Geochemistry and Mineralogy of the Bembridge and Hamstead Beds (Oligocene), Isle of Wight
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GEOCHEMISTRY AND MINERALOGY OF THE BEMBRIDGE AND HAMSTEAD BEDS (OLIGOCENE), ISLE OF WIGHT i IAN FREDERICK HOLMES A thesis submitted in partial fulfillment of the degree Ph. of D. in the Dept. of Geology, University of Sheffield. February, 1980 GEOCHEMISTRY AND MINERALOGY OF THE BEMBRIDGE AND HAMSTEAD BEDS (OLIGOCENE), ISLE OF WIGHT I. F. HOLHES SUMMARY Samples were collected from exposures of the Bembridge and Hamstead Beds in Whitecliff Bay, Hamstead Cliff and Bouldnor Cliff. Samples representative of various depositional environments were analysed for twenty-six major and trace elements. Mineralogical investigation by X-ray diffraction included quantification of the clay minerals, calcite and quartz. Attempts to utilise geochemical indicators of palaeosalinity proved fruitless. Pyrite occurs in association with the two marine transgressions, suggesting that the source of sulphur was from solution. Alteration of pyrite to goethite and gypsum occured during Pleistocene weathering of the Corbula Beds and the movement of ions in solution associated with this affected the original exchangeable cation contents. An increase in zirconium content was found in samples deposited in high energy environments, although exceptions to this occur. The Oligocene sediments are enriched in lead, compared to average shales, due to lead fixation in clay minerals formed from the Cornubian granites. Aragonite occurs only in samples from the Bembridge Oyster Bed, in other samples only low-magnesium calcite was identified. The calcite in the Oligocene samples is poor in substituent trace elements. The clay mineralogy is an illite/smectite/kaolinite assemblage, with traces of chlorite. The clay minerals are of a dominantly detrital origin, from Mesozoic and Tertiary sediments which lay to the north-west. The Lower Bembridge Beds in Whitecliff Bay show evidence for derivation from a kaolinite-poor, north-easterly source. There is evidence that transformation of smectite into illite and illite-smectite occurred, possibly following periods of more intense weathering in the hinterland. Two samples show evidence for the neoformation of smectite. One contains nontronite formed in a palaeosol, the other contains a smectite which is thought to have been formed from volcanic material. No variation in clay mineralogy was observed between marine and non-marine samples. I ACKNOWLEDGEMENTS , The work embodied in this thesis was made possible by financial support frcf the Natural Environment Research Council. As well as acknaaledging my indebtedness to that organisation, I should like to express rmy appreciation to the folla ling : - Dr. D. A. Spears was ny supervisor at Sheffield University and the many discussions with him helped to produce this thesis; 'Dr. R. K. Sotirioü helped with all of the X-ray techniques; Mr. V. A. Sc ogyi and Mrs. S. M. Rhodes helped with the wet chemical procedures; Mr... H. Brockley prepared the electron micrographs; Prof. D. Murchison and the staff at the organic Geochemistry Unit, Newcastle-upon-Tyne assisted with the organic geochemistry techniques; Prof. R. E. Ferrell Jr. spared time for many helpful discussions while he was in Sheffield; Miss S. K. Holmes, my sister, for her invaluable assistance in the production of this thesis. I 2 LIST OF CONTENTS Page no. SUMMARY 1 ACKNOWLEDGEMENTS 2 LIST OF CONTENTS 3 LIST OF FIGURES 6 LIST OF TABLES 8 LIST OF PLATES 10 I INTRODUCTION 11 1(A) Aims of the Thesis 11 1(A)(i) Area of study 11 1(A)(ii) The relationship of depositional environment and 11 geochemistry 1(A)(iii) The relationship of depositional environment and 13 mineralogy 1 (A) (iv) Statement of the aims of the thesis 14 2 PREVIOUS WORK 16 2(A) General Geology 16 2(A)(i) Geological setting 16 2(A)(ii) Location of the exposures 16 2(B) Palaeontology and Sedimentology 17 2(B)(i) Age of the deposits 17 2(B)(ii) Depositional environments 18 2(C) Mineralogy and Geochemistry 20 2(C)(i) Mineralogy 20 - 2(C)(ii) Geochemistry 21 3 FIELD WORK 22 3(A) Sample Collection 22 3(A)(i) Sampling aims 22 3(A)(ii) Sampling technique 22 3(A)(iii) Location and description of the outcrops 22 3(B) Features Associated with Slumping 24 3(B)(i) Large scale slumping 24 3(B)(ii) Incompetence of the Corbula Beds 25 4 GEOCHEMISTRY 26 4(A) Major Element Analyses 26 4(A)(i) Sample preparation 26 4(A)(ii) X-ray fluorescence 26 4(A)(iii) Wet chemistry 27 4(A)(iv) Duplicate precision 28 4(B) Trace Element Analyses 29 4(B)(i) Preparation and analysis 29 3 Page no. L(B)(ii) The use of acid pretreatment in determining the 30 locations of the trace elements 4(B)(ii) a) Method and results 30 4(B)(ii) b) Interpretation 30 4(C) Organic Geochemistry 32 4(C)(i) Organic contents 32 4(C)(ii) Reflectivity measurements 33 4(D) Exchangeable Cations 34 4(D)(i) Relationship with palaeosalinity 34 4(D)(ii) Statement of the problem 34. 4(D)(iii) Development of the method 34 4(D)(iv) Results obtained 39 5 MINERALOGY 41 5(A) Determination of Non-clay Minerals by X-ray Diffraction 41 5(A)(i) Sample preparation and analysis 41 5(A)(ii) Mineral identification 41 5(A)(iii) Quantification 42 5(A)(iii) a) General considerations 42 5(A)(iii) b) Calcite contents 44 5(A)(iii) c) Quartz contents 46 5(A)(iii) d) Other minerals 48 5(B) Determination of Clay Minerals by X-ray Diffraction 49 5(B)(i) Sample preparation and analysis 49 5(B)(i) a) Size fraction used 49 5(B)(i) b) Sample preparation 50 5(B)(1) c) Method of analysis 51 5(B)(ii) Mineral identification 51 5(B)(ii) a) Methods of sample pretreatment 51 5(B)(ii) b) Diagnostic properties of the clay minerals 52 5(B)(iii) Quantification 54 5(B)(iii) a) Measurements of crystallinity 54 5(B)(iii) b) Mineral content. 56 5(B)(iii) c) Conclusions 59 5(C) Clay Mineral Examination by Electron Microscopy 59 5(D) Mineralogical Quantification by Geochemical 60 Recalculation 5(D)(i) Introduction 60 5(D)(ii) The calculation of non-clay minerals 60 5(D)(iii) The calculation of clay minerals 63 5(D)(iv) Comparison of the methods of quantifying clay 65 mineralogy 4 Page no. 6 STATISTICAL ANALYSIS 67 6(A) Introduction 67 6(B) Cluster Analysis 67 6(B)(i) Introduction 67 6(B)(ii) Major elements 68 6(B)(iii) Trace elements 68 6(C) Discriminant Analysis 70 6(c)(i) Introduction 70 6(c)(ii) Results obtained 71 6(D) Correlation Analysis 72 6(D)(i) Introduction 72 6(D)(ii) Results obtained 73 7 GEOLOGICAL INTERPRETATION 76 7(A) Geochemical Interpretation 76 7(A)(i) Conclusions on the locations of the trace elements 76 7(A)(ii) Comparison of the mean element contents with the 81 results of other workers 7(A)(iii) Use of geochemistry as an indicator of 84 palaeoenvironment 7(B) Mineralogical Interpretation 89 7(B)(i) Non-clay mineralogy 89 7(B)(ii) Clay mineralogy 92 7(C) Conclusions 97 REFERENCES 100 5 LIST OF FIGURES Following page no. 1 Generalised stratigraphy of the Tertiary deposits in the 16 Hampshire Basin 2 Location map showing generalised geological structure 16 3 The effect of acid pretreatment on the trace element 30 contents of sample 31 4 The effect of acid pretreatment on the trace element 30 contents of sample 74 5 Graphs of exchangeable Ca against Mg for calcite-spiked 38 aliquots of sample 74 6 X-ray diffractogram of sample 36 41 7 Graph % MgCO d (1104. ) for 44 of mole 3 against spacing calcite (from GOLDSMITH et al, 1961) 8 Graph of calcite % against calcite (110W peak area 46 9 Diffractogram of sample 45 showing overlap of non-basal 48 clay mineral reflections and (1100) quartz peak 10 Effect of various pretreatments on the (001) clay 53 mineral peaks in sample 47 11 Recalculation of (001) glycol-smectite peak from sample 55 95 to a flat background 12 Recalculation of untreated (001) smectite and illite 55 peaks for sample 112 13 (001) illite peaks produced by the recalculation procedure 55 for samples 2 and 37 14 Method of determining smectite crystallinity (from 56 BISCAYE, 1965) 15 Method of determining % expandable layers in smectite ( 56 from WEIR et al, 1975) 16 Dendrogram obtained by cluster analysis of major element 68 contents 17 Dendrogram obtained by cluster analysis of a restricted 68 number of major elements 18 Dendrogram obtained by cluster analysis of trace element 68 contents 19 Example of the output of the correlation analysis 72 program of TILL (1969) 20 Distribution of certain elements above and below a 77 carbonaceous bed in the Hamstead Beds 21 Distribution of clay minerals in the Hamstead and Bouldnor 95 cliff sections 6 Following page no. 95 22 Distribution of the clay minerals in the Whitecliff Bay section 7 LIST OF TABLES Following or on page no. I Stratigraphic succession of the Bembridge and Hamstead 23 Beds in Hamstead and Bouldnor cliffs, showing sampled beds 2 Stratigraphic succession of the Bembridge Beds in 24 Whitecliff Bay, showing sampled beds 3 X. R. F. major element analyses 26 4 Precision of the X. R. F. determinations 26 5 Accuracy. of the X. R. F. determinations 27 6 H20+ and H2O contents 28 7 duplicate determinations 28 . Standard deviations of the 8 Trace element analyses 29 30 9 The effect of acid pretreatment on trace element concentrations 10 Extractable organic contents 33 11 Mean and standard deviation for the exchangeable 35 cations and C. E. C. in sample 74 12 Exchangeable cations determined for spiked aliquots 36 of sample 74 13 C.