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And Mineralization in the United Kingdom Faculty Of A THESIS entitled THE INTERPRETATION OF LEAD Ate ZINC STREAM SEDIMENT ANOMALIES RELATED TO CONTAMINATION AND MINERALIZATION IN THE UNITED KINGDOM Submitted for the degree of DOCTOR OF PHILOSOPHY in the FACULTY OF SCIENCE OF THE UNIVERSITY OF LONDON by DENNIS TAYLOR Royal School of Mires Imperial College. May 1968 ABSTRACT Using the results of a multi-element stream sediment survey previously carried out over the environs of the Halkyn-Minera and Derbyshire Pb-Zn orefields as a base, a study was made of the relationship of anomalous metal contents to both natural and contaminated sources. Pb, Pb-Zn, and. Zn anomalies were found to be associated with contamination from mining and smelting and to various natural sources, with Mo, Ba, Cu and Ag as the principal associated elements. Smelting methods have changed with time and these variations are reflected in the metal associations found in the contaminated sediments, Pb or Pb-Ba anomalies with little or no Zn characterize smelters of early date and increasing amounts of Zn are found in more modern smelters, while very high Zn levels characterize anomalies derived from later metallurgical sites such as brass or galvanized iron industrial sites. The Pb:Zn ratio varies widely in natural anomalies, being influenced by the metal content of the primary mineralization, the history of leaching and erosion of the deposit and the mode of derivation of the stream sediment anomaly. The chemical form of the Pb and Zn in stream sediment anomalies differs systematically in a manner rslated to the nature of the source and the method of derivation of the anomaly. Different forms of the metal were found to be variously extracted by weak nitric acid attack. This allows anomalies to be classified by the extrac- tabilities of their Pb and/or Zn content. By combining this information with the Pb:Zn ratio and considering also the other associated elements, anomalies can be classified into groups, and most of the anomalies due to contamination distinguished from natural anomalies. The use of these diagnostic criteria greatly facilitates the interpretation of the Pb-Zn anomalies found during regional geo- chemical surveys in the test areas and carefUlly used, should be applicable to other areas in Britain where similar geology and secondary environment prevail. Most natural anomalies related either to mineralization or to other bedrock concentrations of Pb or Zn can be identified and exploration directed to the correct targets with minimal interference from spurious metal concentrations. 1.1 ACKNOWLEDGEMENTS This work forms part of a programme of research in applied geochemistry being carried out by the Applied Geochemistry Research Group of Imperial College under the direction of Professor J.S. Webb, and is supported by a N E R C Research Contract awarded through the Institute of Geological Sciences. The writer has been supported during the execution of this work by a NERC studentship and an RTZ Educational Trust Research Bursary and wishes to express his thanks to both organisations for their assistance. The writer wishes to acknowledge the assistance of all members of the A.G.R.C. and in particular to thank Dr. I. Nichol for his friendly help and encouragement at all stages of the work. Professor J.S. Webb, Mr. R.E. Stanton and Dr. E. Newman are also thanked for many stimulating discussions and opportune suggestions which have greatly assisted with the execution of this research. Thanks are also due to the analytical staff of the department who undertook much of the routine analysis and whose assistance greatly expedited the research. Dr. H.E. Hawkes is thanked for visiting the field area and for stimulating discussion of the problems involved. Thanks are also due to the County Libraries of Flintshire, Denbighshire and Derbyshire and to the County Archivist of Flintshire for their assistance in the literary part of the research and to the Cominco and Rio Tinto-Zinc companies for the provision of useftl sample material. iii The Institute of Geological Sciences and Glebe Mines Ltd, are thanked for allowing the writer to sample borehole cores of Namurian rocks in Derbyshire. Dr. Frost of the I.G.S. Leeds office is thanked for his assistance in the field in the Hulland Triassic area, for stimulating discussion of the origin of the base metal dispersions in these rocks and for the supply of samples of typical Coal Measure ironstones for analysis. iv CONTENTS Volume One Page Abstract Acknowledgements ii List of tables List of figures xiii Chapter 1. INTRODUCTION 1 A. The underlying concepts of the regional geochemical approach to prospecting. 1 B. The development of geochemical prospecting techniques - A historical review. 2 C. Lead and zinc in soils and stream sediments in the British Isles. 4 D. Difficulties encountered in applying regional geochemical methods in the British mining areas. 5 E. Scope of the present research. 6 F. Choice and location of field study areas 7 G. Layout of thesis 9 Chapter 2. GENERAL HISTORY OF LEAD-ZINC MINING AND SMELTING IN BRITAIN 10 A. Early development by the Romans. 10 B. The pre-industrial era 1000-1550 A.D. 10 (1) Mining Methods 10 (2) Smelting Methods 12 C. The early industrial era 1550-1700 A.D. 14_ (1) Improved mining techniques 1I. (2)Developments in smelting 15 D. The industrial revolution in mining 1700-1870. 16 (1) Steam pumps, winding engines and deep levels 16 (2) The cupola furnace 17 (3)The rise in the importance of zinc 19 (4)Decline of the British industry 20 E. Summary of significant features. 20 Chapter 3. DESCRIPTION OF THE =ID AREAS 22 A. Derbyshire. 22 (1) Location and size 22 (2) Topography, drainage and climate 22 (3) General geology 23 (a) Principal rock types and basic stratigraphy 23 CO Structural geology 27 v. Page (4.) Mineralization. 29 (a)Distribution of ore producing districts 29 (b) Geological controls of ore distribution 30 (5) Local mining and smelting history 34- (a) Roman mining 34. (b) The pre-industrial era 34 (c) The industrial era 37 (d) Copper mining and smelting 41 (e) Modern times 41 (6) Speculative possibilities of new ore 42 (7) Glacial history 43 (8) Soils 45 B. Flint-Denbigh. 49 Location and size 49 2) Topography, drainage and climate 49 (3) General geology 50 (a)Principal rock types and basic stratigraphy 50 (b) Structural geology 55 (4) Mineralization 58 (a)Location of principal metal producing areas 58 (b) Geological controls of ore deposition 59 (5) Local mining and smelting history 64 (a) Evidence of Roman mining activity 64. (b) Mining before 1600 64 (c) The beginnings of development 1600-1700 65 ((a) The main period of exploitation 1700-1900 66 (e) The modern era 70 (6) Speculative possibilities of new ore 71 (7) Glacial history 72 (8) Soils 74. Chapter 4. THE RESULTS OF THE REGIONAL STREAM SEDIMENT RECONNAISSANCE SURVEY 77 A. DERBYSHIRE. 78 (1) Distribution of the elements 78 (a)Lead 78 (b) Zinc 80 (c) Associated elements 82 (d)Lead:Zinc ratio 84. (2) Correlation of minor element associations with bedrock geology 85 (3) Correlation of mining and smelting activities with metal distribution 89 vi Page B. FLINT DENBIGH. 92 (1) Distribution of the elements related to mineralization 94 (a) Lead 94 -1:)) Zinc 95 (c) Associated Elements 97 (d)Lead:Zinc Ratio 98 (2) Correlation of bedrock geology with metal distribution 99 (3) Correlation of mining and smelting sites with metal distribution 100 C. GENERAL FEATURES OF THE METAL PATTERNS. 101 Chapter 5. SECONDARY DISPERSION PATTERNS ASSOCIA1ED WITH VARIOUS METAL SOURCES 103 1. Introduction 103 2. Descriptions of the dispersion patterns studied in detail 104 Subsection A. Natural sources 107 (1) Anomalies derived from mineralization at shallow depth 107 (a) In Lower Palaeozoic country rock Llantysilio Mountain, Denbighshire 107 (b) In Carboniferous Limestone or chert 112 1. Holywell, Flint shire 112 2. Pentre Halkyn, Flintshire 125 (c) In Carboniferous sandstone or grit 134 1. Bwlchgwyn, Denbighshire 134 (2) Anomalies derived from leakage dispersions 140 (a)Leakage dispersion in barren caprock 140 1. Gregory Vein, Derbyshire 140 (b)Leakage dispersion along faults 145 1. Westminster-Belgrave area, Denbighshire 145 (3) Anomalies derived from natural base metal concentrations in sedimentary rocks not directly related to mineralization 150 (a) High background source rock, zinc definitely syngenetic 150 1. Eriale Shales, North Staffs/ Derbyshire 150 (b) High lead or zinc in the New Red Sandstone, source of metals unknown 152 1. Bunter Pebble Beds, Hulland Ward area 152 vii. Page Subsection B. Contamination Anomalies. 168 (1) Early wind—blown lead smelters 168 1. Ramsley Moor Bole, Derbyshire 168 2. Ashover Bole, Derbyshire 173 3. Butterley and Coldharbour Bolehills, Derbyshire 176 (2) Ore—hearth lead smelters 178 1. Mansellpark, Hulland, Derbyshire 178 2. Bodfari, Flintshire 181 (3) Reverberatory or cupola furnace lead works. 183 1. Baslow cupola works, Derbyshire 183 2. Stone Fiage cupola works, Derbyshire 187 3. Gadlys smelting works, Bagillt, Flintshire 191 4. Tinkers Dale smelting works, Hawaraen, Flintshire 196 (4) Zinc Works 201 1. Wynne Hall Spelter Works, Denbighshire 201 2. Pant furnace Rho sllanerchrugog, Denbighshire 203 3. Summary of results and selection of representative examples of geochemical dispersions from different metal sources. 205 A. Natural anomalies 205 B. Contamination anomalies 207 Chapter 6. INVESTIGATION OF THE FORM OF THE LEAD AND ZINC IN SF'TiRCTED SAMPLES FROM THE TYPE AREAS 210 General 210 A. The selective extraction of lead 212 (1) Analytical technique 212 (2) Location of type samples 213 (3) Extractability from different types of sample with varying strength of sample attack 217 (4) Relationship of extractability to reaction time 223 (5) Selection of optimum conditions for maximum discrimination 224 (6) Extractability of Pb from common mineral forms 224 (a)Preparation of samples 225 (b) Observed variations of extractability 226 (7) Comparison of stream sediment and mineral form extractabilities.
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