M . L . ; Berkheiser, V . E . ; Clayton, R . N . ; Rex, R . W . 1 9 6 9 : Eolian sediment influence on pedogenesis during the Quaternary . Soil science 1-7 : 421-427 . Syrnes , R . E . ; Wells, N . 1 97 3 : Mineral content of topsoils on coastal terraces from Mount Egmont to Palrnerston North, New Zealand . New Zealand journal of geology and geophysics 1 6 : 6 5 1 - 65 6 . Tada , R . ; I i j ima , A . 1 9 8 3 : Identification of mixtures of opaline s ilica phases and its implication for silica diagenesis . Pp 229- 2 44 . In Iijirna, A . ; Hein , J . R . ; Siever, H . C . ed. Siliceous deposits in the Pacific region . Amsterdam, Elsevier . Tarbuck, E . J . ; Lutgens , F . K . 1 9 8 4 : The Earth, an int roduction to physical geology . Charles E . Merrill , Colurnbus , Ohio . Taylor , B . E . ; Dunbar, N . ; Kyle, P . R . 1 98 6 : Stable isotope studies of the volatile history and degassing of rhyolitic magmas in the Taupe Volcanic Zone, New Zealand . Abstracts of the International Volcanologic Congress, 1 98 6, Auckland. P 2 1 7 . 3 34 Taylor, H . P . ; Epstein, S . 1 9 62 : Relationship between o1 8 : o1 6 rat ios in coexisting minerals of igneous and metamorphic rocks . Part 2 . Application to pet rologica l problems . Bulletin of the geological society of America 73 : 67 5- 6 9 4 . Taylor , H . P . ; Epstein, S . 1 9 7 0 : Stable isotope geochernistry of lunar samples . Geological Society of America Abstracts . In Henderson et al . ( 1 97 2 ) Soil Science Society American proceedings 3 6 : 830-835 . Taylor , N . H . 1 9 48 : Soil map of New Zealand . New Zealand Soil Bureau map No . S . B . 280 . Taylor, N . H . 1 953 : The ecological significance of the cent ral North Is land ash showers - the soil pattern . New Zealand ecological society proceedings 1 : 1 1 - 12 . Te Punga , M . T . 1 953a : A late P leistocene land bridge across Cook Strait , New Zealand . New Zealand journal of science and technology 35B : 16 1-192 . Te Punga , M . T . 1 953b : Radiocarbon dating of a Rangitikei River terrace . New Zealand journal of science and technology B35 : 45-4 8 . Te Punga , M . T . 1 95 3c : The geology of Rangitikei valley . New Zealand Geological Survey memoir B . Te Punga , M . T . 1 95 4 : Late P le istocene Buckshot Gravels from western Wellington, New Zealand . New Zealand journal of science and technology B36 : 1-13 . Te Punga, M . T . 1 957 : Live anticlines in Western Wel lington . New Zealand journal of science and technology B38 : 433-44 6 . Te Punga , M . T . 1 958 : Evidence for a low sea level 9 9 0 0 years ago . New Zealand journal of geology and geophysics 1 : 92-94 . Te Punga, M . T . 1 9 62 : Some geological features of the Otaki-Waikanae district . New Zealand journal of geology and geophysics 5 (4) : 51 7 -53 0 . Thiede , . J . 1 97 9 : Wind regimes over the late Quate rnary southwest Pacific Ocean . Geology 7 : 2 5 9-2 62 . Thompson, C . S . 1 98 1 : The c limate and weather of the Taranaki region . New Zealand meteorological service miscellaneous publication 1 1 5 . Thompson, L . G . ; Mosley-Thompson, E . 1 98 1 : Temporal variablity of microparticle properties in polar ice sheets . Journal of volcanology and geothermal research 11 : 1 1-27 . Thomson, J . A . 1 9 1 6 : The Hawera Serie s or the so-called "Drift Format ion" of Hawera . Transactions of the New Zealand Institute 4 9 : 4 14-417 . Thorson, R .M . ; Bender, G . 1 9 8 5 : Eolian deflat ion by ancient katabatic winds : A Late Quaternary example from the North Alaska Range . Geological Society of America 9 6 : 7 02-7 0 9 . 3 3 5 Tokashiki , T ; Wada , K . 1 97 5 : Weathering implications o f the mineralogy of clay fractions of two ando soils , Kyushu . Geoderma 1 4 : 47-62 . Tokuda , T . 1 9 6 0 : The X-ray powder patterns and the natural lattice constants of natural cristobalite . Mineralogical journal 3 : 1-8 . Tonkin, P . J . 1 9 7 0 : The soils of the southeastern sector of Egmont National Park . Earth science journal 4 : 3 6-5 9 . Tonkin, P . J . ; Runge , E . C . A . ; Goh, K . M . ; Walker, T . W . 1 97 3 : A study of Late Pleistocene loess deposits and associated paleosols , South Canterbury, New Zealand . Abstracts of the 9th INQUA Congress, 1 9 73, Christchurch . p 371 . Tonkin , P . J . ; Runge , E . C . A . ; Ives , D . W . 1 97 4 : A study of Late Pleistocene loess deposits , South Canterbury, New Zealand . Pt . I I Paleosols and their stratigraphic implications . Quaternary research 4 : 2 1 7 -231 . Topping, W . W . 1 97 3 : Tephrostratigraphy and chronology of late Quaternary eruptives from the Tongariro Volcanic Centre , New Zealand . New Zealand journal of geology and geophysics 1 6 : 397- 4 2 4 . Topping, W . W . ; Kohn, B . P . 197 3 : Rhyolitic tephra marker beds in the Tongariro are a , North Island, New Zealand . New Zealand journal of geology and geophysics 1 6 (3) : 37 5-423 . Turner , M . A . 1 9 4 4 : Geology of northern Wellington and southern Hawkes Bay . Unpublished Ph . D . thesis , held in the Geology Department , Victoria University of Wellington . Twiss , P . C; Suess , E . ; Smith, R . M . 1 9 6 9 : Morphological classification of grass phytoliths . Soil Science Society of America proceedings 33 : 1 0 9-115 . Urey, H . C . 1 947 : The thermodynamic properties of the isotopic substances . Journal of the Chemistry Society 98 : 5 62-58 1 . Urey, H . C . ; Lowenstam, H . A . ; Epstein, S . ; McKinney, C . R . 1 9 51 : Measurement of paleotemperatures and temperatures of the Upper Cretaceous of England, Denmark, and the southeastern United States . Geological society of America bulletin 62 : 3 9 9-4 1 6 . Van Der Linden, W . J . M . 1 9 6 9 : Off-shore sediments , north west Nelson, South Island, New Zealand . New Zealand journal of geology and geophysics 1 2 : 8 7-103 . Van Der Linden , W . J .M . ; Norris , R . M . 1 97 4 : St ructure and Quaternary history of Karamea Bight , South Island, New Zealand . New Zealand journal of geology and geophysics 1 7 : 37 5-3 8 8 . 3 3 6 Vella, P . 1 9 8 3 : Upper Pleistocene succession in inland Wairarapa Valley . Transactions of the Royal Society of New Zealand, Geology 2 : 63-7 8 . Veneman , P . L .M . ; Lidbo, D . L . 1 98 6 : Fragipan formation . Abstracts of the 1 3th International Society of Soil Science Congress, 1 986, Hamburg III : 1310-1 311 . Verhoogen, J . 1 937 : Mount St . Helens , a recent Cascade volcano . California University, Department of Geological Sciences bulletin 24 : 2 63-302 . Vucet ich, C . G . ; Birrell , K . S . 1 9 7 7 : Pre 4 0 , 0 0 0 year rhyolitic tephras in "Hamilton Ash Formation" . New Zealand soil news 25 : 8 4-87 . Vucetich, C . G . ; Birrell , K . S . ; Pullar, W . A . 1 97 8 : Ohinewai Tephra Formation : a c . 1 50 0 0 0 -year-old tephra marker in New Zealand . New Zealand journal of geology and geophysics 21 : 7 1- 7 3 . Vucetich , C . G . ; Howorth, R . 1 97 6 : P roposed definition of the Kawakawa Tephra , the c . 2 0 0 0 0 years B . P . marker horizon in the New Zealand region . New Zealand journal of geology and geophysics 1 9 : 4 3-50 . Vucetich, C . G . ; Kohn, B . P . 1 97 3 : The st rat igraphic significance of a dated late Pleistocene ash bed near Amberley, South I sland, New Zealand . Abstract of the 9th INQUA conference, 1 9 73, Christchurch . p 3 9 0 . Vucetich, C . G . ; Kohn, B . P . ; Pullar , W . A . 1 9 8 1 : Correlation of Arotora Tephra , Ahuroa coverbed type section, Te Kuiti . Pp . 1 1 6-130 . In Boworth, R . ; Froggatt , P . ; Vucetich, C . G . ; Collen, J . D . ed. Proceedings of the tephras workshop, June 30th-July 1st , 1 9 8 0 , Victoria University o f Wellington . Victoria University of Wellington, Geology Department publication 20 . 3 3 7 Vucetich, C . G . ; Pullar, W . A . 1 9 6 9 : St ratigraphy and chronology of Late Pleistocene ashbeds in central North Is land, New Zealand . New Zealand journal of geology and geophysics 12 : 7 8 4-837 . Wada , K . 1 9 8 0 : Mineralogical characteristics of andisols . Pp 8 7 - 1 0 7 . In Theng, B . K . G . ed . Soils with variable charge . Lower Hutt , New Zealand Soil Science Society . Wada , K . ; Kakuto , Y . 1 9 8 4 : Summary of clay minerals analyses of Chile soil samples for the Sixth Internat ional Soils Classificat ion Workshop . Anonymous Classification and management of andisols, 1 984 : Sixth International Soil Classification Workshop, Chile and Equador . Tour guide part 1 , Chile . Walker, P . H . ; Cost in, A . B . 1970 : Atmospheric dust accessions in south­ eastern Australia . Australian journal of soil science 9 : 1 - 6 . Walker, T . W . 1 9 65 : The significance of phosphorus in pedogenesis . In Experimental Pedology . Proceedings of the 1 1 th Easter School of Agricultural Science, University of Nott ingham: 2 95-31 6 . Walker , T . W . ; Adams , A . F . R . 1 95 8 : Studies on soil organic matter . I . Influence of phosphorus content of parent materials on accumulation of carbon, nitrogen, sulphur , and organic phosphorus in gras s land soils . Soil Science 85 : 30 7 - 3 1 8 . Wallace , R . C . ; Alloway, B . V . ; Stewart , R . ; Neall, V . E . 1 9 8 6 : The mineral chemistry as an indicator of petrogenesis at Egmont Volcano . Abstracts of the International Volcanologic Congress, 1 98 6 New Zealand : 2 3 . Wallace , R . C . ; Neall, V . E . 1 9 8 4 : The sand mineralogy of Tokomaru s ilt loam as an indicator of parent material provenance . Pp . 8 6-92 . In Bruce , J . G . ed . Soil Groups of New Zealand . Part 7 , Yellow-grey eart hs . New Zealand Society of Soil Science , Lower Hutt , New Zealand . 123 p . Wallace , R . C . ; Stewart , R . B . ; Neall, V . E . 1 9 8 5 : Volcanic glass field laboratory test and procedure to prepare thin sections of the sand f raction of soils . Massey University Department of Soil Science occasional report, number 7 . Wang, C . ; Nowlands , J . L . ; Kodama, H . 1 974 : Properties of two fragipan soils in Nova Scotia including scanning e lectron micrographs . Canadian journal of soil science 5 4 : 159-1 7 0 . 3 3 8 Ward W . T . 1 9 67 : Volcanic ash beds o f the lower Waikato Basin, North Is land New Zealand . New Zealand journal of geology and geophysics 1 0 : 110 9-1135 . Ward, W . T . 1 967 : Volcanic ash beds in the lower Waikato basin, North Is land, New Zealand . New Zealand journal of geology and geophysics 1 0 : 1 1 0 9-1 135 . Wardle , P . 1 9 63 : Evolution and distribution of the New Zealand flora as effected by Quaternary climate . New Zealand journal of botany 1 : 3-17 . Weaver , F . M . ; Wise , S . W . 1 972 : Ultramorphology of deep sea cristobalite chert . Nature, physical sciences 23 7 : 5 6-57 . Weaver, F .M . ; Wise , S . W . 1 97 4 : Opaline sedirnent s of the southeast coastal plain and horizon A: biogenic o rigin . Science 184 : 8 9 9 - 901 . Wellman H . W . 1 972 : Rate of horizontal fault displacement in New Zealand . Nature 23 7 : 2 75-2 7 7 . Wenk, H . R . ; Champnes s , P . E . ; Christie , J . M . ; Cowley, J . M . , Cowley, A . H . ; Thomas , G . ; Tighe N . J . 1 97 6 : Electron microscopy in mineralogy . New York . Springer-Verlag . Westgate , J . A . ; Fulton, R . J . 1 9 7 5 : Tephrastratigraphy of Olympia interglacial sedirnents in south-central British Columbia, Canada . Canadian journal of earth science 12 : 4 8 9-50 2 . Westgate, J . A . ; Gorton, M . P . 1 98 1 : Correlation techniques in tephra studies . In Self, S . ; Sparks , R . S . T . eds . Tephra studies as a tool in Quaternary research . Proceedings of the NATO Advanced Studies Institute, 1 98 0, Iceland. Pp 7 3-94 . Westgate, J . A . ; Smith, D . G . W . ; Tomlinson, M . 1 97 0 : Late Quaternary tephra layers in southwest Canada . Pp 13-3 4 . Proceedings of the Second Annual Paleoenvironmental Workshop. Calgary, Students Press . Whalley, W . B . 1 97 9 : SEM examination of loess - a progress report . Loess letter 2 : 16-18 . Whalley, W . B . ; Marshal!, J . R . ; Smith, B . J . 1 9 82 : Origin of .desert loess from some experimental observations . Nature 300 : 433-435 . White , A . F . ; Claasen, H . C . 1 9 8 0 : Short term dissolution of rhyolitic glass . Chemical geology 28 : 91-1 0 9 . White, D . E ; Brannock, W . W . ; Murata , K . J . 1956 : Silica in hot-spring waters . Geochimica et cosmochimica acta 1 0 : 2 7 . Wilding, L . P . ; Drees, L . R . 1 97 1 : Biogenic opal in Ohio soils . Soil Science Society of America Proceedings 35 : 1 0 0 4 - 1 0 1 0 . Wilding, L . P . ; Drees, L . R . 1 9 7 4 : Cont ribut ions of forest opal and as sociated crystalline phases to fine silt and clay fract ions of soils . Clays and clay minerals 22 : 2 95-30 6 . 3 3 9 Wilding, L . P . ; Smeck, N . E . ; Drees , L . R . 1977 : Silica in soils : quartz , cristobalite, tridymite and opal . Pp 471-552 . In Dixon, J . B . ; Weeds , S . B . eds . Minerals in Soil Environments . Madison, Soil Science Society of America . Willet R .W . 1 950 : The Pleistocene snowline , climatic conditions and suggested biological effects . New Zealand journal of science and technology 32B : 1 8-48 . Wilson, C . J . N . 1 9 8 5 : The Taupo eruption, New Zealand . I I . The Taupo ignimbrite . Philosophical transactions of the Royal Society of London A31 4 : 22 9-3 10 . Wilson, C . J . N . ; Walker , G . P . L . 1 9 8 5 : The Taupo eruption , New Zealand . I . General aspects . Philosophical Transactions of the Royal Society of London A31 4 : 1 9 9-22 8 . Wilson, M . J . ; Russell , J . D . ; Tait , J . M . 1974 : A new interpretation of the structure of disordered a lpha-cristobalite . Contributions to mineralogy and petrology 4 7 : 1- 6 . Windom, H . L . 1 9 7 5 : Eolian contributions to marine sediments . Journal of sedimentary petrology 4 5 : 520-52 9 . Wintle, A . G . 1 9 8 1 : Thermoluminescence dating of loess . Loess letter 6 : 5-9 . Wintle , A . G . 1 9 82 : Thermoluminescence properties of fine grained minerals in loess . Soil science 134 : 164-17 0 . Wise, S .W . ; Hsu, K . J . 1 97 1 : Genesis and lithification of a deep sea chalk . Eclogae Geologica Helvetica 64 : 27 3 . Wise, S . W . ; Kelts , K . M . 1 9 7 2 : Inferred diagenetic history of a weakly silicified deep sea chalk . Transactions of the Gulf Coast Geological Associations 22 : 117 . Wise, S . W . ; Weaver , F .M . 1 972 : Origin of deep sea cristobalite chert . Geological society of America abstract 4 : 1 1 6 . Worthington, T . J . 1 98 5 : Geology and petrology of the Tauhara Volcanic Complex, Taupo , New Zealand . Unpublished M . Sc . thes is , held in the Library, Victoria University . Yaalon, D . H . 1 9 62 : Mineral composition of the average shale . Clay minerals bulletin 5 : 31-36 . Yamada , I . ; Sho j i , S . 1 9 7 7 : Crystalline silica minerals in air-borne pyroclastic materials . Soil science and plant nutrition 23 : 5 41- 5 4 4 . Yoshida , S . ; Onishi , Y . ; Kitagishi , K . 1 9 5 9 : The chemical nature of silicon in rice p"lant . Soil and Plant Food 5: 23-2 7 . Yoshida , S . ; Onishi, Y . ; Kitagishi, K . 1 9 62a : Histochemistry of silicon in rice plant . II . Localisat ion of silicon within rice t issue . Soil Science and Plant Nutrition 8 (1 ) : 3 6-41 . 3 4 0 Yoshida , S . ; Onishi, Y . ; Kitagishi , K . 1 9 62b : Histochemistry of silicon in rice plant . III . The presence of cuticle-s ilica double layer in epidermal tissue . Soil Science and Plant Nutrition 8 (2) : 1-5 . Young, D . J . 1 9 6 4 : Stratigraphy and pet rology of northeast Otago loess . New Zealand journal of geology and geophysics 7 : 8 3 9-8 6 3 .