A THESIS entitled GEOCHEMICAL RECONNAISSANCE IN RELATION TO COPPER DEFICIENCY IN LIVESTOCK IN THE SOUTHERN PENNINES AND DEVON Submitted for the degree of DOCTOR OF PHILOSOPHY in the FACULTY OF SCIENCE OF THE UNIVERSITY OF LONDON by WILLIAM KENNE2H FLETCHER Royal School of Mines, Imperial College. April, 1968 ABSTRACT The results of multi-element stream sediment reconnaissance in south-west England, North Wales and the South Pennines are described and the geochemical patterns related to the incidence of trace element problems in agriculture. Particularly striking correlations are found between anomalous patterns of Mo and the incidence of copper deficiency in cattle in the South Pennines, and between low Co levels and cobalt pine in sheep on Dartmoor. Detailed studies in the South Pennines have shown that the extensive Mo anomalies delineated by the stream sediment survey correspond to areas in which Mo-rich lower Namurian and Visean shales give rise to molybdeniferous soils. Elsewhere, where the shales are concealed beneath barren drift and on other parent materials, the Mo content of both soils and sediments is normal The distribution of trace elements in soil profiles developed on the anomalous soils is described. The Mo content of pasture herbage is significantly higher on the anomalous soils than on the control plots, though the contrast between herbage samples is considerably less than between the corresponding topsoils. The relatively low uptake of Mo from the molybdeniferous soils is attributed to its retention by the weathered residues of the parent material and to its fixation, after mobilization, by secondary ferric oxides. The Mo-Cu-SO status of herbage growing on the Mo-rich soils 4" is within the range associated with molybdenum-induced hypocuprosis in cattle. Complementary studies by I. Thornton and J.S. Webb have shown that 77 per cent of the cattle (excluding those receiving mineral supplements) within the molybdenum stream sediment anomaly are affected by copper deficiency, compared to 37 per cent outside the anomaly,. Furthermore, copper therapy results in a marked improvement in live weight gain by affected animals. These results confirm that the agricultural problem area is considerably more extensive than was suspected prior to the stream sediment reconnaissance. Similar relationships between the Mo content of rock, soils, sediments and herbage are described in Mo-anomalous catchments detected during stream sediment reconnaissance on the Culm Measures west of Dartmoor, Devon. The results of the research clearly demonstrate the applicability of sediment surveys to detecting and delineating areas wherein abnormal trace element levels in rocks and soils may give rise to both clinical and sub-clinical problems in agriculture. ii CONTENTS VOLUME I page .. .. ABSTRACT 00 .9 PO 00 .. O . .. .. •• i LIST OF TABLITS oil tor se oe to to Ape oke se viii LI6T OF FIGURES .. .. .. • • • • • • • • O• xiii CHAPTER 1 INTRODUCTION .. .. .. .. • 09 • 0 1 (i) REGIONAL GEOCHEMISTRY .. .. .. .. .. 2 (ii) ECOLOGICAL APPLICATIONS OF REGIONAL GEOCHEMISTRY 4 (iii) PRESENTATION OF THESIS .. .. .. .. .. 10 (iv) ACKNOWLEDGEMENTS .. .. .. .. .. • • 11 PART A CHAPTER 2 SAMPLING) ANALYTICAL TECHNIQUES AND DATA HANDLING 13 (i) SEDIMENT SAMPLING AND SAMPLE PREPARATION .. .. 15 (ii) ANALYTICAL TECHNIQUES .. .. .. .. .. 16 (a)Spectrographic method .. W. .. .. 17 (b)Colorimetric methods .. .. .. .. •• 22 A rsenic 00 .. .. .. .. O. .. 22 Zinc .. 00 60 so 0.. 06 0.1. es 23 (iii) DATA HANDLING 00 0 • .. .. 06 .. 23 CHAPTER REGIONAL GEOCHEMICAL RECONNAISSANCE DEVON AREA 25 (i) DESCRIPTION OF THE AREA .. • .. .. .. 25 A. LOCATION .. .. .. .. • • • • • • 25 B. GEOLOGY AND MINERALISATION .. .. .. 25 C. TOPOGRAPHY AND DRAINAGE .. .. .. 28 D. CLIMATE 40 .. .. Of .. .. .. 30 E. SOILS .. .. .. .. .. .. .. 30 F. AGRICULTURE .. .. .. .. • • 31 ..- (ii) THE REGIONAL GEOCHEMICAL PATTERNS .. .. • • 31 A. PATTERNS RELATED TO THE GRANITE AND THE ASSOCIATED MINERALISATION .. .. .. .. 32 B. PATTERNS RELATED TO BEDROCK GEOLOGY .. .. 35 C. PATTERNS RELATED TO SECONDARY ENVIRONMENT 38 (iii) CORRELATIONS BETWEEN THE GEOCHEMICAL PATTERNS AND THE INCIDENCE OF AGRICULTURAL DISORDERS .. .. 39 A. COBALT .. .. .. • • • • • • • • • • 39 B. MANGANESE .. .. .. .. .. .. .. 40 C. COPPER AND MOLYBDENUM .. .. .. O. .. 40 D. ARSENIC AND LEAD .. .. .. .0 .. 41 iii page CHAPTER 4 REGIONAL GEOCHEMICAL RECONNAISSANCE NORTH WALES 42 (i) DESCRIPTION OF THE AREA .. • • • • • • 42 A. LOCATION .. .. .. .. .. .. • • 42 B. GEOLOGY AND MINERALISATION .. .. .. 42 C. TOPOGRAPHY AND DRAINAGE .. .. .. .. 46 D. CLIMATE 00 60 40 66 Oa 0. 40 47 E. SOILS .. .. .. .. 00 ao 04 00 47 F. AGRICUL=RE 00 .. .. O. .. .. 49 (ii) THE REGIONAL GEOCHEMICAL PATTERNS .. .. .. 50 A. GEOCHEMICAL PATTERNS RELATED TO BEDROCK GEOLOGY AND GLACIAL DEPOSITS .. .. .. 50 B. PATTERNS RELATED TO THE SECONDARY ENVIRONMENT 53 C. GEOCHEMICAL PATTERNS RELATED TO MINERALISATION 56 (a)Cu, Pb and Zn anomalies near Llanwrst 56 (b)Cu-Pb and Pb-Zn anomalies on the Silurian 57 (c)Cu, Pb and Zn anomalies related to mineralisation in the Halkyn-Minera district 58 (iii) CORRELATIONS BETWEEN THE GEOCHEMICAL PATTERNS AND THE INCIDENCE OF AGRICULTURAL DISORDERS 59 A. COBALT.. .. SO .. .. .. O. .. 59 B. MANGANESE .. 00 60 00 .0 .0 66 60 C. COPPER AND MOLYBDENUM .. .. .. 06 60 C. OTHER METALS.. .. 06 O. CHAPTER 5 REGIONAL GEOCHEMICAL RECONNAISSANCE DERBYSHIRE AREA AREA 62 (i) DESCRIPTION OF THE AREA .. • • • • • • .. 62 A. LOCATION 6. .. 66 .. se 00 so 62 B. GEOLOGY 4* *8 .4 .. .. .. .. 62 C. TOPOGRAPHY AND DRAINAGE .. .. .. .. 65 D. CLIMATE .. • • .. .. .. .. .. 66 E. SOILS .. , • • • • . • • • • .. 68 F. AGRICULTURE .. •• of .. .. .. 68 (ii) THE REGIONAL GEOCHEMICAL PATTERNS .. .. .. 69 A. GEOCHEMICAL PATTERNS RELATED TO BEDROCK GEOLOGY AND GLACIAL DEPOSITS .. .. .. 69 B. GEOCHEMICAL PATTERNS RELATED TO MINERALISATION 72 (iii) CORRELATIONS BETWEEN THE GEOCHEMICAL PATTERNS AND THE INCIDENCE OF AGRICULTURAL DISORDERS .. • • 74 A. COBALT.. .. .. .. 04 *6 .. .. 74 B. MANGANESE .. .. .. .. .. 00 .. 74 C. COPPER AND MOLYBDENUM .. .. .. .. 75 D. OTHER METALS .. .. .. .. .. .0 76 CHAPTER 6 CONCLUSIONS.. .. 00 60 SO OS 77 iv page PART B CHAPTER 7 SAMPLING AND ANALYTICAL TECHNIQUES 81 (i) SAMPLING .. •• •• •• •• f• •• •• 81 •• •• •• •• •• 82 (a) Rocks .. • • • (b) Soils .. •• •• •• •• •• •• •• 82 (c) Herbage •• •• •• •• •• 83 (ii) SAMPLE PREPARATION •• •• •• •• •• •• 83 (a)Rocks .. •• •• •• •• •• •• •• 83 (b)Soils .. •• •• •• •• •• •• •• 83 (c)Herbage •• •• •• .• •• •• • • 84 (iii) ANALYSIS .. •• •• •• •• • • •• 85 (a) Molybdenum .. .• .0 •• •• 85 colorimetric determination of molybdenum 85 Ammonium acetate extractable molybdenum in soils .. •• •• •• •• •• •• 86 (b) Copper O. .0 •0 •• •• •• 88 Copper in herbage •• •• •• •• 88 EDTA-extractable copper in soils •• •• 89 (c) Sulphate •• •• •• •• 90 Soil sulphate .• •• •• •• •• •• 90 Inorganic herbage sulphate •• •• •• 90 (d) Organic carbon •• •• •• •• 90 (e) PH •• •6 00 0. •• •• •• 90 (f) Mechanical analysis of soils .• •• •• 91 Rapid estimation of size analysis using the Bouyoucos hydrometer .. •• 93 Separation of size fractions for trace element analysis .. .. • • •• 94 CHAPTER 8 DRSCRIPTION OF THE DETAILED STUDY AREA 95 (i) LOCATION .. Ow • .0 00 •• 95 (ii) GEOLOGY .. .. • .. •• •• 95 (a)Pre-Quaternary geology 40 4. •• •• 95 (b)Quaternary geology of 40 04 •• •• 100 (iii) TOPOGRAPHY e6 •• •• 101 (iv) CLIMATE .. 00 .. es Os 06 •• •• 102 (v) SOILS Se 00 •• •• 102 (a) Dominantly residual soils •• •• •• •• 103 (b) Non-residual soils •• •• •• •• 105 Soils derived from drift •• •• •• •• 105 Soils derived from loess •• •• •• •• 105 Alluvial soils • • •• •• •• •• 106 AGRICULTURE .. 04 O. •• •• •• •• 106 page CHAPTER 9 TRACE ELEMENT CONTENT OF THE BEDROCK (i) TRACE ELEMENT CONTENT OF THE MAJOR ROCK UNITS AND LITHOLOGIES .. 00 06 00 40 De 108 (a)Argillaceous rocks .. 00 00 .. .. 110 (b)Arenaceous rocks O. 00 00 .. .. 114 (c)Limestones .. .0 .. em 00 • • • • 114 (ii) DISTRIBUTION OF TRACE ELEMENTS IN THE LOWER NAMURIAN AND VISEAN SHALES es 00 00 0. 114 (a)Lateral and vertical distribution of trace elements in the lower Namurian and Visean shales 00 .. .. 00 0. O. .. 115 M olybdenum .. 00 .. .. •• •• •• 115 Other trace elements .. .. .. .. 120 (b)Trace element content of the lower Namurian shale facies .. • • • .. .. •• 122 (iii) DISCUSSION • • 129 CHAPTER 10 REGIONAL DISTRIBUTION OF METAL IN THE OVERBURDEN AND THE RELATIONSHIP BETWEEN THE METAL CONTENT OF THE BEDROCK, STREAM SEDIMENTS AND OVERBURDEN 135 (i) MOLYBDENUM .. .. 00 .. 00 .. .. .. 135 (a)Residual soils .. .. • • .. 00 .. 135 (b) Transported soils .. We 00 00 0. 138 Loess .. .. .. .. .. .. .. .. 138 Older Drift .. .. .. 00 .. .. 139 Newer Drift .. .. .. .. .. .. 140 (c)Relationship between the distribution of Mo in the bedrock, stream sediments and overburden 140 (ii) OTHER ELEMENTS .. 00 w0 00 .. 00 00 143 (a)Geochemical patterns in the overburden related to primary syn3enetic dispersion .. .. 144 (b)Geochemical patterns in the overburden related to mineralisation ea 00 00 .. .. 145 Mineralisation in the lower Namurian shales and Visean shales with limestones .. .. 145 Mineralisation on the margins of the limestone massif .. .. .. .. .. O. .. • • 148 Pb and Zn anomalies on the Bunter Sandstones 148 (c)Relationship between the distribution of trace elements (other than molybdenum) in the bed- rock, stream sediments and overburden .4 148 CHAPTER 11 METAL DISTRIBUTION IN THE OVERBURDEN 153 (i) METAL DISTRIBUTION IN SOIL PROFILES .. .. 153 vi page