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Regional geochemical reconnaissance and compositional variations in grain and forage crops on the Southern.. Doyle, Patrick J. 1977-02-19

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REGIONAL GEOCHEMICAL RECONNAISSANCE AND COMPOSITIONAL VARIATIONS IN • GRAIN AND FORAGE CROPS ON THE SOUTHERN CANADIAN INTERIOR PLAIN by PATRICK J. DOYLE B.Sc, University of Ottawa, 1969 M.Sc, University of Brithish Columbia, 1972 A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in THE FACULTY OF GRADUATE STUDIES (Department of Geological Sciences) We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA September,. 1977 © Patrick J. Doyle, 1977 In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the Head of my Department or by his representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Depa rtment The University of British Columbia 2075 Wesbrook Place Vancouver, Canada V6T 1W5 ABSTRACT The distribution of Cu, Fe, Mn, Zn, Mo and Se in earth surface materials on the Southern Canadian Interior Plain was examined with the aim of recommending appropriate methods of producing regional geochemical maps. Investigations were undertaken in three separate areas, one in each of the prairie provinces, selected to represent a range of environmental con ditions. In the Swan River - Dauphin area emphasis was placed on investigating the regional distribution of Mo in both soil and stream sediment. These patterns were related to data on the Mo status of plants and to information on Mo-induced Cu deficiency in cattle. In the Rosetown area of Saskatchewan, and the Red Deer area of Alberta, attention v/as focussed on examining variations in the Cu, Fe, Mn, Zn and Se content of soils; in the Rosetown area concentrations of these elements in whole wheat plants were also determined. Procedures for regional geochemical mapping using stream sediment are well established. On the Southern Canadian Interior Plain, however, stream density is generally inadequate for routine application of these techniques. Although tributary drainages are relatively common in parts of southern Manitoba, results of investigations in the Swan River - Dauphin area in dicate that Mo concentrations in stream sediment typically reflect Mo levels in upstream soil, but not those of associated plants. In contrast to findings reported by V7ebb and his assoc iates in the United Kingdom, Manitoba stream sediment data are of little value in identifying areas where potentially toxic Mo concentrations are likely to occur in forage. Reconnaissance surveys based on soil sampling, on the other hand, can be applied throughout the Canadian prairies. Results of studies around Rosetown and Red Deer indicate that regional compositional trends for soil may be efficiently des cribed in terms of variations among means estimated for indiv idual soil parent materials. In the Rosetown area, for example, over 70% of the total variance for Cu, Fe, Mn and Zn in A hor izons is attributable to differences among parent material means. This parent material effect appears, in turn, to be mainly a function of textural variations, with lowest concent rations associated with sand-rich and highest with clay-rich deposits. The importance of differences among means for soil associat ed with individual surficial deposits is also emphasized, in the Rosetown area, by relatively strong positive relationships (r>0.73) between parent material based Mn, Fe and Cu means for wheat and soil. When data are considered on an individual sample basis relationships between plant and soil concentrations are generally much weaker (r< 0.40). It is suggested, therefore, that on the Southern Canadian Interior Plain, regional geochemical maps can be efficiently produced using parent material based soil compositional data. The procedure recommended involves collection of A horizon samples at randomly chosen sites over each of the major parent i materials recognized, and estimation of geometric mean and deviation values for each deposit. Duncan's New Multiple Range test is used to identify significant differences among means, iv and results are summarized in map form, showing only composition-ally distinctive parent materials or parent material groups. In view of close relationships noted between parent material based means for soils and plants, maps produced in this fashion should be useful in identifying areas where trace element excesses or deficiencies are limiting crop or livestock productivity. V TABLE OF CONTENTS CHAPTER PAGE I INTRODUCTION A. ENVIRONMENTAL GEOCHEMISTRY AND HEALTH 1 1. TRACE ELEMENTS IN PLANT AND ANIMALHEALTH 2. TRACE ELEMENT STATUS OF PLANTS AND 2 ANIMALS 3. REGIONAL GEOCHEMICAL RECONNAISSANCE 7 TECHNIQUES a. Stream Sediment Sampling 8 b. Soil, Plant, Rock and Water Sampling 10 B. SOUTHERN CANADIAN INTERIOR PLAIN 14 1. REGIONAL DESCRIPTION 1a. Physical Settingb. Agricultural Trace Element Disorders 19 2. STUDY OBJECTIVES 21 3. OUTLINE OF APPROACH 2 II SAMPLE COLLECTION, PREPARATION AND ANALYSIS, AND DATA HANDLING PROCEDURES A. SAMPLE COLLECTION AND PREPARATION 26 1. COLLECTION 22. PREPARATIONB. SAMPLE ANALYSIS 6 1. COPPER, IRON, MANGANESE AND ZINC 2 8 a. Digestion of Plants 28 b. Digestion of Soilsc. Analysis 29 2. MOLYBDENUM 31 a. Digestion of Plants 3b. Digestion of Geological Materials 34 c. Analysis 5 3. SELENIUM 37 4. SOIL REACTION 40 C. STATISTICAL METHODS1. DATA TRANSFORMATION 42 2. ESTIMATION OF POPULATION PARAMETERS 44 3. IDENTIFICATION OF OUTLIERS 4 5 4. TESTS OF SIGNIFICANCE 46 a. Correlation 4b. Analysis of Variance 46 c. Duncan's New Multiple Range Test 46 d. Median Test 47 vi CHAPTER III ROSETOWN AREA PAGE A. DESCRIPTION OF STUDY AREA 48 1. GENERAL 42. BEDROCK 50 3. SOIL PARENT MATERIAL 52 4. SOIL 6 5. AGRICULTURAL LAND USE AND TRACE 57 ELEMENT IMBALANCES B. SAMPLE COLLECTION AND ANALYSIS 59 1. COLLECTION 5a. Soilb. Plant-Soil 60 c. Bedrock 1 2. ANALYSIS 63 C. RESULTS - COPPER, IRON, MANGANESE AND ZINC 63 1. AMONG PARENT MATERIAL SOIL COMPOSITIONAL 6 5 VARIATIONS 2. WITHIN PARENT MATERIAL SOIL COMPOSITION- 72 AL VARIATIONS a. Vertical 7b. Geographic 8 2 3. RELATIONSHIPS BETWEEN SOIL AND PLANT 86 COMPOSITIONAL DATA D. DISCUSSION - COPPER, IRON, MANGANESE AND ZINC 89 1. C HORIZON SOIL 82. A HORIZON AND 30-46 CM DEPTH SOIL 96 3. RELATIONSHIP BETWEEN PLANT AND SOIL 99 CONENTRATIONS 4. GEOCHEMICAL MAPS 101 a. Method of Presentation 10b. Patterns and Their Significance 104 E. RESULTS - SELENIUM 105 1. BEDROCK CONCENTRATIONS 102. SOIL AND PLANT COMPOSITIONAL VARIATIONS 107 F. DISCUSSION - SELENIUM 111 1. BEDROCK 112. C HORIZON SOIL 4 3. PLANTS 5 G. CONCLUSION 117 IV RED DEER AREA A. DESCRIPTION OF STUDY AREA 1. GENERAL 118 118 vii CHAPTER PAGE 2. BEDROCK 120 3. SOIL PARENT MATERIAL 122 4. SOIL 12 5 •5. AGRICULTURAL LAND USE AND TRACE ELEMENT 125 IMBALANCES B. SAMPLE COLLECTION AND ANALYSIS 12 6 1. COLLECTION 12 6 2. ANALYSIS 126 C. RESULTS 127 1. AMONG PARENT MATERIAL SOIL COMPOSITIONAL 127 VARIATIONS 2. WITHIN PARENT MATERIAL SOIL COMPOSITION- 136 ,AL VARIATIONS a. Vertical 13b. Geographic 140 D. DISCUSSION 141. C HORIZON SOIL 2. A AND B HORIZON SOIL irVl 3. GEOCHEMICAL MAPS , 144 CONCLUSION 146 V SWAN RIVER - DAUPHIN AREA A. DESCRIPTION OF STUDY AREA 147 1. GENERAL 142. BEDROCK 9 3. SOIL PARENT MATERIAL 151 4. SOIL 155 5. AGRICULTURAL LAND USE AND TRACE 157 ELEMENT IMBALANCES B. SAMPLE COLLECTION AND ANALYSIS 160 T. COLLECTION 16a. Bedrockb. Stream Sediment 160 c. Soil 161 d. Plants 2 2. ANALYSIS 3 3. ADDITIONAL INVESTIGATIONS 16C. RESULTS - MOLYBDENUM AND COPPER 163 1. BEDROCK 162. STREAM SEDIMENT 16 5 3. SOIL AND PLANTS 167 a. Nitric-Perchloric Acid Extraction 167 b. Acid Ammonium Oxalate Extraction 186 viii CHAPTER PAGE D. DISCUSSION - MOLYBDENUM AND COPPER 188 1. BEDROCK 182. SOIL 9 3. PLANTS 192 4. AGRICULTURAL SIGNIFICANCE OF THE 196 DATA E. RESULTS - SELENIUM 199 F. DISCUSSION - SELENIUM 191. BEDROCK 192. SOIL 203 3. PLANTS 4 G. APPLICATION OF REGIONAL GEOCHEMICAL 205 RECONNAISSANCE TECHNIQUES 1. SOIL 202. STREAM SEDIMENT 205 H. CONCLUSION 207 VI CONCLUSION A. STATEMENT OF THE PROBLEM 209 B. SUMMARY OF RESULTS 210 1. ROSETOWN AND RED DEER AREAS 212. SWAN RIVER-DAUPHIN AREA 212 C. RECONNAISSANCE GEOCHEMICAL SURVEYS 214 1. INTRODUCTION 212. RECOMMENDED PROCEDURES 215 3. DISCUSSION 6 a. Choice of Size of Area 21b. Identification of Target Populations 217 c. Selection of Soil Horizon 219 d. Choice of Number and Distribution 220 of Sample Sites e. Sample Preparation and Analysis 222 f. Data Presentation 224 D. GENERAL CONCLUSIONS 22 5 E. SUGGESTIONS FOR FURTHER WORK 227 BIBLIOGRAPHY 231 APPENDIX A PROCEDURE FOR THE FLUORQMETRIC DETERMINATION 243 OF SELENIUM IN BOTH PLANT AND GEOLOGICAL MATERIALS ix PAGE APPENDIX B COMPUTATIONAL PROCEDURES FOR 247 STATISTICAL TREATMENT OF THE DATA APPENDIX C LISTING OF INDIVIDUAL DATA VALUES 2 53 USED FOR MEAN (OR MEDIAN) AND VARIABILITY ESTIMATES X LIST OF TABLES TABLE PAGE I Comparison of typical trace element 4 concentrations associated with various sedimentary rock types. II Preliminary comparison of estimated within 24 and among township C horizon soil variance components, southern portion of Rosetown area and Red Deer area. Ill Approximate numbers and types of samples 27 collected in each of the three major study areas. IV Relative extraction efficiencies of soil 30 digestion Procedures 1 and 2 for selected C horizon Rosetown area samples. V Instrumental settings for Techtron AA-4 32 spectrophotometer. VI Precision of Cu, Fe, Mn and Zn analyses at 33 the 9 5% confidence level. VII Comparison of Mo concentrations obtained 36 by this and other laboratories on selected plant samples. VIII Precision of Mo analysis, at the 95% con- 38 fidence level, based on duplicate deter minations on randomly selected samples. IX Percentage of estimated total soil Mo 39 content removed by acid ammonium oxalate and nitric-perchloric acid extractions. X Comparison of accepted Se concentrations 41 for selected standard biological samples with values determined in this study. XI Results of chi-square normality tests on 43 plant and soil Cu, Fe, Mn and Zn data from the Rosetown area. XII Physical and chemical properties of selected 58 Rosetown area soil profiles. XIII Approximate number and types of analyses 64 performed on Rosetown area samples. xi TABLE XIV XV XVI XVII XVIII XIX XX XXI XXII XXIII XXIV XXV Trace element content of C horizon soil from individual morainal types, Rosetown area. Results of application of Duncan's New Multiple Range test to log 10 C horizon soil data for individual morainal types, Rosetown area. Trace element content and pH of A and C horizon and 30-46 cm depth soil from individual soil parent material types, Rosetown area. Comparison of estimated within and among parent material logarithmic variance components, Rosetown area. Results of application of Duncan's New Multiple Range test to A and C horizon and 30-46 cm depth log 10 soil data for individual soil parent materials, Rosetown area. Trace element distribution in selected Orthic Brown and Dark Brown Chernozemic soil profiles, Rosetown area. Correlation coefficients relating log 10 trace element concentrations for A horizon and 30-46 cm depth samples to C horizon values, Rosetown area. Comparison of logarithmic within and among sample site variance components for C horizon soil, Rosetown area. Comparison of logarithmic within and among township variance components for C horizon soil, Rosetown area. Trace element content of wheat (dry weight basis) and associated Ap and C horizon soil and.soil pH, Rosetown area. Results of application of Duncan's New Multiple Range test to log 10 wheat and soil data for individual parent materials, Rosetown area. Correlation coefficients relating log 10 wheat and soil trace element data, Rosetown area. PAGE 66 67 68 70 71 79 80 84 85 87 88 90 xii TABLE XXVI XXVII XXVIII XXIX XXX XXXI XXXII XXXIII XXXIV XXXV XXXVI XXXVII XXXVIII Numbers of randomly selected soil samples (n) required from each Rosetown area parent material to give adjustable variance ratio (Vm) values of 1.0 and 5.0. Se content of Bearpaw Formation bedrock, Rosetown area. Se content of wheat-(dry weight basis) and C horizon soil, and soil pH values, Rosetown area. Results of application of Median test to wheat and C horizon soil Se values, Rosetown area. Correlation coefficients relating log 10 Se concentrations in wheat to those in associ ated C horizon soil, and' arithmetic soil pH values, Rosetown area. Trace element content of C horizon, soil from individual morainal types, Red Deer area. Results of application of Duncan's New Multiple Range test to log 10 C horizon soil data for individual morainal types, Red Deer area. Trace element content and pH of A and C horizon soil associated with major parent materials, Red Deer area. PAGE 102 106 109 112 113 128 130 131 Results of application of Duncan's New Multiple 132 Range test to log 10 C horizon soil data for major parent materials, Red Deer area. Comparison of estimated within and among 137 parent material C horizon logarithmic vari ance components, Red Deer area. Correlation coefficients relating log 10 138 trace element concentrations for A and C horizons, Red Deer area. Trace element content of selected Black and 139 Dark Brown Chernozemic soil profiles, Red Deer area. Comparison of logarithmic within and among 141 township variance components for C horizon glacial till, Red Deer area. xiii TABLE XXXIX XXXX XXXXI XXXXII XXXXIII XXXXIV xxxxv XXXXVI XXXXVII XXXXVIII XXXXIX LI LII LIII Numbers of randomly selected C horizon soil samples (n) required from each Red Deer area parent material to give adjustable variance ratio (Vm) values of 1.0 and 5.0. Mo content of Manitoba bedrock units. Chemical properties of some representative Swan River-Dauphin area soil profiles. Approximate numbers and types of analyses performed on Swan River-Dauphin area samples, Mo content of Cretaceous bedrock, west-central Manitoba. Mo content and pH of A and C horizon soil associated with individual soil parent materials, Keld area. Mo content of shale-till parent material and underlying bedrock, Keld area. Mo and Cu content of-vegetation (dry weight basis) associated with individual soil parent materials, Keld area. Mo content and pH of A and C horizon soil associated with major soil parent materials, Swan River Valley. Mo content of Mo-toxic area Kenville Soil Series parent material. Mo and Cu content of vegetation (dry weight basis), Swan River Valley. Mo content and pH of A and C horizon soil associated with individual soil parent materials, Favel area. Mo content of Favel Series shale-clay and underlying shale, Favel area. Mo and Cu content of vegetation (dry weight basis) associated with individual soil parent materials, Favel area. Acid ammonium oxalate extractable Mo content of selected C horizon soils associ ated with both Mo-rich and Mo-poor grass samples. PAGE 145 152 158 164 166 174 175 176 178 180 181 183 184 185 187 xiv TABLE LIV LV LVI PAGE Se content of selected Mo-rich bedrock 200 samples, west-central Manitoba. Se content of selcted C horizon soil 201 samples, west-central Manitoba. Se content of selected plant samples (dry 202 weight basis), west-central Manitoba. XV LIST OF FIGURES FIGURE PAGE 1• Diagramatic representation of movement of 3 trace elements from bedrock through soil to plants and animals. 2. Location of agriculturally settled Southern 15 Canadian Interior Plain,. 3. Major physiographic subdivisions of the 16 Southern Canadian Interior Plain. 4. Vegetation-type areas of Southern Canadian 16 Interior Plain. 5. Soil zones of the Southern Canadian Interior 17 Plain. 6. Bedrock geology of the Southern Canadian 17 Interior Plain. 7. Areas of known or suspected trace element 20 imbalances on the Southern Canadian Interior Plain. 8. Topography and drainage, Rosetown area. 49 9. Bedrock geology, Rosetown area. 51 10. Soil parent materials, Rosetown area. 54 11. Characteristic surf ace morphologies associated with 55 individual parent materials, Rosetown area. 12. Lithological logs of sampled Bearpaw Formation 62 drill holes. 13. Cu, Fe, Zn content and pH of A horizon soil, 73 Rosetown area. 14. Mn content and pH of A horizon soil, Rosetown 74 . area. 15. Cu, Fe, Mn, Zn content and pH of 30-46 cm 75 depth soil, Rosetown'area. 16. Cu, Fe, Zn content and pH of C horizon soil; 76 Rosetown area. 17. Mn content and pH of C horizon soil, Rosetown 77 area. 18. Scatter diagram of log 10 Cu content of A vs 81 C horizon soil. Scatter diagram of log 10 Cu content of wheat vs that of C horizon soil. Scatter diagram of log 10 Fe content of wheat vs that of C horizon soil. Scatter diagram of log 10 Mn content of wheat vs that of C horizon soil. Scatter diagram of log 10 Zn content of wheat vs that of C horizon soil. Histograms of Se content of wheat and C horizon soil Rosetown area. Se content, wheat material (dry weight), Rosetown area. Topography and drainage, Red Deer area. Bedrock geology, Red Deer area. Soil parent material, Red Deer area. Characteristic surface morphologies associated with individual parent materials, Red Deer area. Cu and Zn content and pH, C horizon soil, Red Deer area. Fe content and pH, C horizon soil, Red Deer area. Mn content and pH, C horizon soil, Red Deer area. Topography and drainage, Swan River-Dauphin area. Bedrock geology, Swan River-Dauphin area. Soil parent materials, Swan River-Dauphin area. Soil parent material and bedrock, Keld area. Soil parent material and bedrock, Favel area. Mo content of minus 8 0-mesh stream sediment, Swan River-Dauphin area. Mo content of minus 8 0-mesh stream sediment and A horizon bank soil. Mo-toxic area, Swan River Valley. Mo content of minus 80-mesh stream sediment southwest of Dauphin. Mo content of selected C horizon soil samples, southwest of Dauphin. Mo content of C horizon soil, Keld area. Mo content of C horizon soil, Swan River Valley. Mo content of C horizon soil, Favel area. xviii ACKNOWLEDGEMENTS Sincere gratitude is extended to Dr. K. Fletcher Drs. V.C. Brink, CA. Rowles and H.V. Warren Mr. Mike Waskett-Myers Mr. Dhillpn, Ms. Anne Baxter and Mr. David Marshall Drs. S. Nash, A. Kozak and A.J. Sinclair Mr. Bob Drysdale Mr. Ed Montgomery and the technical staff of the Department of Geological Sciences for having suggested and funded this project (NRC Grant #67-7714) and especially for having provided much enthusiastic advice and en couragement throughout its five year duration. for interest and guidance freely offered. for his assistance in the laboratory and for having drafted many of the illustrations. for having done much of the sample preparation and analyses. for advice on the statistical aspects of the investigation. for his keen interest and active cooperation in the study undertaken in the Swan River-Dauphin area of Manitoba. for technical assistance willingly rendered, but especially for Tuesday and Thursday morning hockey, Finally I would especially like to thank the many friends and relatives without whose encouragement and prayers the completion of this thesis would not have been possible. CHAPTER I INTRODUCTION 1 A. ENVIRONMENTAL GEOCHEMISTRY AND HEALTH 1. TRACE ELEMENTS IN PLANT AND ANIMAL HEALTH The first suggestion that trace elements could be an important factor in human and animal nutrition came in the early part of this century with the recognition that in some areas the lack of I in food and water supplies is the primary cause of endemic goitre (Underwood, 1962). Beginning in the late 1920's, chiefly through the feeding of highly purified diets to laboratory animals, the list of trace elements consider ed essential for animal health has been continuously expanding. At present at least fourteen elements are included in this group -I, Cu, Fe, Mn, Zn, Cr, Co, Mo, Se, F, Cl, Si, Sn and V (Frieden, 1972). Experimental work in the field of plant nutrition has demonstrated that Cu, Fe, Mn, Zn, Mo, Co and B are needed for the maintenance of plant health. Deficiency states involving most of the plant micronutrients have been reported, primarily in agricultural crops (Sauchelli, 1969). Field cases of trace element deficiencies in livestock, on the other hand, have been mainly limited to those involving Co, Cu, Mn and Se (Underwood, 1962). Given sufficiently high exposure any trace element can be injurious to both plants and animals. Some elements however are more noted for their toxic properties than others. The damaging effects of As> Pb, Hg and Cd on human health., for example, have been well documented. In addition 2 Se and Mo toxicity are recognized in livestock over wide areas, and Mn is well known for its locally toxic effect on crops. 2. TRACE ELEMENT STATUS OF PLANTS AND ANIMALS As illustrated diagramatically in Fig 1, local bedrock, soil, plant and animal populations may be regarded as comprising a mote or less interrelated hierarchical series. Although the trace element status of any one member of the series is determined, to a greater or lesser extent, by those of the underlying levels, a variety of factors may intervene to alter the nature of this chemical interdependency. Hodgson (1970) discusses many of these factors in relation to rock,soil and plant interactions. Bedrock, which lies at the base of the series, may vary considerably in its total trace element content (Table I). Mo levels in black shale for example (median lOppm), are generally an order of magnitude above those in sandstone (mean 0.2ppm).. Variations of a similar magnitude characterize most of the other elements cited. The extent to which bedrock composition is reflected in the overlying soil is, in part, a function of the nature of the geomorphic processes involved in soil parent material, formation. For example, in areas where parent materials are composed mainly of overburden which has been transported long distances by glacial or alluvial processes, bedrock and associated soil would 3' © © ANIMAL availability and consumption PLANT t SOIL plant species and availability A geomorphic and pedogenic processes © BEDROCK Figure I. Diagramatic representation of movement of trace elements from bedrock, through soil to plants and animals. 14 Table I Comparison of typical trace element concentrations associated with various sedimentary rock types. Trace Element Content * ** ** ** Element Black Shale Sandstone Carbonates Shale Mo (ppm) 10.0 2.6 0.2 0.4 Se (ppm) — 0.6 0.05 0.08 Cu (ppm) (%) 70.0 45.0 — 4.0 Fe 6.7 4.72 0.98 0.38 Mn (ppm) 150.0 850.0 — 1100.0 Zn (ppm) 300.0 95.0 16.0 20.0 B (ppm) 50.0 100.0 35.0 20.0 Co (ppm) 10.0 19.0 0.3 0.1 * Vine and Tourtelot (19 70); median values quoted. ** Turekian and Wedepohl (1961); average values quoted. i 5 not necessarily be expected to be compositionally similar. On the other hand, where parent materials are residual, or have been transported only short distances and have not been subjected to extensive weathering, rock and soil compositions are normally closely related. Bedrock-soil relationships are also influenced by pedogenic processes which may result in either the removal or redistribu tion of trace elements in the soil. Biocycling, for example, which is the process by which nutrients are removed from lower soil horizons by plant roots, accumulate in surface organic layers and are in varying degrees solubilized and carried back into the solum, may result in the accumulation of trace elements, such as Mn and Zn, in surface soil (Mills and Zwarich, 1975). As Mitchell (1964) has noted however, pedogenic processes have generally had a more limited effect on soil composition in regions influenced by Pleistocene glaciation, because soil parent materials in these areas are comparatively young. Trace elements incorporated within the structures of resistant soil minerals or strongly complexed by organic phases exert little influence on the composition of associated plants. On the other hand those which are either water-soluble or which are bound in a readily exchangeable form, are at least potentially available for plant uptake. Plant-available elements typically comprise a relatively small proportion of the total soil trace element content. Their concentration in the soil 6 solution depends, to a large extent, on soil reaction (pH) and drainage (Eh). In oxidizing environments, for example, Mo occurs as the molybdate anion (Mo0~), which at low pH values is strongly adsorbed by soil clays and hydrous iron oxides, but as pH levels rise is progressively released into soil solution (Jones, 1957). Doyle et al. (1973) have noted that plants grow ing in Mo-rich acidic soils contain relatively little Mo, where as those associated with similar neutral to alkaline soils may contain., large quantities (^50 ppm) of this element. Because different plant genotypes vary in their ability to absorb particular elements, plant trace element status is also dependent on the kinds of plants growing in an area. Mitchell (1957) has reported, for instance, that under conditions of abundant supply, clovers tend to be enriched in Mo relative to grasses growing in the same soil. Similarly, some species, such as Astragalus bisulcatus and A. pectinatus, are known to accumu late Se in concentrations of over 1000 ppm when growing in soils containing less than 2 ppm (Williams et al. 1941). The extent to which the nutritional status of animals re flects local plant concentrations of trace elements depends on both the degree to which they rely on local food sources and on the availability of the nutrients ingested. Thus, grazing live stock, for example, would be expected to be particularly influenc ed by trace element concentrations in local plant communities. With respect to nutrient availability Cu retention in cattle 7 and sheep, for instance, has been shown to decrease considerably in the presence of high dietary intakes of Mo (Underwood, 1962). Despite the apparent complexity of this rock-soil-plant-animal chain trace element disorders in both plants and animals can, in some instances, be more or less directly related to con centrations in associated bedrock or soil parent materials. Thus, in the United Kingdom Thornton and Webb (197 0) have demonstrated a relationship between the incidence of Mo-induced Cu deficiency in cattle and the distribution of Mo-rich black shale bedrock and, in North America, an association has been observed between the distribution of Se-rich Upper Cretaceous shale and Se toxi city in livestock (Rosenfeld and Beath, 1964) . 3. REGIONAL GEOCHEMICAL RECONNAISSANCE TECHNIQUES Because rock and soil composition can influence the trace element status of associated plants and animals, information on the distribution of trace elements in these materials is of potential interest to both agricultural and medical scientists concerned with relationships between trace elements and health. The problem of developing suitable methods of collecting and presenting regional trace element data for use by these and perhaps other environmental scientists, however, has only recently been investigated. To date two distinct approaches have been adopted; differing both in the types of material col lected (stream sediment vs. soil, plant, rock or water) and in overall sampling design. 8 a) Stream Sediment Sampling Stream sediment sampling procedures were first developed by Hawkes and Webb (Hawkes et al., 1956) in the early 1950's for application in the mining industry. The method is based on the premise that, by virtue of its origin, stream sediment may be considered a composite sample of rock, overburden and soil in the catchment area upstream from the sample site. As a result relatively few samples are required to determine rapidly, generalized trace element distribution patterns over large areas. Reconnaissance stream sediment sampling programs have been used to prepare geochemical atlases showing baseline data on the regional distribution of 26 elements in Northern Ireland, England and Wales. These maps reflect not only the natural composition of bedrock, overburden and soil but also indicate areas of indus trial metal contamination (Thornton and Webb, 197 5). Procedural details are described by Hawkes and Webb (1962). Briefly the method involves the collection of active stream sediment from tributary drainage and subsequent analysis of the minus 8 0-mesh fraction. Sampling is carried out in one operation at a predetermined density which, depending on the purpose of the study and the size of the area being investigated,.can vary be tween about 1.5 samples per square kilometer (4/sq.mi) to one sample per 180 square kilometers (1/7 0 sq mi). Trace element data for individual sample sites are conventionally either con toured or represented by variable-sized black dots. Recently however considerably more sophisticated computerized plotting 9 systems involving the production of smoothed gray-tone, as well as colour maps, have been developed for application to stream sediment data by Howarth (1971) and Lowenstein and Howarth (1973). The great advantage of stream sediment lies in the relative ease and speed with which it can be collected, processed and ana lysed. However the technique is only applicable in areas where a well developed tributary drainage system exists. Furthermore, because of the large number of factors influencing sediment com position interpretation can, in some cases, be complex (Horsnail et al., 1969). Nevertheless, with a few notable.exceptions, an encouraging degree of correlation has been observed between trace element concentrations in stream sediments and associated rock, soil and even plant, materials (Thornton and Webb, 1970) . Uses for this technique have been suggested in such diverse fields as land-use planning, pollution and epidemiology. Its applications in agriculture were pioneered iby Webb and his associ ates (Webb, 1964) in the mid-1960's in the United Kingdom and Ireland. Since then these investigators have been successful in relating regional stream sediment data to such previously recognized disorders as Mo-induced Cu deficiency, Mn deficiency and Se toxicity in cattle (Webb and Atkinson, 19 6 5'; Thornton and Webb, 1970) and Mn deficiency and Zn toxicity in cereals (Webb et al., 1968). Perhaps more significantly however, stream sediment data have proven useful in delineating areas where previously . unrecognized, subclinical nutritional disorders are adversely affecting agricultural productivity 10 (Thornton et al., 1972 a, b). b) Soil, Plant, Rock and Water Sampling More statistically rigorous sampling procedures for general application in environmental investigations have recently been developed at the Branch of Regional Geochemistry of the United States Geological Survey. These techniques were designed to de scribe regional variations in the chemical characteristics of soils, plants, rock and water in the State of Missouri. They t. were originally outlined by Connor et al. (197 2), and have since been described in greater detail by Miesch (1976). Initially earth surface materials to be investigated are subdivided into several mapable "categories" which are expected to be more or less compositionally homogeneous. Soil, for exampl could be classified on the basis of parent material type, as was done in this study. As described by Connor et al. (197 2) two phases of sampling are involved, with two stages occurring within each phase: "Phase 1: Sampling to describe differences among categor Stage la: Preliminary sampling designed to determine the extent to which the categories are indeed geo-chemically distinct, and to provide the basis for planning stage lb. Stage lb: Final sampling to derive reliable estimates of differences among categories, and the amounts of compositional variability within each category. "Phase 2: Sampling to describe patterns of variation within categories. Stage 2a: Preliminary sampling within each category to determine the sampling locality spacing that would be most efficient for describing the geochemical variation patterns within each category, and the number of samples required from each locality. Stage 2b: Final sampling to describe the geochemical patterns within each category." 11 The purpose of Phase 1 sampling is to describe major (among category) geochemical patterns only, whereas Phase 2 provides information on more detailed (within category) compositional variations. Because Miesch and his coworkers consider that geochemical surveys should initially focus on providing useful background or baseline data, Phase 2 sampling was generally not undertaken in Missouri. A hierarchical sampling plan is used during Stage la such 2 that the total data variability (s ) can be partitioned into 2 2 . several components ( sa, s^ etc.) using an analysis of variance procedure: s2 = s2 + s2 + s2 + s2 + ... (1-1) X a B y o Although the number and type of components may vary with the object of the study, four are commonly examined reflecting vari-2 ations among categories (sa), as well as both regional and 2 2 local variation within categories (s^ and s^, respectively), 2 and variation due to laboratory procedures (s 5) . A statistic referred to as the "adjustable variance ratio" (Vm), which compares the among category variance with the vari ance of category means, is used to assess the adequacy of Stage la sampling (Tidball, 1970). The variance of category means 2 (s ) is estimated from: m sm = SB + SY + S5 + •••' (1_2) nB n8 nY nBnYn6 12 where n^., riy and n5 are the number of sampling units in each of the three lower levels of the design. Vm is calculated as: 2 Vm = Sa- . (1-3) 2 s m For surveys aimed at describing broad compositional varia tions across an area with an acceptable degree of confidence Vm must be at.least equal to 1.0. If the purpose, however, is to describe reliably more detailed compositional patterns a Vm value of 5.0 or more is desirable (Tidball, 1973). When a low Vm value indicates that Stage lb sampling is required, a new hierarchical design is chosen by adjusting the values for the subscripted 2 n's in equation (1-2) until s is sufficiently small. In the J m case that a large proportion of the total data variability occurs within areas of relatively small geographic size, Stage lb sampling efficiency can be maximized by concentrating pri marily on increasing the number of samples collected within these smaller areas (Miesch, 1976). When reliable estimates of category means have been obtained, Duncan (1955)'s New Multiple Range test may be used to identify groups of categories among ' which mean compositional differences are not statistically significant. Results can finally be summarized in the form of statistical tables and modified category maps showing compositionally distinctive categories or groups of categories for each element examined. The principal originality of this approach lies in the 13 statistically rigorous nature of its multi-stage design. Because the number of samples required for a particular study depends on the relative chemical uniqueness of the categories being compared and not directly on the size of the area being examined, it is possible to produce regional maps quickly and inexpensively, using relatively few samples. Maps showing the trace element distribution in Missouri vegetation, for example (Shackletteet al. 1971), were produced using an average sample 2 density of about one site ,per 650 km (1/250 sq mi). Problems, however, may arise in the initial selection of criteria for category definition. After Stage la sampling, for example, Tidball (1971) found that none of the taxonomic divisions of Missouri soil were suited to regional geochemical map production. Furthermore, probably in part due to the very general nature of the maps produced, Miesch and his associates have had little success in attempts to relate trace element distribution patterns in Missouri to information on the distri bution of particular disease states in either livestock or man. 14 B. SOUTHERN CANADIAN INTERIOR PLAIN The Southern Canadian Interior Plain, as referred to in this study, comprises the agriculturally settled portion of the North American Interior Plain north of the Canada-United States boundary (Fig 2). 1. REGIONAL DESCRIPTION a) Physical Setting The Southern Canadian Interior Plain is divided into two major physiographic regions, the Great Plain and the Central Lowland (Bostock, 1969). The Great Plain region, locally refer red to as the Alberta Plain, is the highest (average elevation 750 m or 2/500 ft) and displays the greatest relief (Fig 3). The Manitoba Escarpment divides the Central Lowland in the east into the Saskatchewan Plain (average elevation 600 m or 2,000 ft) and the Manitoba Plain (average elevation 240 m or 800 ft). Climate is of the continental type, characterized by short hot summers and long cold winters. Highest summer temperatures and lowest precipitation levels occur in the semi-arid southeast ern portion of Alberta and southwestern Saskatchewan. Tempera tures decrease and precipitation increases more or less radially outward from this area. As indicated in Fig 4, semi-arid areas are characterized by grassland vegetation whereas boreal forests prevail in the more northern sub-humid regions (Coupland, 1961). Relatively low precipitation levels (typically 30-40 cm or 15 Figure 2. Location of agriculturally settled Southern Canadian Interior Plain. 16 Boundary of Interior Plain mi m I n Northern limit ot agricultural settlement — •—Boundary of Interior Plain subdivisions Detailed Study Areas I Rosetown H Red Deer IH Swan River-Dauphin ( Modified from Bostock , 1969) 'A. Interior Plain Subdivisions Great Plain A Alberta Plain Central Lowland B Saskatchewan Plain C Manitoba Plain Figure 3. Mojor physiographic subdivisions of the Southern Canadian Interior Plain. Figure 4. Vegetation-type areas of Southern Canadian Inferior Plain. 17 Figure 5. Soil zones of the Southern Ccnadian Interior PIcin. Figure 6. Bedrock geology of the Southern Canadian Interior Plain. 18 12-16 in/year) are primarily responsible for the general absence of tributary drainage systems, which in turn prohibits the under taking of reconnaissance stream sediment surveys through most of the region. The four major soil zones recognized (Atlas of Canada, 1957) are shown in Fig 5. Profile development is generally relatively weak in the Brown, Dark Brown and Black Zones. Most soils in these zones belong to the Chernozemic Order, although Solonetzic soils also occupy large areas. Luvisolic soils with well devel oped Ae and Bt horizons characterize the sub-humid Greywooded Zone. An additional intrazonal class of "High-lime" soils occurs on the Manitoba Plain. Generalized bedrock geology (Douglas, 1968) is illustrated in Fig 6. Limestone and dolomite-rich Ordovician to Devonian bedrock formations (Unit 6) occur beneath the Manitoba Plain in the east and are the source material for the High-lime soils in this region. These rocks are overlain by a relatively thin sequence of Jurassic and Cretaceous shale and sandstone (Units 4 and 5.) Unit 4, which is composed, for the most part, of organic-rich shale has been reported by Oddy (1966) to contain exceptionally high Mo concentrations. Most of the Alberta and Saskatchewan Plains are underlain by thick deposits of Upper Cretaceous marine silts and clays (Unit 3) and non-marine sand stone (Unit 2). Non-marine Tertiary sandstone, siltstone, mud-stone and conglomerate (Unit .1) locally overlie these Cretaceous strata. Bedrock units are covered by up to 100 m (300 ft) of Pleistocene till and stratified drift. Surficial deposits typically consist of a relatively complex intermixture of glacial till, glaciolacustrine sands, silts and clays, and lesser amounts of aeolian sand and recent alluvium. Mineralogical and chemical studies of till deposits indicate that the composition of these materials is controlled, to a large extent, by local bedrock l.ithologies (Pawluk and Bayrock, 1969). b) Agricultural Trace Element Disorders A variety of trace element excess and deficiency problems are recognized in both crops and livestock throughout the South ern Canadian Interior Plain. Cu, Fe, Mn, Zn and B deficiencies and Mn toxicity have been noted in agricultural crops. Se deficiency and Mo and Se toxicity are also known to affect live stock of the region. A map showing some areas where trace element problems are either known or suspected, compiled from both published reports and personal communications with local agricultural scientists, is presented in Fig 7. Micronutrient imbalances affecting vegetation are typically attributed to problems of trace element availability as opposed to total trace element concentrations in soils. For example, deficiencies of Fe and Mn reported in some plant species in parts of Manitoba are generally attributed to high levels of calcium carbonate and alkaline soil conditions which limit the availabil ity of these elements to plants (Hedlin, 1972). Similarly in central Alberta,, availability factors have been implicated in the IIUUO L.IVIIIVIII III llfHI VII I W V*W Boundary of Interior Plain i m iII m Northern limit of agricultural settlement Detailed Study Areas I Rosetown H Red Deer UI Swan River-Dauphin Crops Local B deficiency Cu deficiency . © Mn deficiency 0 Cu and Zn deficiency Livestock Mo toxicity Se toxicity Se deficiency Cu deficiency Regional ' Figure 7. Areas of known or suspected trace element imbalances on the Southern Canadian Interior Plain. 21 incidence of Cu and Mn deficiency in cereals grown on peaty soil (Massey, 1972). Low total soil trace element concentrations, however, probably contribute to at least some plant deficiency problems, particularly those associated with relatively coarse textured or highly leached soils. Se deficiency is recognized as a major agricultural problem affecting livestock over wide areas of the prairies. This disease is particularly prevalent in west-central Alberta (Walker, 1971) , where it has been suggested that its distribution is re lated to the presence of sandy Luvisolic soils. Se toxicity, on the other hand, has been reported only locally in cattle grazing selenium accumulator plants in southeastern Alberta and southwestern Saskatchewan (Byers and Lakin, 1939). Mo-induced Cu deficiency has been reported in cattle from a small area in the Swan River Valley of Manitoba where it was related to enhanced bedrock and soil Mo levels (Oddy, 1966^ Smith 1955). Furthermore, partly as a result of the present investiga tion, Cu deficiency has recently been recognized in livestock over wide areas of west-central Manitoba. The financial benefit which would accrue from routine Cu supplementation of cattle in this region has been conservatively estimated at nearly two million 1974 dollars per annum (Drysdale, 1975). 2. STUDY OBJECTIVES The purpose of this study was to investigate trace element distribution patterns in earth-surface materials on the Southern Canadian Interior Plain with the aim of recommending suitable procedures for efficiently collecting and presenting regional geochemical information in this area. Throughout most of the Canadian prairies tributary drainages are too scarce to permit reconnaissance mapping using stream sediment, and consequently an alternate medium is required for routine sampling purposes. In view of the fact that soil is everywhere available and can be collected with relatively little effort, emphasis was placed on examination of trace element compositional variations in this material, in order to assess the usefulness of soil data for reconnaissance geochemical mapping. Because tributary streams are locally common in southern Manitoba, an important aspect of this study involved the direct comparison of results from soil and stream sediment surveys. 3. OUTLINE OF APPROACH Three areas (I - Rosetown, II - Red Deer and III - Swan 2 River-Dauphin) varying in size from about 6,000 up to 15,000 km (2,400 to 5,800 sq mi) were selected for study. As indicated in Figs 3 to 6 these areas span a wide variety of environments, ranging from comparatively dry grassland around Rosetown to sub-humid boreal forest in the Swan River-Dauphin area. Trace ele ment imbalances, recognized, or suspected in livestock in each of these areas are, Cu deficiency (in part Mo-induced) in the Swan River-Dauphin area, Se toxicity near Rosetown and Se deficiency in the Red Deer region. In the Rosetown and Red Deer areas, where tributary streams are rare, attention focussed on an examination of the nature of both regional and detailed soil compositional variations. Originally it was thought that regional trace element patterns for soil could simply be described in terms of differences among 2 means for individual 94 km (36 sq mi) townships within the area being examined. Accordingly township means were estimated on the basis of analyses for soils obtained from two randomly select ed sites within each township. However comparison of "within" and "among" township data variability for C horizon soil (Table II) indicated that the variation among township means typically accounted for a relatively small portion (< 25%) of the total data variance. Furthermore, in the majority of cases variations among township means were not statistically significant (at the 95% confidence level): consequently most map patterns based on these means could.be attributed to chance. Inspection of the data indicated that soil composition tended to be controlled, to a large extent, by the nature of soil parent materials. In fact, as will be described in sub sequent chapters, analysis of variance shows that depending upon the area being considered up to 78% of the total soil data variance can be attributed to differences among parent material means. Consequently it was decided to describe regional soil composition al variations in terms of these among parent material mean differences. As recommended by Miesch (1976), Duncan (1955)'s New Multiple Range test was used to identify means which do not 24 Table II Preliminary comparison of estimated within and among township C horizon soil variance components, southern portion of Rosetown area and Red Deer area. Number Estimated Partitioned Variance Area of Element Total log 10 Town- Variance Within Township Among Township Ships & g. Component of Component of total total Rosetown 54 (southern portion) Cu 0.0496 Fe 0.0212 Mn 0.0203 Zn 0.0296 0.0371 74.8 0.0182 85.8 0.0177 85.3 0.0231 78.0 0.0125* 25.2 0.0030 14.2 0.026 14.7 0.0065* 22.0 Red Deer 66 Cu 0.0335 Fe 0.0141 Mn 0.0368 Zn 0.0192 0.0324 96.6 0.0141 100.0 0.0368 100.0 0.0192 100.0 0.0011 3.4 0.0000 0.0 0.0000 0.0 0.0000 0.0 Significantly greater than zero at P = 0.05. differ significantly, and results were summarized in map form showing the distribution of chemically distinctive parent mate rials or parent material groups for each element examined. In the Rosetown area the agricultural significance of parent materi al based soil compositional maps was assessed in relation to regional variations in the trace element content of associated wheat plants. In the Swan River - Dauphin area, where tributary streams are relatively common, emphasis was placed on comparison of the relative merits of soil sampling and reconnaissance stream sediment sampling procedures. Attention was focussed primarily on the distribution of molybdenum. Geochemical maps were evaluated in relation to information of the Mo content of forage plants and the distribution of Mo-induced Cu deficiency in cattle CHAPTER II SAMPLE COLLECTION, PREPARATION AND ANALYSIS AND DATA HANDLING PROCEDURES 26 A. SAMPLE COLLECTION AND PREPARATION 1. COLLECTION Approximate numbers and types of samples collected in each of the three study areas are summarized in Table III. In the Rosetown and Red Deer areas attention focussed mainly on soil sampling. A limited number of plant and rock samples were also taken in the Rosetown area. In the Swan River - Dauphin area soil, and lesser amounts of stream sediment, vegetation and bed rock were collected. Because procedural details for obtaining these materials varied somewhat from one area to the next, they are described separately in subsequent chapters. 2. PREPARATION Both soil and stream sediment were initially disaggregated in a porcelain mortar. Stream sediment was then passed through an 8 0-mesh (17 7 u) nylon sieve and the fines retained for analysis. After sieving to minus 10-mesh (2 mm), soil was ground to approximately minus 100-mesh (149 u) in a Spex "Shatterbox". Rock chips were successively passed through a jaw crusher and between ceramic plates, and were finally reduced to minus 100-mesh in a "Shatterbox". Air-dried vegetation was ground in a Wiley mill prior to analysis. B. SAMPLE ANALYSIS Trace element analysis were carried out using a combina tion of atomic absorption, colorimetric and fluorimetric 27 Table in Approximate numbers and types of samples collected in each of the three major study areas. Number of Samples Collected Sample Type Red Swan River- Total Rosetown Deer Dauphin Stream Sediment Soil Vegetation Rock 1250 600 105 50 215 215 600 2450 110 215 65 115 28 techniques. Atomic absorption was used to measure nitric-perchloric acid extractable Cu, Fe, Mn and Zn levels in Rosetown and Red Deer area plants and soils, and Cu concentrations in Swan River - Dauphin area plant samples. A colorimetric proce dure was used to determine the Mo content of both geological and plant samples from the Swan River - Dauphin area. Se was deter mined fluorimetrically in selected Rosetown and Swan River -Dauphin area plants, soils and bedrock. 1. COPPER, IRON, MANGANESE AND ZINC a) Digestion of Plants Milled vegetation (0.500 g) was placed in a large, 25 x 300 mm, pyrex test tube and 10 ml of 4:1 nitric per chloric acid added. After standing overnight the acid -sample mixture was placed on a hot air bath at moderate heat (approximately 150° C) and evaporated slowly to dry ness. 2.5 ml of 6M HCl were then added to the partly cooled test tube to dissolve the residue. Distilled water was used to bring the final sample volume to 10 ml prior to analysis. b) Digestion of Soils Two slightly different nitric-perchloric acid extrac tion procedures (#1 and 2) were employed. Procedure 1 was the first to be used and was applied to Red Deer area samples only. (i) Procedure 1 1 ml of 4:1 nitric:perchloric acid was added to a 20 X 170 mm pyrex test tube containing 0.200 g of ground soil. Test tubes were placed on a hot o air bath at 100 C for three hours. After cooling sample volume was made up to 10 ml with 1.5M HCI. (ii) Procedure 2 Either 0.200 or 0.500 g of minus 100-mesh soil were weighed into a pyrex test tube. 2 ml of 4:1 nitric:perchloric acid were then added and the mix ture placed on a hot air bath at approximately o 200 C. Evaporation was allowed to proceed to dry ness overnight. After partial cooling the residue was taken up in 2.5 ml 6M HCI and 7.5 ml of distilled water. Although Procedure 1 had the advantage of being relatively rapid, the effectiveness of trace element extraction was very sensitive to temperature, which was difficult to maintain con-o stant at 100 C. Procedure 2 was subsequently introduced in order to overcome this difficulty. As indicated in Table IV the extraction efficiencies of the two procedures differ only slightly for the elements examined. Comparison of nitric-perchloric extraction data with results for a hydrofluoric-nitric-perchloric digestion for selected samples indicates that these nitric-perchloric attacks liberate from 60 to 75% of the total soil concentrations. c) Analysis Digested samples, in 1.5 M HCI solutions, were aspirated into the air-acetylene flame of a Techtron AA-4 spectrophotometer 30 Table IV Relative extraction efficiencies of soil digestion Procedures 1 and 2 for selected C horizon Rosetown area samples. Relative Extraction Efficiency* (%) Soil Parent Number of Material Analyses Cu Fe Mn Zn Lacustrine 26 97.2 95.1 114.6 89.0 clay Lacustrine 31 94.0 89.4 102.5 98.2 silt and sand Aeolian 27 84.1 100.0 103.5 93.8 sand Relative extraction efficiency =a/ x 100. b where a = me.an_,trace element content using digestion Procedure 1, and b = mean trace element content using digestion Procedure 2. and absorbance values recorded manually. Details of standard preparation and instrumental operation procedures are described by Fletcher (1971). Instrumental settings for the four elements measured are given in Table V. An IBM 360/7 0 computer was used to convert absorbance data into concentrations, and to punch concentration values onto cards (Fletcher, 1970). Each analytical batch of 24 samples contained one blank, one laboratory standard sample used to estimate among batch analytical variations, and one randomly selected sample which was analysed in duplicate in order to assess within batch analytical variability. Computational procedures for both within and among batch precision estimation are outlined in Appendix B. As indicated in Table VI precision estimates using both procedures compare favourably and generally range within acceptable limits (+ 5 to 25%). 2. MOLYBDENUM A variety of sample extraction.procedures were employed prior to the colorimetric determination of molybdenum. A dry-ashing/HCl procedure was used routinely on plant materials where as a "partial" nitric-perchloric digestion was generally applied to geological materials. An attempt was made to measure the plant-available Mo status of selected soil samples employing an acid ammonium oxalate procedure. Residues from the oxalate ex traction were digested in a mixture of hydrofluoric, nitric and perchloric acids so that the "total" sample Mo content could be estimated. a) Digestion of Plants Milled vegetation (1.000 g) was ashed overnight in a 32 Table V Instrumental settings for Techtron AA-4 spectrophotometer. Element Wavelength Air Pressure Fuel Slit Lamp (A) (psi) Gauge Width Current Setting (u) (mA) Cu 3247.5 20 2.5 50 3 Fe 2483.3* 20 2.5 50 5 3719.9 Mn 2794.8 20 2.5 50 5 Zn 2138.6 20 2.5 100 6 * 2483.3 used for plants; 3719.9 used for soils. 33 Table VI Precision of Cu, Fe, Mn and Zn analyses, at the 95% confidence level. Precision (+ %) Type of Element „ , „„ . . , r,1 . , Geological Material Plant Estimate M . . „ , _ j Material Procedure Procedure Among Batch* Cu Fe Mn Zn 17.0 15.4 13.1 26.4 23.2 18.8 10.8 32.8 7, 25. 18. 9, Within Batch** Number of Analyses Cu Fe Mn Zn 73 8.6 14.2 7.4 9.0 52 10 14 5 17 18 21.8 28.1 24.9 8.9 Number of Paired Analyses 61 74 17 Based on one analysis of U.B.C. Standard Rock #1 (geological material) or of alfalfa sample #73-PD-1508 (plant material) per analytical batch. ** Based on duplicate analyses of one randomly selected sample per analytical batch. 34 o 20 x 80 mm pyrex test tube at 625 C. The residue was taken up in 10 ml 6M HCI and 5 ml of this solution was set aside for Mo determination. b) Digestion of Geological Materials (i) Nitric-perchloric acid extraction Ground soil and rock, and sieved stream sediment were digested as described for Cu, Fe, Mn and Zn Procedure 2. After evaporation to dryness 4 ml of 6M HCI were used to dissolve the residue. A 2 ml aliquot of this solution was transferred to a separate test tube and dilluted to 5 ml with 6M HCI in preparation for determination of molybdenum. (ii) Acid ammonium oxalate extraction This procedure was modified from that described by Reisenaur (1965). 100 ml of acid ammonium oxalate solution (pH 3.3) wer.e added to 10.00 g of unground minus 10-mesh soil in a plastic centrifuge bottle. Samples were placed on a horizontal shaker for 12 hours and then centrifuged at 4000 rpm for 2 0 minutes. A 50 ml aliquot of the supernatant liquid was trans ferred to a 100 ml beaker and evaporated to dryness on a hot plate. The residue was placed in a muffle furnace at 450° C for about 3 1/4 hours. The resul tant ash was taken up in 10 ml of 6M HCI and half of this solution was used for Mo analysis. (iii) Hydrofluoric-nitric-perchloric acid extraction Ammonium oxalate treated soil was washed in distilled water and a 2.0 g subsample was ignited at o 600 C for about 3 hours. 0.500 g of this material were digested in a teflon evaporating dish in 5 ml hydrofluoric acid and 2.5 ml 4:1 nitric:perchloric acid., After evaporation to dryness sample residues were dissolved in 10 ml 6M HCl of which 5 ml were set aside for determination of molybdenum. c) Analysis Mo was measured colorimetrically according to the dithiol procedure of Stanton and Hardwick (1967). Sodium iodide, however, was used in place of the recommended potassium iodide to supress Cu interference (Delavault, 1972), because use of the latter re agent resulted in the formation of a white potassium perchlorate precipitate when the sample residue was leached with 6M HCl. Also a few drops of acetone were added to clarify clouded petro leum ether extracts as suggested by Hoffman and Waskett-Myers (1974). Mo values obtained in this study are compared in Table VII with those obtained by two other laboratories using atomic absorp tion procedures. Generally good agreement between the two sets of data suggests that the accuracy of the colorimetric method employed was satisfactory, at least for plants. Analytical precision, estimated from the results of duplicate analyses (see Appendix B for computational procedures), ranged between 36 Table VII Comparison of Mo concentrations obtained by this and other laboratories on selected plant samples. Mo Content (ppm) Sample U.B.C. Other Number Values* Values 74-11271T21.6 1.0-1.6 (4) 74-1128 1.7 , 1.2-2.4 1.3 (4) 74-1176 1.6 , 1.2-2.0 1.3 (4) 74-1207 2.9 , 2.0-4.0 3.0 (4) 74-1852 0.7 n 0.4-1.0 0.3 (4) 74-1858 1.9 1.4-2.0 0.31 (4) 74-M-47 7.0 9.0 (1) 7 4-M-56 11.3 12.0 (1) 74-M-106 12.1 10.0 (1) 74-M-116 24.3 24.0 (1) 2 2 2 2 Mean and range: number of analyses in parentheses. Concentrations measured by atomic absorption by the Manitoba Dept.-of Agriculture, Winnipeg; number of determinations uncertain. 'Concentrations measured by atomic absorption at the Canada Dept. of Agriculture Research Station, Agassiz, B.C.; number of determinations uncertain. 37 about + 25 and + 35%, depending upon the method of extraction used (Table VIII). Comparison of nitric-perchloric extraction results with the combined results for oxalate and hydrofluoric-nitric-per chloric extractions (Table IX) indicates that the nitric-per chloric digestion released an average of only about 38% of the total amount of Mo present in the soil, but that this percentage varied considerably from one sample to the next (range 12.5 to 64.0%). Acid ammonium oxalate treatment liberated, on the average, a similar proportion (35%) of the total soil molyb denum. Amounts removed from individual samples by these two "partial" extractants however generally were not closely related. 3. SELENIUM The fluorometric procedure developed for the determination of Se is described in detail in Appendix A. Briefly, the tech nique involved digestion of 0.500 g of either plant or gelogical material in a mixture of nitric and perchloric acids as recom mended by several workers (Lane, 1966; Levesque and Vendette, 1971: Olson, 1969; Watkinson, 1960). Evaporation was continued to the first appearance of white perchloric acid fumes and then for an additional 15 minutes (Olson, 1969). Se was separated from potentially interfering elements such as Fe by coprecipita-tion with As (Allaway and Cary, 1964). After reaction with 2, 3-diaminonapathalene (DAN) in the presence of EDTA, Se was extracted into a; n-hexane layer (Wilkie and Young, 1970). 38 Table VIII Precision of Mo analysis, at the 95% confidence level, based on duplicate determinations on randomly selected samples. Extraction Sample Number of Precision Type Duplicate Analyses (+%) Nitric-perchloric Plant 27 26.4 Rock, Soil 29 29.4 Stream Sediment Acid Ammonium Soil 12 35.9 Oxalate Hydrofluoric-nitric- Soil 9 25.7 perchloric 39 Table IX Percentage of estimated total soil Mo content removed by acid ammonium oxalate and nitric-perchloric acid extractions. „ , i • Percentage of Extraction Estimated Total Procedure Removed* Nitric-Perchloric 38.2 Acid 12.5- 64.0 Acid Ammonium 35.2 Oxalate 3.0 - 62.5 Arithmetic mean and range; based on analysis of 20 samples. 40 A Turner Model 111 Fluore,meter was used for fluoresence measure ments. A detection limit of approximately 20 ppb was achieved, and this could have been improved by increasing the sample weight. The accuracy of the method for biological materials, as checked by the analysis of four interlaboratory standard samples, was satisfactory (Table X). Recovery of 0.5 ug of Se added to 0.500 g of 15 soil samples averaged 94%, and ranged from 88 to 115%. Precision, determined from the results of duplicate analyses of 30 randomly selected plant, soil and rock samples (see Appendix B for computational procedures), was approximately + 25% at the 95% confidence level. 4. SOIL REACTION 10 ml of distilled water were added to approximately 10.0 g unground (minus 10-mesh) soil in a 3 oz disposable Dixie cup. Additional water was added to particularly organic-rich samples. Soil-water mixtures were allowed to equilibrate for at least one hour with regular stirring. Measurements were made with an Orion specific ion meter (Model 404) equipped with calomel reference and Ag/AgCl pH electrodes. The instrument was cali brated periodically in buffer solutions of pH 4.0 and 7.0. C. STATISTICAL METHODS The purpose of this section is to describe, in general 41 Table X Comparison of accepted Se concentrations for selected standard biological samples with values determined in this study. Sample Se Content (ppm) Description Accepted This Values** Study* Standard Reference Materials #1571 0.080+0.010 0.074 Orchard Leaves 0.065 - 0.080 (6) #1577 1.100+0.100 1.136 Bovine Liver 0.940 - 1.34 0 (11) International Atomic Energy Agency Inter-comparison Samples #A - 2 Dried Whole Animal 0.585 0.594 Blood 0.580 - 0.600 (6) #A - 6 3.070 2.953 Fish Solubles 2.900 - 2.980 (3) Mean and range; number of analyses in parentheses. * Values For Standard Reference Materials from Orvini et al. (1974), and for IAEA Intercomparison Samples A-2 and A-6 from Gorski et al. (1974) and International Atomic Energy Agency (1975) respectively. 42 terms only, the various statistical methods employed in this investigation. Details of computational procedures are given in Appendix B. Calculations were carried out, for the most part, on an IBM 360/70 computer, using programs supplied by the Univer sity of British Columbia Computing Centre. 1. DATA TRANSFORMATION Trace element data were log-transformed (base 10) prior to most statistical manipulations. Several authors have suggested that the distribution of trace elements in geological materials approximates lognormality (Ahrens, 1954; Hawkes and Webb, 1962; Miesch, 1967). Futher-more, Duval et al. (1971), using computer based simulation studies, have shown that the concentrations of trace constituents in a variety of earth surface environmental materials including plants, may under appropriate circumstances, be expected to ap proach a iognormal distribution. Although data sets in this study are typically relatively small (< 30 observations), a limited number of the largest sets were tested for deviations from both normality and lognormality using a chi-square procedure. Results, shown in Table XI indi cate that approximately 60% of the sample sets tested are not likely (95% confidence level) to be drawn from normally distri buted parent populations. However, log-transforming the data had little effect on the outcome of the test, and the null 43 Table XI Results of chi-square normality tests on plant and soil Cu, Fe, Mn and Zn data from the Rosetown area. Soil Parent Sample Data Number Chi-Prob* Material Type Type** of — Values Cu Fe Mn Zn Lacustrine clay Lacustrine silt and sand Glacial till Aeolian sand Wheat N 28 0.40 0.31 0.59 0.82 L 28 0.42 0.20 0.46 0.92 A Horizon N 51 0.04 0.10 0.27 0.28 Soil L 51 0.14 0.16 0. 30 0.19 C Horizon N 96 0.01 0.56 0.60 0.24 Soil L 96 0.00 0.08 0.75 0.00 Wheat N 24 0.01 0.03 0.11 0.24 L 24 0.03 0.01 0.12 0.32 A Horizon N 37 0.00 0.00 0.00 0.00 Soil L 37 0.00 0.00 0.00 0 .00 C Horizon N 59 0.00 0.00 0.00 0.00 Soil L 59 0.00 0.00 0.00 0.00 Wheat N 20 0.03 0.25 0.00 0.00 L 20 0.01 0.00 0.00 0.00 A Horizon N 48 0.43 0.26 0.63 0.17 Soil L 48 0.43 0.19 0.74 0.01 C Horizon N 94 0.00 0.44 0.51 0.33 Soil L 94 0.10 0.59 0.28 0. 39 Wheat N 21 0.03 0.00 0.01 0.04 L 21 0.03 0.01 0.00 0.08 A Horizon N 38 0.00 0.00 0.00 0.00 Soil L 38 0.00 0.00 0.00 0.00 C Horizon N 57 0.00 0.00 0.00 0.00 Soil L 57 0.00 0.00 0.00 0.00 A chi-prob value of less than 0.05 indicates that the sample tested is not likely (95% confidence) to have been drawn from a normally distributed parent population. N = natural values: L = log 10 values. 44 hypothesis was also rejected for about 60% of the log 10 data sets. Nevertheless, as Miesch (1976) has pointed out, log- trans formation of trace element data can be justified on other grounds. For example, for minor constituents in natural materials variance arising both from analytical sources and that actually present in the material being examined, is generally approximately pro portional to the average amount of the constituent present. Log-transformation of the data sets tends to homogenize the data variance over the entire concentration range. This is particularly usefulbecause homogenous variance is assumed for both analysis of variance and Duncan's New Multiple Range tests which were used extensively in this study. Deviations of log 10 data from the normal form,noted in Table XI,are not considered serious because the assumption of lognormality does not, in most cases, greatly affect the results of average and variability estimates (Miesch, 1970). Although it is more important for analysis of variance based methods of significance testing, even these procedures are considered to be relatively insensitive to small deviations from normality. 2. ESTIMATION OF POPULATION PARAMETERS Either the geometric mean (GM) or, less commonly the median (M), was used to estimate the central tendency of sampled popu lations. The geometric mean was computed (Le and Seagraves, 1974) as the antilogarithm of the arithmetic mean of 45 log-transformed trace element values. Variability of data sets was expressed either as the geometric deviation (GD) or the range of observed concentrations. The geometric deviation was calculated (Le and Seagraves, 197 4) as the antilogarithm of the standard deviation of log-transform ed concentrations. In the case where log-transformed data ap proximate a normal distribution, the limits within which about 95% of the parent population values occur can be estimated as GMxGD2 and GM-^GD2. 3. IDENTIFICATION OF.OUTLIERS Examination of analytical results indicated the presence, in some data sets, of one or more anomalously high values which were considered unlikely to be representative of the populations from which they were taken. Such values could reflect, for example, the effects of sampling or analytical error, or perhaps local secondary enrichment processes. Consequently, to avoid biasing of means it was decided to reject all samples for which the log 10 concentration of any element was greater than the log 10 arithmetic mean plus two standard deviation values. Although effective for larger sample sets ( > 20 observations) , for smaller ones this procedure is of limited usefulness. Samples rejected in this fashion are indicated in the data listings in Appendix C. 46 4. TESTS OF SIGNIFICANCE a) Correlation The linear correlation coefficient, r, was computed (Le and Seagraves, 1974) to measure the strength of relationships between data for different types of associated samples, such as trace element concentrations in plant and soil material obtained at the same site. A bivariate normal population is assumed, but this statistic is generally considered to be relatively in sensitive to deviations from normality. b) Analysis of Variance A single classification analysis of variance procedure was used to partition the total data variability into within and among group components. Data groups were defined either on the basis of geographic areas of fixed size (townships or sample sites) or according to parent material type. Although this test assumes that sampled populations are normally distributed and have equal variances, results are changed very little by moderate violations of these assumptions. It has been documented for general use on the U.B.C. IBM 360/7 0 computer by Coshow (1971). c) Duncan's New Multiple Range Test This test was used to evaluate the significance of dif ferences among means for various groups of data defined on the basis of soil parent material. It has been described in detail by Duncan (1955), and compared with other similar tests by Steel and Torrie (1960). As Miesch (1976) has noted, it may be considered an extension of the "t" test to the case of more than two means. Like the analysis of variance it assumes that samples are drawn randomly from normal populations with a common variance. A U.B.C. Computing Centre program documented by Halm (1971) was employed for all calculations. d) Median Test This procedure was used to test the hypothesis that samples were drawn randomly from populations having identical medians. Essentially it involves determining the number of values within each data set which occur above and below the over all median of the combined sets, and comparing these numbers with those expected from the null hypothesis using a chi-square test (Walker and Lev, 1953). Though based on the assumption that all populations have the same form, it is generally believed that the test is not sensitive to variations in population form. CHAPTER III ROSETOWN AREA 48 A. DESCRIPTION OF STUDY AREA 1. GENERAL 2 The Rosetown area includes approximately 9,900 km (3,900 sq mi) in west-central Saskatchewan, southwest of Saskatoon (inset map, Fig 8). Semi-arid climatic conditions prevail throughout the region. The mean July temperature is o o © approximately 19 C (66 F) whereas that for January is about -16 C (3 F). Total precipitation is about 35 cm (14 in), half of which falls during the growing season from May through September (Ellis et al., 1970). Physiographically the area includes portions of both the Saskatchewan Plain and Alberta High Plain Regions of the Canadian Interion Plain (Bostock, 1970). The Saskatchewan Plain Region is represented by both the Saskatchewan River Plain and the Howarden Hills Upland, and the Alberta High Plain by the Missouri Coteau Upland (Fig 8). The Saskatchewan River Plain, which oc cupies the central lowland area is generally flat to gently rolling, and ranges in elevation from about 600 m (2,000 ft) adjacent to the uplands to about 500 m (1,600 ft) in the north east. The Howarden Hills Upland in the east rises to a maximum elevation of only about 615 m (2,050 ft) and is characterized by an undulating to rolling surface. Considerably higher eleva tions (up to 750 m or 2,500 ft) and more rugged relief occur on the Missouri Coteau Upland, both in the south and in the northwest. K>80OO' Figure8. Topography and drainage, Rosetown area. 50 Primarily because of the relatively low rainfall, perennial streams are rare throughout most of the region and discharge, particularly in upland areas, is controlled mainly by evapora tion. The South Saskatchewan River, which flows northward through the eastern portion of the area, receives only a small amount of local runoff. 2. BEDROCK The subcrop of bedrock units is indicated in Fig 9. These units consist of an essentially flatlying sequence of clays, silts, sands and gravels, ranging in age from Upper Cretaceous through Quaternary. The oldest unit, the Lea Park Formation, a noncalcareous grey to black clay (Fraser et al., 1935), subcrops only along the base of the Tyner Valley, a preglacial bedrock depression which traverses the region from southwest to northeast. This formation grades upwards into the silty grey deltaic sands (McLean, 1971) of the Judith River Formation, which in this area has a maximum thickness of about 75 m (250 ft). The Judith River Formation is, in turn, overlain by the Bearpaw Formation, the most widespread bedrock unit. The Bearpaw, which locally ranges up to 285 m (950 ft) in thickness, has been divided by Caldwell (196,8) into six silty clay and five somewhat thinner silty sand members. X-ray analysis of Bearpaw Formation material from the vicinity of Gardiner Dam indicates 3° 00' 106° 43' RI4 RI2 RIO R8 BEDROCK GEOLOGY Tert iary- Qua ternary |Oj Interbedded silt,marl.sand and gravel Cretaceous | 2 | Bearpaw Formation: noncalcareous silt and clay [:-:&:\ Judith River Formation: fine sand and silt | ^ | Lea Park Formation: silty clay Figure 9. Bedrock geology, Rosetown area. that montmorillonite is the major clay mineral, and that lesser amounts of illite and kaolinite and/or chlorite are also present (Forman and Rice, 1959). This formation, which has been reported by Williams et al. (1941) to contain up to 3.5 ppm Se, correlates with the Se-rich upper portion of the Pierre Shale of South Dakota.(McLean, 1971; Lakin, 1961). Up to 75 m (250 ft) of Tertiary and Quaternary sediments locally overlie both the Bearpaw and Judith River Formations. These relatively young deposits include a variety of non-marine lithologies ranging from clayey marls, through very fine to medium grained sands, to well rounded gravels (Christiansen and Meneley, 1971). 3. SOIL PARENT MATERIAL Bedrock units are typically overlain by from 30 to about 150 m (100 to 500 ft) of Pleistocene drift of glacial, glacio-fluvial and •glaciolacustrine origin (Scott, 1971). This drift cover is characteristically composed of successive layers of glacial till from 12 to more than 60 m (40 to 200 ft) thick, and sand and gravel, silt and clay layers ranging from 1 to over 30 m (100 ft) in thickness (Christiansen, 1973). Organic material beneath the uppermost till sheet has been radiocarbon dated at approximately 10,000 years before present (Scott, 1971). The distribution of surficial deposits which constitute the parent materials for soils in the Rosetown area is illustrated 53 in Fig 10. Five major types are recognized - lacustrine clay, lacustrine silt and sand, alluvium, aeolian sand and glacial till. Calcareous till deposits underlie both the Missouri Coteau and the Howarden Hills Uplands. They have been subdivid ed into ground (Fig 11a), hummocky (Fig lib), washboard and ridged end moraines on the basis of surface morphology (Scott, 1971). In many areas moraines are mantled by variably textured, discontinuous ablation deposits ranging from less than 1 to 5 m (15 ft) in thickness. Texturally moraines range from silty clay to sandy loam, with abundant pebbles and cobbles of igneous metamorphic and carbonate rocks. The clay size fraction is relatively rich in montmorillonite, which according to Scott (1971), reflects contributions from the underlying shales. Lacustrine clay (Fig lie), lacustrine silt and sand (Fig lid) and aeolian sand underlie the Saskatchewan River Plain. These deposits generally display gradational contacts and are under lain by till at depths of up to 30 m (100 ft). The clay size fraction of lacustrine deposits, like that of the tills, is montmorillonite-rich, indicating that both types of deposits were either derived from the same source or from sources with similar mineralogy. Parabolic dunes, and to a lesser extent undulating sand plains (Fig lie), characterize areas of aeolian surface deposits. Most dune areas have been stabilized by vegetation, but in some 108° 00" RI4 [Z—Z\ Lacustrine clay 1 | Lacustrine silt and sand L° o °.1 Alluvium Aeolian sand RI2 RIO R8 SOIL PARENT MATERIAL { j Ground moraine Hummocky moraine DL [~~3~1 Washboard moraine t 4 | Ridged end moraine j Glacial Till Figure 10. Soil parent materials, Rosetown area. Figure 11. Characteristic surface morphologies associated with individual parent materials, Rosetown area. 56 localities dune migration is actively taking place. The fine to medium grained sands of the dunes generally consist of from 80 to 90% quartz (Scott, 1971). Alluvial deposits (Fig llf) are of both glacial and post glacial origin. They are derived from a variety of sources and include a wide range of textures, from fine clays through to coarse gravels. Because the aerial extent of the various textural classes is generally limited, no attempt has been made to differentiate them on the present map. 4. SOIL Chernozemic soils cover over 90% of the area, although Regosolic, Solonetzic, and Gleysolic soils are also present (Ellis et al., 1970). Soils north of the boundary between Townships 24 and 25 generally belong to the Dark Brown Zone, whereas those south of this line belong mainly to the Brown Zone. Profile development throughout the area is generally weak, due in part to the relatively young age of the surficial deposits as well as the comparatively low precipitation. Pedogenic processes have had little effect on noncalcareous aeolian sands where Orthic Regosols predominate, on the moderately calcareous lacustrine clays which typically support both Rego Dark Brown and Rego Brown Chernozems, and on most alluvial deposits where Rego Chernozemic, Regosolic and Gleysolic soils are widespread. Horizon differentiation is more advanced, however, on lucustrine silts and sands and glacial tills which are characterized by Orthic and to a lesser extent Calcareous and Eluviated Brown and Dark Brown Chernozems. Bm and Bt horizons in these soils, which range in thickness from a few centimeters on tills and lacustrine silts to over 38 cm (15 in) on lacustrine sands, are commonly underlain by carbonate enriched Cca horizons. Physical and chemical properties obtained from Ellis et al. (1970) for selected soil profiles representing some of the more common soil types are given in Table XII. Results of size fraction analysis of Ap and B horizons are typically very similar to those for underlying C horizons. Soil pH values generally fall within the neutral to mildly alkaline range (6.6 to 7.8) and tend to increase with depth. The majority of A,horizons contain between 1.5 and. 3.5% organic matter, and B horizon contents generally range between about 0.5 and 1.5%. Cation exchange capacity values are strongly influenced by variations in soil parent material. Highest values, of over 40 meq/100 g, are associated with clay-rich fine lacustrine deposits, whereas values for lacustrine sands may be less than 10 meq/100 g. 5. AGRICULTURAL LAND USE AND TRACE ELEMENT IMBALANCES Cereal grain production, principally wheat, is the main agricultural activity on lacustrine clay, silt and sand deposits. Because of the low rainfall annual yields on clay soils (>20 bu/acre) are at least twice those on sands. Mixed farming Table XII Physical and chemical properties of selected Rosetown area soil profiles (from Ellis et al-, 1970). . . Soil Parent Material Subgroup Associ ation Hor izon Depth (cm) Particle Size Distribution (%) Sand Silt Clay Organic Matter (%) Lacustrine Rego Regina Ap 0-•10 clay Dark Brown C 10+ Rego Sceptre Ap 0-•8 Brown ck1 8-•25 25-•40 ck3 40+ Laucstrine Orthic Elstow • Ap 0-•8 silt and sand Dark Brown AB 8-•15 Bm 15-•23 Cca^ 23-•40 Ccaj 40-•53 C 53-•75 Eluviated Elstow Ap 0-•20 Dark Brown AB]_ 20-•35 ABn 35-•48 Brr£ 48-•58 Brt^ 58-•68 Bca 68-•81 C 81+ Orthic Asguith Ap 0-•23 Dark Brown Bm1 23-•35 Bm2 35-•63 C 63+ Glacial Orthic Weyburn Ap 0-•10 till Dark Brown Bt 10-•20 Bm 20-•25 Cca 25-•48 C 48+ Cation Exchange Capacity (roac^iOOg) pH 15.0 13.2 4.7 3.5 3.8 3.3 11.6 10.8 7.4 4.4 1.4 3.9 35.5 41.8 37.5 35.9 12.9 3.0 21.8 83.6 83.2 82.8 87.8 52.8 56.0 58.8 59.5 58.7 26.3 28.1 36.5 28.2 27.7 27.0 56.1 58.1 54.7 57.5 60.4 60.0 38.5 33.2 38.2 38.9 55.6 67.6 53.2 7.4 6.6 5.5 2.7 28.9 20.2 20.1 20.7 21.2 59.4 58.7 58.8 68.3 68.5 69.7 32.4 31.1 37.8 38.1 36.2 36.1 24.3 25.0 24.3 25.1 31.5 29.4 25.1 9.0 10.2 11.8 9.4 18.3 23.8 20.8 19.8 20.0 1.78 2.73 2.92 2.94 1.83 3.58 1.19 0.71 1.32 0.78 2.07 0.83 0.53 44.7 30.7 31.6 29.5 25.8 19.1 22.7 22.4 12.0 11.0 10.5 9.1 18.1 17.1 13.6 7.7 7.9 7.5 7.0 7.5 7.6 7.5 7.7 7.7 7.6 7.8 7.9 6.4 5.7 6.5 6.7 6.6 7.2 7.5 7.1 6.9 7.2 7.3 7.1 6.5 7.4 7.9 8.1 CO 59 is generally practiced in till areas, and regions underlain by aeolian sand are used mainly for pasture. Trace element imbalances of major economic significance are not at present recognized within the region. Bolton (1938), however, has suggested the possibility of isolated cases of Se toxicity in cattle grazing accumulator plants, A. bisulcatus and A. pectinatus, which are widespread on lacustrine clay and glacial till respectively. Bolton (1938) further suggested that wheat produced in this area could locally contain concentrations of Se within the toxic range for livestock. B. SAMPLE COLLECTION AND ANALYSIS 1. COLLECTION a) Soil Attention focussed on examination of soil compositional variations. As was mentioned in Chapter I (p.23 ), the original intention was to describe trace element patterns in terms of 2 differences among means for soil from individual 94 km 2 (36 sq mi) townships. Consequently, two 2.6 km (1 sq mi) sections were randomly selected for sampling within each town ship to give a total of approximately 200 sampling localities for the entire area. If sections initially chosen were not easily accessible by road alternate ones were selected. One sample site was located within each designated section. When, 60 during the course of the study, emphasis shifted toward an attempt to describe differences among means for individual soil parent material types, it became necessary that soil at the localities sampled be representative of the parent material indicated on the surficial geological map. Several sites had to be resampled to comply with this requirement. Universal Transvers Mercator (U.T.M.) grid coordinates of individual site locations are listed in Appendix C(l). Sample sites were normally situated about 90 m (300 ft) from section boundary roads, at intermediate topographic positions, if possible in summerfallow.' At each site a 30-46 cm (12-18 in) depth and C (usually Cca) horizon sample was obtained using a small post-hole digger. The maximum depth for C horizon collection was about 1 m (3 ft). Although the ma jority of 30-46 cm (12-18 in) depth samples were in C horizons, one-third to one-half of till and lacustrine silt and sand samples in this depth range represented B horizon material. A composite A (usually Ap) horizon sample was obtained from sever al localities within a few meters of the subsurface sample site. At approximately one-quarter of the localities a duplicate set of samples was obtained about 30 m (100 ft) from the original subsurface sample hole. All samples were placed in kraft paper bags and air-dried in the field. b) Plant-Soil A separate sampling program was undertaken for plants, which also included collection of associated soil material. 61 Wheat was chosen for sampling purposes because of its widespread occurrence throughout the area. The sample design differed from that employed for soils in that sections for sampling were chosen on a parent material rather than an individual township basis. Approximately 25 sections were randomly select ed over each of the four most widespread;•parentmaterial types -lacustrine clay, lacustrine silt and sand, aeolian sand and glacial till. As for soil investigations, within each designated section one sample site was chosen, at least 90 m (300 ft) from roads, to be more or less representative of the prevalent sur face geological deposit. U.T.M. coordinates for plant-soil sample sites are given in Appendix C(2). At each site Ap and C horizon soil were collected as described in the preceding section. Wheat plants were cut at about 5 cm (2 in) above the ground surface within a 30m x 30m quadrat centered on the soil sample site. Samples were placed in brown paper bags and air-dried in the field and again in the laboratory at 70 C. Sampling extended over a two week period in mid-July 1974 and the growth stage of collected material generally ranged between early flag leaf and anthesis. c) Bedrock Bearpaw Formation samples were obtained from cores for two structure test holes (Imperial Oil S.T.H. 67 and 168) and one stratigraphic test hole (Geol. Surv. of Can. 61-1) stored at the provincial government's Subsurface Geological Laboratory in Regina (Fig 12). Although not within the Rosetown area 62 FORMATION MEMBER Number.. Location DRILL HOLE STHI68 STH67 GSC 6!-l 6-2I-6W3 I0-20-6W3 27-2I-9W3 White Mud Eostend Bearpaw Oldman Aquadeil Cruikshank Snakebite Ardkenneth Beechy De m a ine Sherra rd Matador Broderick Outl ook Unnamed _SC_ALL r 200ft 50-m • 100ft 0 LITHOLOGIES j Silty clay Sand Bentonite seam Sam pled Interval (from Caldwell, 1968) Figure 12. Lithological logs of sampled Bearpaw Formotion drill holes Township-Range-Section). proper, these holes are located near the South Saskatchewan River, only a few kilometers south of the southern boundary of the area. Here the Bearpaw Formation is nearly 360 m (1,200 ft) in thickness, and the cores sampled represent the uppermost 240 m (800 ft) of this sequence. Approximately 50 composite chip samples were taken, each representing a strati-graphic interval of about 6 m (20 ft). The width of sampled intervals was modified when necessary, however, to insure that distinctive lithologies were collected separately. 2. ANALYSIS Numbers and types of samples analysed are summarized in Table XIII. Most of the wheat samples and about 700 of the 1250 soil samples collected were analysed for nitric-perchloric acid extractable Cu, Fe, Mn and Zn by atomic absorption spectro photometry. Soil determinations were carried out using digestion Procedure #2 (p.29 ). Se concentrations were measured fluori-metrically for about half of the wheat and associated C horizon soil and Bearpaw Formation rock samples collected. pH values were determined for about one-third of the collected soils. Procedures for sample preparation and analysis are described in detail in Chapter II. C. RESULTS - COPPER, IRON, MANGANESE AND ZINC In view of the strong influence of parent material on soil trace element content, data are described in terms of "among" and "within" parent material variations. Description 64 Table XIII Approximate number and types of analyses performed on Rosetown area samples. Sample Number of Analyses Types Description pH Cu, Fe Mn, Zn Se Soil A Horizon 70 70+ 30-45 cm 0 70T C Horizon 70 265* Plant-Soil Wheat - 85 60 Ap Horizon Soil 105 105 C Horizon Soil 105 105 60 Rock Bearpaw - - 25 Formation +No duplicate site samples analysed. * Includes analyses of about 50 samples from duplicate si.t'e:a. of the effects of pedogenic processes is included in the "within" parent material section. 1. AMONG PARENT MATERIAL SOIL.- COMPOSITIONAL VARIATIONS Five major parent materials are recognized in the Rosetown area - lacustrine clay, lacustrine silt and sand, glacial till, alluvium and aeolian sand. Glacial till, however, is subdivided on the basis of surface morphology into ground, hummocky, ridged end and washboard moraines. Geometric mean trace element concentrations for C horizon soil associated with various types of till (Table XIV) are generally quite similar. Mn values, for example, range between only 2 64 ppm for ridged end morairie and 278 ppm for ground moraine. Although differences among means for other elements are somewhat larger, application of Duncan's New Multiple Range test (Table XV) indicates that none of these differences are statistically significant. Data for the four morainal types have consequently been grouped together for the purpose of further statistical analysis. Geometric means and deviations for A and C horizon and 30-46 cm (12-18 in) depth soil associated with each of the five major parent materials are given in Table XVI. Mean concentra tions increase from relatively low values for aeolian sand, through intermediate concentrations for alluvium, lacustrine silt and sand, and glacial till, to highest values for lacustrine 66 Table XIV Trace element content of C horizon soil from individual morainal types, Rosetown area. Morainal Type Trace Element Content' Cu (ppm) Fe (%) Mn (ppm) Zn (ppm) Number of Analyses Ground 16.1 (1.33) 1.46 (1.23) 278 (L22) 46. 3 (1.30) Hummocky 14.6 1.44 271 46.0 (1.50) (1.40) (1.35) (1.51) 30 Washboard 15.4 1.44 (1.22) (1.18) 273 58.3 (1.26) (1.38) 23 Ridged End 18.3 1.81 (1.24) (1.22) 264 56.1 (1.22) (1.22) a) Geometric mean (GM); geometric deviation (GD) in parenthesis. b) Individual data values listed in Appendix C (1). 67 Table XV Results of application of Duncan's New Multiple Range test to log 10 C horizon soil data for individual morainal types, Rosetown area. Geometric Mean Cu (ppm) 14.6 15.4 16.1 18. 3 hummocky washboard ground ridged end moraine moraine moraine moraine Fe (%) 1.44 1.44 1.46 1. 81 hummocky washboard ground ridged end moraine moraine moraine moraine Mn (ppm) 264 271 273 278 ridged end hummocky washboard ground moraine moraine moraine moraine Zn (ppm) 4 6.0 46.3 56.1 58.3 hummocky ground ridged end washboard moraine moraine moraine moraine Means not underscored by same or overlapping lines are significantly different at P = 0.05. 68 Table XVI Trace element content and pH of A and C horizon and 30-46 cm depth soil from individual soil parent material types, Rosetown area. Trace Element Content* Nuraber Df Soil Parent Cu Fe Mn Zn pH** Trace Material (ppm) (%) (ppm) (ppm) Element Analyses A Horizon 30-46 cm C Horizon Lacustrine 21.7 2. 25 392 78.7 7. 4 22 clay (1.30) (1. 28) (1.15) (1.18) (0. 5) Lacustrine 14.3 1. 58 340 65.1 7. 0 11 silt and sand (1.36) (1. 28) (1.20) (1.29) (0. 7) Glacial till 14.8 1. 63 370 60.1 7. 5 21 (1.14) (1. 12) (1.17) (1.20) (0. 5) Alluvium 12.1 1. 55 328 61.0 7. 3 9 (1.76) (1. 44) (1.26) (1.41) (0. 6) Aeolian sand 4.94 0. 73 164 26.6 6. 8 8 (1.15) (1. 10) (1.23) (1.13) (0. 5) Lacustrine 21.8 2. 28 341 71.1 7. 8 21 clay (1.36) (1. 27) (1.20) (1.31) (0. 4) Lacustrine 13.6 1. 60 272 53.2 7. 6 11 silt and sand (1.40) (1. 24) (1.31) (1.35) (0. 7) Glacial till 15.0 1. 59 272 48.7 7. 8 22 (1.32) (1. 29) (1.26) (1.40) (0. 7) Alluvium 11.9 1. 35 239 50.9 7. 9 9 (1.77) (1. 53) (1.40) (1.44) (0. 8) Aeolian sand 3.70 0. 67 131 17.2 7. 2 8 (1.34) (1. 13) (1.37) (1.21) (0. 6) Lacustrine 24.0 2. 08 319 70.2 8. 1 66 clay (1.32) (1. 30) (1.18) (1.30) (0. 3) Lacustrine 14.7 1. 47 248 50.3 8. 4 33 silt and sand (1.56) (1. 40) (1.37) (1.41) (0. 2) Glacial till 15.4 1. 48 272 51.0 8. 3 67 (1.37) (1. ,30) (1.29) (1.44) (0. 2) Alluvium 11.1 1. 22 232 39.3 8. 4 20 (1.53) (1. ,35) (1.29) (1.49) (0. 4) Aeolian sand 5.65 0. ,75 133 24.8 7. 9 27 (1.41) (1. ,39) (1.43) (1.44) (0. 6) a) Geometric mean (GM); geometric deviation (GD) in parentheses. b) Individual data values listed in Appendix C (1) . r Arithmetic mean; arithmetic deviation in parentheses. clay. Largest relative differences among means occur for Cu, whereas among mean Mn differences are characteristically small. For example, the mean for Cu in 30-46 cm depth lacustrine clay is nearly 7 times as large as that for aeolian sand, whereas in the case of Mn the highest mean value in 30-46 cm depth material is only 2.6 times that of the lowest mean. N An analysis of variance procedure (see Appendix B) was used to estimate the relative magnitudes of within and among parent material log 10 data variance components. Results (Table XVII) indicate that compositional variations among parent materials account for well over half (54 to 78%) of the total data variability. Comparing estimates for different horizons, among parent material variations account for an average of 74% of A horizon data variability and only 60% of C horizon varia tions. Results of application of Duncan's New Multiple Range test to mean A horizon and 30-46 cm (12-18 in) depth soil values are nearly identical (Table XVIII). Means for aeolian sand are generally identified as being significantly lower and those for lacustrine clay significantly higher than other mean values. No significant differences, on the other hand, are noted among means for alluvium, lacustrine silt and sand and glacial till. Results for C horizons are similar in that extreme mean values (for sands and clays) are recognized as being distinctive. However, mean alluvium concentrations are normally indicated to be significantly lower than values for lacustrine silt and 70 Table XVII Comparison of estimated within and among parent material lcigarithmic variance components, Rosetown area. Soil Element Estimated Partitioned Variance Total log 10 ^ wit±in Variance Parent Material Parent Material 9- S-•S -6 Component of Total Component of Total A Cu 0.0600 0.0444* 74.0 0.0156 26.0 Horizon Fe 0.0349 0.0255* 73.1 0.0094 26.9 Mn 0.0219 0.0163* 74.4 0.0056 25.6 Zn 0.0320 0.0236* 73.8 0.0084 26.2 30-4.6 cm ' Cu 0.0779 0.0605* 77.7 0.0174 22.3 Fe 0.0399 0.0295* 73.9 0.0104 26.1 Mn 0.0285 0.0176* 61.8 0.0109 38.2 Zn 0.0569 0.0396* 69.6 0.0173 30.4 C Cu 0.0710 0.0488* 68.7 0.0222 31.3 Horizon Fe 0.0316 0.0241* 60.9 0.0155 39.1 Mn 0.0300 0.0174* 58.0 0.0126 42.0 Zn 0.0468 0.0252* 53.9 0.0216 46.1 Significantly greater than zero at P = 0.05. 71 Table XVIII Results of application of Duncan's New Multiple Range test to A and C horizon and 30-4.6 cm depth log 10 soil data for individual soil parent materials, Rosetown area. . Soil Element Geometric Mean Concentrations* A Cu (ppm) 4.9 12.1 14.3 14.8 21.7 Horizon Aeolian Alluvium Lacustrine Till. Lacustrine sand silt arid sand clay Fe (%) 0.73 1.55 1.58 1.63 2.25 Aeolian Alluvium Lacustrine Till Lacustrine sand silt arid sand clay Mn (ppm) 164 328 340 370 392 Aeolian Alluvium Lacustrine Till Lacustrine sand silt arid sand clav Zn (ppm) 26.6 60.1 61.0 65.1 78.7 Aeolian Till Alluvium Lacustrine Lacustrine sand silt and sand clay 30-46 Cu (ppm) 3.7 11.9 13.6 15.0 21.8 cm Aeolian Alluvium Lacustrine Till Lacustrine sand silt and sand clay Fe (%) 0.67 1.35 1.59 1.60 2.28 Aeolian Alluvium Till Lacustrine Lacustrine sand silt and sand clay Mn (ppm) 131 239 272 272 341 Aeolian Alluvium Lacustrine Till Lacustrine sand silt and sand clay Zn (ppm) 17.2 48.7 50.9 53.2 71.1 Aeolian Till Alluvium Lacustrine Lacustrine sand silt and sand clay C Cu (ppm 5.7 11.1 14.7 15.4 24.0 Horizon Aeolian Alluvium Lacustrine Till Lacustrine sand silt and sand clay Fe • '(%) 0.75 1.22 1.47 1.48 2.08 Aeolian Alluvium Lacustrine Till Lacustrine sand silt arid sand clay Mn (ppm) 133 232 248 272 319 Aeolian Alluvium Lacustrine Till Lacustrine sand silt and sand clay Zn (ppm) 24.8 39.2 50.3 51.0 70.2 Aeolian Alluvium Lacustrine Till Lacustrine sand silt and sand Clay Means not underscored by the same or overlapping lines are significantly different at P = 0.05. sand and glacial till, between which no significant mean differences are detected. Consistent with trace element data, mean soil pH values are lowest for materials associated with aeolian sand (Table XVI). Overall differences among soil pH means, however, tend to be relatively small; C horizon soil values, for example, range between only 7.9 and 8.4. Duncan's New Multiple Range test failed to detect significant among parent material differences in mean pH values for any of the horizons examined. 7Among parent material soil compositional variations are summarized in map form in Figs 13 to 17. Only chemically dis tinctive parent materials or parent material groups as identified by Duncan's test are distinguished. Weighted geometric means were calculated for parent material groups for which no signifi cant among mean differences were detected. Concentration ranges, given in brackets below category mean values include an estimated 95% of population concentrations. Mean soil pH values given for each compositional category are, in contrast to the trace element data, not significantly different. 2. WITHIN PARENT MATERIAL SOIL COMPOSITIONAL VARIATIONS a) Vertical For a given parent material, mean A and C horizon and 30-46 cm (12-18 in) depth Cu values are generally very similar. Although mean Fe values tend to decrease with depth, absolute 73 K>8°00' 106° 43' '51° 58* L„„ro .., cu Fe Zn content and pH of A horizon soil, Rosetown area. F,9Ure '3- a^tSeXiZ-laeus'rine. sin and sand.till and alluv.um, 3=aeolian sand). Figure 14. Mn content and pH of A horizon soils, Rosetown area. (I-lacustrine clay, silt and sand,till,and alluvium; 2=aeolian sand) tts'oo1 pH TRACE ELEMENT CONTENT Cu(ppm) Fe(%) Mn(ppm) Zn (ppm) 21-8 2-28 341 71-1 (11-7-40-4) (1-41-3-68) (235-495) (41-6-120 7-8 6-3-8 6 7-8 141 1-55 269 49-4 6.3-8-6 (6< 7-2 6-2-8-4 12 5-63-29-9) (0-87-2-76) (152-479) (231-105) 3-7 0-67 131 17-2 (2-05-6-66) (0-37-0-86) (69-8-247) (11-8-25-0) Number of samples 21 43 8 * Geometric mean: range= GM -rGDf GM xGD2 **Arithmetic mean:true range Figure 15. Cu,Fe,Mn,Zn content and pHof30-46cm depth soil, Rosetown area. (|=lacustrine clay;2=lacustrine silt and sand, till and alluvium; 3°aeolian sand) 106° 43' Tp34 TP32 Tp30 Tp28 Tp26 Tp24 51° 00' 8-1 7-7-8-7 8-3 7-8-8-7 8-4 7-8-9-3 7-9 6-6-8-5 ra TRACE Cu(ppm) 240 (13-7-420) 15-2 (7-37-31-3) III (4-76-25-9) 5-65 (2-83-11-3) ELEMENT Fe(%) 208 (1-24-3-48) CONTENT* Zn(ppm) 70-2 (4I-3-II9) 1-47 50-7 (0-83-2-63) (24-8-104) 1-22 (0-52-2-21) 0-75 (0-39-1-43) 39-3 (16-8-87-7) 24-8 (12-0-51-4) Number of samples 66 100 20 27 • Geometric mean:range=GM-*-GD,GMxGD **Arithmetic mean-.true range Figure 16. Cu,Fe,Zn content and pH of C horizon soil, Rosetown area. (Macustrine clay;2=lacustrine silt and sand,till;3=alluvium; 4»aeolian sand) Figure 17. Mn content and pH of C horizon soil, Rosetown area. (Macustrine clay;2=lacustrine silt and sand,till and alluvium; 3«aeolian sand) 78 compositional differences are also very slight. In the case of Mn and Zn, on the other hand, A horizon concentrations are considerably enhanced relative to 30-46 cm (12-18 in) depth and C horizon values, which are approximately equal. Mean concentrations for alluvium, for example, are Mn 328 ppm and Zn 61.0 ppm for A horizons, Mn 239 ppm and Zn 50.9 ppm for 30-46 cm (12-18 in) depth material, and Mn 2 32 ppm and Zn 39.3 ppm for C horizons. Trace element data for individual soil profiles, where recognizable B horizon material was obtained in the 30-46 cm (12-18 in) depth sample, are presented in Table XIX. Although, most of the soils represented are Orthic Dark Brown Chernozems, one Brown Chernozemic profile is also included. Among horizon Cu, Mn and Zn compositional trends, previously noted for geometric mean values are generally also apparent in these profiles. For Fe," on the other hand, B horizons, particularly those developed on glacial till, tend to contain slightly higher concentrations than both A and C horizons. This enrichment is not characteristic of all profiles however, and where present represents a maximum of only about a 20% increase over adjacent A and C horizon values. Correlation coefficients relating both individual sample values and geometric means for A horizon and 30-46 cm (12-18 in) depth samples to C horizon values are given in Table XX. A more or less typical scatter diagram showing the relationship between compositional data for A and C horizons is illustrated in Fig 18. Although coefficients for individual data values 79 Table XIX Trace element distribution in selected Orthic Brown and Dark Brown Chernozemic soil profiles, Rosetown area. Trace Element Content Soil Great Parent Group Material Site NO. Depth (cm) Hor izon Cu (ppm) Fe (%) Mn (ppm) Zn (ppm) 218 0-15 A 16.0 1.63 504 73.0 Brown Glacial 30-46 B 13.8 1.75 353 62.0 Till 90-105 C 13.8 1.56 271 50.1 Dark Brown Glacial 78 0-10 A 16.0 1.60 372 66.7 Till 30-46 B 16.7 1.76 351 59.0 75-90 C 17.5 1.52 274 51.9 230 0-15 A 15.0 1.73 488 65.0 30-46 B 16.7 2.33 398 70.0 90-105 C 28.8 2.00 448 83.3 Lacustrine 140 0-15 A 19.2 1.94 421 82.5 silt and sand 30-46 B 13.2 1.87 332 55.2 90-105 C 21.9 2.23 268 63.8 161 0-15 A 11.1 1.26 304 58.0 30-46 B 8.4 1.14 198 35.1 90-105 C 10.7 1.24 219 39.2 178 0-15 A 14.2 1.45 383 75.0 30-46 B 12.4 1.64 198 68.4 90-105 C 18.7 1.40 306 55.0 /Alluvium 92 0-15 A 15.3 1.68 429 77.0 30-46 B 18.0 2.13 404 72.7 55-60 C 16.3 1.60 361 82.3 191 0-15 A 5.3 0.84 222 30.0 30-46 B 4.0 0.72 119 16.7 90-105 C 7.4 0.86 190 31.0 Table XX Correlation coefficients relating log 10 trace element concentrations for A horizon and 30-46 cm depth samples to C horizon values, Rosetown area. Correlation Coefficients Degrees AandC 30-46 cmaridC of Horizon Soil Horizon Soil Freedom Cu Fe En Zn Cu Fe Mi Zn (n-2) Individual Lacustrine clay 0.669** 0.624** 0. 665** 0.522** 0.715** 0.687** 0.562* 0.478* 16 data values Lacustrine silt 0.829** 0.919** 0. 361 0.711;* 0.706* 0.664* 0.257 0.367 8 and sand Glacial till 0.279 0.443* 0. 166 . 0.408 -0.022 0.253 0.113 0.323 18 Alluvium 0.742* 0.818** 0. 607 0.607 0.845** 0.684* 0.638 0.592 7 Aeolian sand 0.504 0.597 0. 609 0.357 0.595 0.321 0.679 0.676 6 All parent 0.878** 0.871** 0. 808** 0.817** 0.862** 0.824** 0.746** 0.791** 62 materials Parent Material 0.988** 0.976** 0. 985** 0.937* 0.978** 0.994** 0.995** 0.973** 3 means Coefficient significantly greater than zero at P = 0.05. Coefficient significantly greater than zero at P = 0.01. OO o Data Type Soil Parent Material 81 Lacustrine clay Lacustrine silt and sand Till Alluvium Aeolian sand r60-f 0-60 0-80 100 1-20 1-40 1-60 Log. 10 Cu (ppm) C Horizon Soi I X rx X 0-6 7 • o 063 # • 0 28 <> 0-74 0 0-50 \ 0-99 Figure 18. Scatter diagram of log 10 Cu content Ippm) of A vs C horizon soil (rcorrelation coefficient). 82 associated with particular parent material types range between -0.02 and +0.92, over 60% of the values exceed +0.50. Relatively high, statistically significant coefficients, tend to be associ ated with lacustrine clay and alluvium, whereas low non-signifi cant coefficients characterize glacial till. When individual data values for all parent materials are considered together, coefficients increase markedly (range +0.75 to +0.88) and are statistically significant at the 99% confidence level. Comparison of parent material mean values, however, gives even larger coefficients (> +0.93), which despite the small number of degrees of freedom, are also highly signifi cant. b) Geographic Geometric deviations for the various horizons associated with individual surficial deposits given in Table XVI may be considered, in part at least, a reflection of the relative homo geneity of the materials examined. Of the parent materials in vestigated alluvium is characterized by the largest geometric deviations, particularly for the uppermost horizons. Comparing values by horizons, those for A horizons are generally low rela tive to values for subsurface materials. This trend is most apparent in the data for Mn, for which the average A horizon geometric deviation is 1.20 compared to an average of 1.31 for both 30-46 cm (12-18 in) and C horizon samples. Because analyses for duplicate C horizon samples are 83 available for nearly one-quarter of the sites sampled, and C horizon soil has been analysed from at least two sites within each township, it is possible to obtain estimates of both within site (sampling) and within township data variability. A single classification analysis of variance procedure was used for this purpose (see Appendix B); results are summarized in Tables XXI and XXII. Considering results for individual parent materials in Table XXI sampling (within site) variations account for a relatively small proportion (<25%) of the total C horizon data variations for alluvium, and among sample site variations are statistically significant for all elements for this parent material. In the case of glacial till, on the other hand, sampl ing variations account for from 61 to 83% of the total variance and estimated among sample site components are all non-signifi cant- For aeolian sand, lacustrine silt and sand and lacustrine clay, estimated, among sample site variance components represent from zero to 88% of total within parent material variations, and are statistically significant in approximately two-thirds of the cases. Estimated within township C horizon compositional varia tions, given in Table XXII, are generally relatively large, accounting for between 55 and 100% of the total individual parent material data variability. Statistically significant among township variations occur only for Cu and Zn in C horizon glacial till. Lack of correspondence between estimates 84 Table XXI Comparison of logarithmic within and among sample site variance components for C horizon soil, Rosetown area. Parent Material Number of Sample Sites Element Estimated Total log 10 Variance Partitioned Variance /Among Sites % Within Sites Component of total Component of total Lacustrine 17 Cu 0. 0210 0. 0135* 64 .3 0. 0075 35 .7 clay Fe 0. 0160 0. 0085* 53 .1 0. 0075 46 .9 Mn 0. 0107 0. 0040 37 .4 0. 0067 62 .6 Zn 0. 0173 0. 0115* 66 .2 0. 0058 33 .8 Lacustrine 6 Cu 0. 0154 0. 0135* 87 .7 0. 0019 12 .3 silt and sand Fe 0. 0027 0. 0000' 0 .0 0. 0027 100 .0 Mn 0. 0095 0. 0036 37 .4 0. 0059 62 .6 Zn 0. 0073 0. 0059* 71 .1 0. 0024 28 .9 Glacial till 16 Cu 0. 0289 0. 0109 37 .3 0. 0180 62 .5 Fe 0. 0103 0. 0024 23 .3 0. 0079 76 .7 Mn 0. 0178 0. 0030 16 .6 0. 0148 83 .4 Zn 0. 0179 0. 0070. 38 .8 0. 0109 61 .2 Aeolian sand 7 Cu 0. 0049 0. 0003 6 .1 0. 0046 93 .9 Fe 0. 0158 0. 0125* 78 .8 0. 0033 21 .2 Mn 0. 0223 0. 0141* 63 .2 0. 0082 36 .8 Zn 0. 0192 0. 0119* 62 • 0 0. 0073 38 .0 Alluvium 5 Cu 0. 0337 0. 0243* 72 .1 0. 0094 27 .9 Fe 0. 0197 0. 0154* 78 .2 0. 0043 21 .8 Mn 0. 0148 0. 0118* 79 .7 0. 0030 20 .3 Zn 0. 0253 0. 0217* 85 .8 0. 0036 14 .2 * Significantly greater than zero at P = 0.05. 85 Table XXII Comparison of logarithmic within and among township variance components for C horizon soil, Rosetown area. Number Estimated Partitioned Variance  of total Among Townships Within Townships Townships Element log 10 Component . % Component % Variance of total of total Lacustrine 19 Cu 0.0131 0.0027 20.2 0.0104 79.8 clay Fe 0.0121 0.0016 12.8 0.0105 87.2 Mn 0.0059 0.0011 17.8 0.0048 82.2 Zn 0.0145 0.0022 14.8 0.0123 85.2 Lacustrine 7 Cu 0.0306 0.0065 21.2 0.0241 78.8 silt and sand Fe 0.0168 0.0057 33.9 0.0111 66.1 Mn 0.0129 0.0009 6.6 0.0120 93.4 Zn 0.0158 0.0000 0.0 0.0158 100.0 Till 21 Cu 0.0189 0.0079* 41.9 0.0110 58.1 Fe 0.0146 0.0039 26.7 0.0107 73.3 Mn 0.0120 0.0037 30.8 0.0083 69.2 Zn 0.0256 0.0115* 45.0 0.0141 55.0 Aeolian sand 5 Cu 0.0193 0.0009 4.4 0.0184 95.6 Fe 0.0144 0.0000 0.0 0.0144 100.0 Mn 0.0112 0.0000 0.0 0.0112 100.0 Zn 0.0187 0.0066 35.0 0.0121 65.0 Parent Material Significantly greater than zero at P = 0.05. 86 of parent material variance in this table and those in Table XXI is attributable to the fact that calculations were based on different data subsets. 3. RELATIONSHIPS BETWEEN SOIL AND PLANT COMPOSITIONAL DATA The geometric mean trace element content, of wheat and as sociated Ap and C horizon soil are summarized, on a parent material basis, in Table XXIII. Mean soil values, though based on a separate sample set, are approximately equal to those given in Table XVI. Accordingly among parent material soil composi tional trends are essentially the same as those previously described, with lowest values associated with aeolian sand, intermediate with glacial till and lacustrine silt and sand, and highest values with' lacustrine clay. With a few exceptions, Duncan's New Multiple Range test results in Table XXIV statisti cally confirm the significance of these patterns. The among parent material pattern of Fe and Mn distribution in wheat is very similar to that for soil, with mean concentra-tions for both elements being lowest for plants grown on aeolian sand and highest for those over lacustrine clay. Although a relationship between mean Cu values for wheat and soil is less apparent, the association of the lowest wheat mean with aeolian sand deposits is consistent with soil data. Further more, as was noted for soil values, application of Duncan's test to the data for Cu, Fe and Mn (Table XXIV), tends to confirm the significance of low aeolian sand and high lacustrine Table XXIII Trace element content of wheat (dry weight basis) and associated Ap and C horizon soil and soil pH, Rosetown area. Sample Parent Trace Element Content* pH** Number Type Material Cu Mn Zn of (ppm) Ippm:wheat \ (ppm) (ppm) Analyses \ %:soil / Wheat Lacustrine 14.3 99.5 35.0 21.9 24 clay (1.11) (1.38) (1.15) (1.17) Lacustrine 15.0 87.1 26.8 23.9 23 silt and sand (1.13) (1.12) (1.19) (1.14) Till 14 .1 84.9 27.4 23.7 20 (1.10) (1.25) (1.23) (1.16) Aeolian sand 12.6 82.6 19:5 25.3 19 - (1.10) (1.20) (1.33) (1.19) Ap Horizon Lacustrine 21.7 2.23 378 78.9 •7.3 28 . Soil clay (1. 32) (1.20) (1.13) (1.13) (0.6) Lacustrine 13.2 1.60 344 67.6 6.9 24 silt and sand (1.30) (1.15) (1.15) (1-23) (0.5) Till 15.5 1.69 361 61.5 7.5 24 (1.20) (1.15) (1.20) (1.23) (0.6) Aeolian sand 7.3 1.01 198 37.5 7.2 27 (1.31) (1.18) (1.30) (1.24) (0.6) C Horizon Lacustrine 23.6 2.12 303 66.8 8.3 29 Soil clay (1.30) (1.19) (1.17) (1.22) (0.2) Lacustrine 12.8 1.54 245 52.7 8.2 26 silt and sand (1.50) (1.24) (1.24) (1.42) (0.5) Till 15.7 1. 56 290 45.3 8.2 23 (1.22) (1.16) (1.18) (1.24) (0.6) Aeolian sand 6.6 1.05 173 29.3 7.8 27 (1.55) (1.30) (1.30) (1.46) (0.7) *a) Geometric mean (GM); geometric deviation (GD) in parentheses, b) Individual data values listed in Appendix c(2) **Arithmetic mean; arithmetic deviation in parentheses. Table XXIV Results of application of Duncan's New Multiple Range test to log 10 wheat and soil data for individual parent materials, Rosetown area. 88 Sample Type Element Geometric Mean Concentrations* Wheat Ap Horizon soil C Horizon soil Cu ppm Fe ppm Mn ppm Zn ppm Cu ppm Fe % Mn ppm Zn ppm Cu ppm Fe % Mn ppm Zn ppm 12.6 Aeolian sand 82.6 Aeolian sand 14.1 Till 19.5 Aeolian sand 21.9 Lacustrine clay 7.3 Aeolian sand 1.01 Aeolian sand 198 Aeolian sand 37.5 Aeolian sand 6.6 Aeolian sand 1.05 Aeolian sand 173 Aeolian sand 29.4 Aeolian sand 14.3 Lacustrine clay 15.0 Lacustrine silt and sand 84.9 87.1 Till Lacustrine silt and sand 26.8 27.4 Lacustrine Till silt and sand  23.7 23.9 Lacustrine Till silt and sand 13.2 .15.5 Lacustrine Till silt and sand 1.60 1.69 Lacustrine Till silt and sand  344 361 Lacustrine Till silt and sand 61.5 67.6 Lacustrine Till silt and sand 12.8 15.7 Lacustrine .Till silt and sand  1.54 1.56 Lacustrine Till silt and sand 245 Lacustrine silt and sand 45.3 Till 290 Till 52.7 Lacustrine silt and sand 99.5 Lacustrine clay 35.0 Lacustrine clay 25.3 Aeolian sand 21.7 Lacustrine clay 2.23 Lacustrine clay 378 Lacustrine clay 78.9 Lacustrine clay 23.6 Lacustrine clay 2.12 Lacustrine clay 303 Lacustrine clay 66.8 Lacustrine clay ic Means not underscored by the same or overlapping lines are significantly different at P = 0.05. 89 clay: mean concentrations for wheat. The among parent material trend for Zn in wheat is excep tional in that, in contrast to the case for soil, the highest mean value .is associated with aeolian sand and the lowest with lacustrine clay. Among mean differences in the Zn content of wheat, however, are not statistically significant (Table XXIV). Correlation coefficients relating data for wheat and soil are given in Table XXV. Relationships between wheat and C horizon compositional data are illustrated graphically in scatter dia- . grams in Figs 19 to 22. Coefficients relating individual Cu, Fe and Zn values tend to be low(< 0.30), and except when data for all parent materials are considered together, are generally non significant. Mn values, on the other hand, are larger (>0.40), and statistically significant in over half of the cases. Absolute coefficient values relating mean concentrations for wheat and soil are large (range 0.74 to 0.94), but are not significant, due in part at least to the small number of degrees of freedom for the comparisons. The high negative correlation between means for Zn should be interpreted with particular caution in view of the apparent lack of significant differences among mean Zn con centrations for wheat. D. DISCUSSION - COPPER, IRON, MANGANESE AND ZINC 1. C HORIZON SOIL Comparison of the relative size of estimated within and among Table XXV Correlation coefficients relating log 10 wheat and soil trace element data, Rosetown area. Data Type Individual data values Parent Material means Parent Material Lacustrine clay Lacustrine silt and sand Glacial till Aeolian sand All parent materials Correlation Coefficients Wheat and A Horizon Soil Wheat and C Horizon Soil Cu Fe Mn Zn Cu Fe Mn Zn Degrees of Freedom (n-2) -0.182 0.106 0.432* -0.303 -0.170 0.274 0.275 -0.226 22 0.305 0.148 0.493* -0.080 0.236 -0.045 0.489* -0.537* 19 0.090 0.627** 0.419 0.051 0.183 -0.027 0.286 -0.045 17 -0.175 -0.216 0.492* 0.010 -0.170 0.193 0.621** -0..294 15 0.275* 0.294** 0.714** -0.264* 0.260* 0.271* 0.697** -0.397* 79 0.747 0.837 0.913 -0.898 0.735 0.887 0.934 -0.932 Coefficient significantly greater than zero at P = 0.05. if Coefficient significantly greater than zero at P = 0.01. o 91 E Q. Q. 3 O Q J= OS* o 1-60 1 KCH 1-20 100 + X ** X Lacustrine clay -0.17 Lacustrine silt and sand 0 024 0 74 Till • 018 a Aeolian sand . o -0:17 ® § o o o °: °o°onD 0o°eo ° 8a -—r- i l I l 060 080 100 1-20 140 Log 10 Cu (ppm) C Horizon Soil 160 Figure 19. Scatter diagram of log 10 Cu content (ppm) of wheat vs that of C horizon soil (r = correlation coefficient). 2-40 i 3 2 2CM ,0) *-^ o " J200H o •80 ^ X rx X Lacustrine clay S7 0 27 • Lacustrine silt and sand O -0 05 © >Q8 9 T ill • -003 Aeolian sand O 0 19 © L9 OO °0 C8> o c§> CDC5 ' —I 1 1 1 1 « -020 0-00 0-20 0-40 0-60 0-80 Log 10 Fe (%) C Horizon Soil Figure 20. Scatter diagram of log 10 Fe content (%) of wheat vs that of C horizon soil (r = correlation coefficient). 92 1-80 n a. a. c o " HO H o 120 H Lacustrine clay Lacustrine silt and sand Till Aeolian sand X X 0-28 • o 0 49 • 0-29 m 0 0-6 2 9 2-10 2-30 0 93 Figure 21. Scatter diagram of that of C hori zon 2-90 3)0 250 270 Log 10 Mn (ppm) Horizon Soil I og 10 Mn content (ppm)of wheat vs soil ( r = correlation coefficient). E a. a. i-eo-i 1-60 H rsi o a> 2 sz |-40 o I 20 Lacustrine clay Lacus trine silt and sand Till Aeolian sand o • o o ° o o • o E #W ^ -0-2 3 -0-5 4 -00 5 -029 O -0-93 1 » I |l I l HO 1-30 1-50 1-70 1-90 2-10 Log 10 Zn (ppm) C Horizon Soil Figure 22. Scatter diagram of log 10 Zn content (ppm) of wheat vs that of C horizon soil ( r = correlation coefficient). 93 parent material variance components for C horizon soil (Table XVII) indicates that among parent material differences account for from 54 to 69% of the total data variability. Examination of mean concentrations for C horizons associated with individual parent materials in Table XVI, and results of applica tion of Duncan's New Multiple Range test to these data in Table XVIII, furthermore suggest that among parent material soil compositional variations are closely related to textural varia tions. Lowest concentrations consistently occur in fine to medium grained sand of aeolian origin, somewhat higher concentra tions in intermediate textured till, alluvium and lacustrine silt and sand deposits, and highest concentrations in clay-rich fine lacustrine deposits. Similar relationships between textur al properties of soil parent material and soil trace element content have recently been noted in Manitoba by Haluschak and Russell (1971) and in Alberta by Pawluk , and Bayrock (1969). Aeolian sand in the Rosetown area consists of 80 to 90% quartz (Scott, 1971), which has very little capacity for either structural inclusion or surface adsorption of trace elements. Finest lacustrine deposits, on the other hand, can contain up to 80% clay size material, of which montmorillonite and to a lesser extent illite and kaolinite are the main crystaline com ponents (Scott, 1971). As Mitchell (1964) has noted, in the montmorillonite structure, Al can be replaced by Fe and Zn as well as small amounts of Mn and Cu, and similar substitutions can occur in illite. Furthermore, experimental studies have shown that appreciable amounts of Cu, Mn and Zn can be adsorbed from solution by both montmorillonite and illite (Krauskopf, 1956; O'Connor and Kester, 1975; Reddy and Perkins, 1974), and by hydrous Fe oxides (Krauskopf, 1956) which are important non-crystaline components of the clay size fraction of many soils. A measure of the effect of clay size material on adsorption capacity of Rosetown area soil is given in Table XII, where the cation exchange capacity of clay-rich Sceptre soil is shown to be 4 4 meq/100 g whereas that for clay-poor Asquith soil is only 12 meq/100 g (Ellis et al., 1970). A comparable association between trace element concentra tions and proportion of clay size material is widely recognized for sedimentary rocks (Mason, 1966). Tourtelot (1962), studying the distribution of trace elements in the stratigraphic equiva lents of the Bearpaw and related Upper Cretaceous Formations in the mid-western United States, concluded that Fe, Mn and Zn are associated with the clay size fraction of these rocks. The relationship between clay content and Rosetown area soil composi tion is, therefore, likely a characteristic inherited from the sedimentary bedrock from which soil parent materials were de rived. Some insight into the nature of within parent material data variability, which .accounts for 31 to 46% of the total, is given in Tables XXI and XXII, where these variations are partitioned into small-scale (sampling) and intermediate-scale (within town ship) components respectively. As is emphasized, however, by the lack of agreement between estimated total within parent material log 10 variance values in these two tables, results are based on separate, comparatively small sample sets, and should therefore be interpreted with caution. Information for alluvium is limited to an estimate of sampling variations only (Table XXI). For this parent material a large proportion of the compositional variability (>7 5%) is attributable to among sample site sources - that is, occurs over distances of more than 30 m (100 ft). These variations re flect, to a large extent, the comparative textural heterogeneity of alluvium. Analysis of variance results for lacustrine clay, aeolian sand, and to a lesser degree lacustrine silt and sand, tend to be similar,in that among sample site variations account for a relatively large amount of within parent material compositional variations, and among township variance components are small and non-significant. Most of the chemical variability in these materials therefore, appears to occur within areas of less than 2 one township (94 km or 36 sq mi) in size. Large-scale within parent material compositional trends, such as might be expected from regional facies changes, are either not present or very weak. Results of sampling variability, estimates for glacial till (Table XXI) indicate that the majority of compositional variabil ity in C horizon till occurs over very short distances (within sites), with among site variations accounting for only 17 to 39% of the total. Examination of estimated within and among 96 township variance components in Table XXII indicates that the magnitude of among township variations, expressed in percentage form, correspond fairly closely to among sample site variance estimates. This implies that much of the estimated among sample site variability noted in Table XXI occurs over areas greater than one township in size. 2. A HORIZON AND 30-46 CM (12-18 IN) DEPTH SOIL Components of variance estimates in Table XVII indicate that among parent material compositional variations for A horizon and 30-46 cm (12-18 in) depth soil account for a larger proportion (62 to 78%) of the total data variability than do among parent material C horizon variations (54 to 69%). Geometric deviation values in Table XVI suggest that A hor izons tend to be more compositionally homogeneous than C horizons, and this probably accounts, to some extent, for the enhanced relative importance of among parent material variations in A horizons. Geometric deviation values for A horizons are also gen erally lower than those for 30-46 cm (12-18 in) depth material. These relatively low A horizon values probably reflect, at least in part, decreased local compositional variability att ributable to the mixing effect of ploughing. In addition subsurface variability would be expected to be increased by the fact that both 30-46 cm (12-18 in) depth and C horizon samples include material from more than one pedogenic horizon — mainly B and Cca horizons in the case of the 30-46 cm (12-18 in) sample, and C as well as Cca horizons in the "C" horizon sample. It should also be noted however that the apparent homogeneity of A horizons could be, to some degree, a reflection of the fact that A horizon samples, as opposed to those of subsurface materials, were composites of soil collected from several sites within an 2 area of about 10 m . Other factors being equal, this procedure would be expected to reduce sampling variability for A horizons. Moderately high positive correlations (> 0.50) relating concentrations in individual A horizon and 30-46 cm (12-18 in) depth samples to C horizon samples for most parent materials (Table XX) imply that within parent material soil compositional var iations are controlled, to a considerable extent, by C horizons. When parent material means are compared correlation coefficients increase to over +0.90, indicating that among parent material variations are even more influenced by C horizon values. Mills and Zwarich (1975) have similarly noted that parent material trace element content exerts a very strong influence on A horizon soil concentrations in Manitoba. Examination of Fig 18 suggests that the strengthening of correlations observed when data for all parent materials are considered together (Table XX) is, in large measure, attributable to extension of the range of concentrations over which the com parisons were made, which has the effect of giving the data a considerably more distinct linear trend. The further strengthening 98 of coefficients when mean values are compared would appear to be primarily an effect of the statistical fact that data vari ability (scatter) is lower for means than for individual observa tions (Dixon and Massey, 1969). The moderate enrichment of mean Mn and Zn levels in A relative to C horizons reported in Table XVI has been noted by other workers for Chernozemic soil on the Canadian prairies (Haluschak and Russell, 1971; Mills and Zwarich, 1975). This effect is attributed by Mills and Zwarich (1975) to removal of these elements by successive generations of plants and their subsequent immobilization in the surface organic layer. It seems likely that a similar explanation applies in the Rosetown area because, although these enrichments could also be attributed for example to fertilization practices or pollution, the observed strong positive correlation between A and C horizon values would, under such circumstances, be very improbable. In well differentiated soil profiles, particularly those associated with Podzols, Fe and other elements leached from sur face soil characteristically accumulate in B horizons (Vinogradov, 1959). Evidence of this pedogenic effect can be seen in the data for Fe in 30-46 cm (12-18 in) depth B horizons in Table XIX. Magnitudes of mean Fe values for 30-46 cm (12-18 in) depth samples given in Table XVI however have not been greatly affected by these accumulations because, in the Rosetown area B horizons are not common within this depth range, and furthermore the observed enrichments are relatively small. 99 3. RELATIONSHIP.. BETWEEN PLANT AND SOIL CONCENTRATIONS The weak relationship between individual wheat and soil Cu, Fe and Zn values (Table XXV) is consistent with the commonly held view that, because of variations in soil availability and plant absorption factors (see discussion p.6 ), total soil trace element concentrations give little indication of amounts likely to be present in associated plants (Mitchell, 1972). High cor relation coefficients for corresponding Mn data (>0.40) are excep tional, and are especially surprising in view of the fact that the availability of this element to plants would be expected to be particularly affected by variations in soil environmental conditions - mainly Eh and pH (Hem, 1972). Because in the Rosetown area regional soil compositional variations can apparently be adequately described in terms of among parent material mean differences (Figs 13 to 17), the close relationship (r> 0.73) between plant and soil Cu, Fe and Mn mean concentrations for individual parent materials is partic ularly noteworthy. These strong mean relationships, however, seem to contradict results of individual sample comparisons. Examination of scatter diagrams in Figs 19 to 22 indicates that although individual data points for a given parent material tend to be fairly widely dispersed, vaguely linear trends are distinguishable when data for all parent materials are considered together. It would appear, as was noted previously for relation ships between means for soil horizons (p.98 ), that the relatively large size of mean coefficients is attributable to the 100 strengthening of these linear trends as a result of the decrease in data variability associated with the use of mean values. High correlations between plant and soil means, however, are not necessarily a result of simple cause-effect relationships. This is emphasized by the strong negative relationship between mean soil and plant Zn concentrations. In this case plant Zn values would appear to be controlled by an additional factor (or factors) which is in turn negatively related to soil Zn content. Stewart and Tahir (1971) have suggested that soil pH and organic matter content, and plant growth stage, are important influences on the distribution of Zn in wheat from Saskatchewan. It is nevertheless possible to interpret positive relation ships between Fe, Mfrand Cu means causally, in which case the scatter of individual data points could be explained, for example, as an effect of local changes in soil environmental conditions (Eh, pH etc.) if these are assumed to vary over similar ranges for the individual parent materials examined. In support of a causal explanation it should be noted that total soil trace element contents have commonly been shown to affect concentra tions in plants in geochemically extreme environments. For example, Cannon (1970) has observed that high Ni concentrations occur in vegetation growing on Ni-rich soil derived from ultra-mafic rocks in Oregon, and that low levels of nutritionally significant trace elements are widespread in crops in the trace element-poor coastal plain sands of the eastern United States. 101 It would seem reasonable to expect to find a similar, though perhaps more subtle relationship, between plant and soil con centrations in other less compositionally extreme environments. 4. GEOCHEMICAL MAPS a) Method of Presentation Geochemical maps in Figs 13 to 17 are essentially graphical summaries of statistically significat among parent material compositional variations as defined by Duncan's New Multiple Range test in Table XVIII. To be useful for environmental studies, these map patterns should be stable - that is they should be fairly readily reproducible by separate sampling programs. In this regard .it is noteworthy that results of application of Duncan's test to mean data for soil collected at wheat sample sites in Table XXIV are very similar to those reported in Table XVIII. The stability of these compositional patterns can be ass essed using Tidball (1970)'s adjustable variance ratio, Vm, as described previously in Chapter I (p. 12). Because Vm values of at least 1.0 and preferably 5.0 are needed for reproducible map patterns, these values were used to determine the minimum number of samples required per parent material (Table XXVI). Results indicate that because of the large among parent material variance components (Table XVII) even for Vm values of 5.0 it is necessary to collect only 2 A or 5 C horizon samples from each surficial deposit. Because mean values for Duncan's test in 102 Table XXVI Numbers of randomly selected soil samples Cn) required from each Rosetown area parent material to give adjustable variance ratio (Vm) values of 1.0 and 5.0. n Horizon Element . Vm = 1.0* Vm = 5.0* Cu <1 1.8 Fe <1 1.8 Mn <1 1.7 Zn <1 1.8 Cu <1 2.3 Fe <1 3.2 Mn <1 3.6 Zn <1 4.3 Vm = S&/S , where Sex = among parent material variance m from Table XVII and, 2 S . = within parent material variance m from Table xVTEr-n. 103 Table XVI were based on no fewer than 8 and up to 67 observa tions, Vm calculations confirm the stability of the map patterns. Although within parent material compositional variations are not shown in Figs 13 to 17, such information could have been presented by, for example, either plotting township means or individual sample values for each element at appropriate sites on separate maps. This, however, would have resulted in doubling the number of maps produced. Furthermore, it would have provided very little useful additional information because, on the one hand, analysis of variance results in Table XXII show that differences among township means are not statistically significant for most parent materials, and on the other, although among sample site variations are commonly significant (Table XXI), low correlation coefficients relating individual soil and plant sample data (Table XXV) indicate that plotting each soil con centration separately would be of little use in predicting local plant compositional variations. Finally, in interpreting these geochemical maps it should be recalled that they are based on a soil parent material map, which because of the scale of presentation, is very generalized. Areas shown in Fig 10 to be underlain by glacial till, for example, are commonly mantled by variable thickness of lacustrine deposits which are too limited in aerial extent to distinguish separately. Because these local deposits were purposefully avoided during sample collection, they generally do not con tribute to category mean and variance estimates. 104 b) Patterns and Their Significance Map Cu, Fe, Mn and Zn patterns for A and C horizon and 30-46 cm(12-18 in) depth soil are basically similar in that soil associated with aeolian sand is identified as being sig nificantly lower and that associated with lacustrine clay significantly higher in trace element content than soil derived from alluvium, glacial till and lacustrine silt and sand. High positive correlation coefficients (>0.70) between mean Fe, Mn and Cu plant and soil values indicate that trace element patterns for soil in Figs 13 to 17 are related to regional compositional variations in wheat. Further evidence of this relationship is apparent in results of applying Duncan's test to wheat means for these three elements (Table XXIV). Results for wheat Mn values are identical to those for soil, with both the low mean for wheat growing on aeolian sand and the high mean for wheat associated with lacustrine clay identified as being significantly different from other estimated means. Similarly, in agreement with soil trends, the high Fe mean for wheat grown on lacustrine clay and the low Cu mean for aeolian sand, are indicated to be significantly different from means associated with other surficial deposits. Maps like those in Figs 13 to 17, but based on sampling of uncultivated B horizon soil, have been prepared for the State of Missouri using vegetation-type areas instead of soil parent materials for category definition (Shacklette et al., 1972). Despite the existence of large differences in soil 105 composition among vegetation-type areas, little relationship was found between soil patterns defined by Duncan's New Multiple Range test and the trace element content of associated plant material. This situation was however attributed, in part at least, to large differences among category mean pH values (range 5.3 to 7.3), which would be expected to considerably affect the availability of trace elements to plants. Differences among mean pH values for soil associated with various parent materials in the Rosetown area are, in contrast, very small (Table XVI). The apparently strong relationships between Cu, Fe and Mn mean plant and soil values suggest that in this, and per haps in other similar Canadian prairie environments, maps such as those presented could be of value in predicting regional plant compositional variations. These maps, therefore, could be useful in identifying areas where trace element im balances in crops or livestock are especially likely to occur. E. RESULTS - SELENIUM 1. BEDROCK CONCENTRATIONS Se levels in Bearpaw Formation drill core are summarized in Table XXVII. Concentrations throughout the nearly 240 m (800 ft) interval examined are generally less than 1.0 ppm. Sandy formation members (Cruikshank, Ardkenneth and Demaine) contain the smallest amounts of Se (0.25 to 0.50 ppm). The 106 Table XXVII Se content of Bearpaw Formation bedrock, Rosetown area. Member Description Thickness (m) Number of Analyses Se Content* (ppm) Aquadell medium grey silty clay 78 7 0.56 0.12-1.12 (0.47) Cruikshank greenish grey sand 12 2 0.46 0.43-0.50 (0.46) Snakebite medium grey clay to silty clay 74 8 0.57 0.37-0.81 (0.59) Ardkenneth greenish grey sand 33 3 0.30 0.25-0.37 (0.29) Beechy greenish grey silty clay 20 2 0.64 0.63-0.65 (0.64) Demaine medium grey sand 17 2 0.26 (0.26) Sherrard greenish grey silty clay 15 2 0. 66 0.58-0.75 (0.66) a) Geometric mean; true range: median in parentheses. b) Individual data values listed in Appendix C(3). 107 geometric mean Se content of all samples analysed is 0.50 ppm. 2. SOIL AND PLANT COMPOSITIONAL VARIATIONS Histograms of the Se content of both wheat and C horizon soil associated with individual parent material types are shown in Fig 23. Although a logarithmic bar interval is used, some . of these distributions appear to be positively skewed (Fig 23h),whereas for others bimodiality is suggested (Fig 23a and b). To avoid biases associated with the use of mean values, therefore, medians were chosen as preferable estimates of the central tendencies of the data sets. Wheat and C horizon soil Se, and soil pH data, are sum marized in Table XXVIII and Fig 24. Compositional trends for Se are similar to those for other elements examined. The Se content of C horizon soil is lowest for aeolian sand (median 0.12 ppm) and highest for lacustrine clay (median 0.37 ppm), with intermediate concentrations occurring in till and lacus trine silt and sand. Although median wheat Se values are con siderably higher than those for soil parent material, the same overall trend is apparent, with the lowest value associated with aeolian sand (median 0.64 ppm) and the highest with lacus trine clay (median 2.18 ppm). The significance of differences among medians was evaluated using the Median test (see Appendix B). Results suggest that 108 WHEAT SOIL TJ C o CO c D O < tA I- Q. ii E p ° 1 « 2 • GMO-96 GD=2I7 n = l5 (0) 6M=0-I3 (b) GD = l-58 n=l5 MA o*io(0cmoo,s" rp^-ipw^-j-i-ip 6 o 6 6 - iii w * Se (ppm, dry weight) OO-=!JZ:NNI9 66666666 Se (ppm) TJ c o CO TJ c o CO a> c IA a> mpl E DS 3 DS 2 H— o I GM=0-85 (C) GD = l-79 n =15 GM=0-32 (d) GD = I-5I n =15 mm/A Q. E o in 3 Z H— 2 ION 10 IO * N * IO Ol lOy <D 00 — IO o r- ao 6666--nn10 Se (ppm, dry weight) I /177Z) (OOjOOIO't — _www**ips 6 66666660 Se (ppm) g 'o o CD a> c E 3 0) 4 JZ3 1 GM=2-20 GD =2-41 n = l5 (e) GM=0-27 GD=l-94 n = !5 (f) S 12 P7P: 'A x> E E «3 3 z f5U 66 — <Si 10 m 00 <vi Se (ppm, dry weight) 'A O-^NNtOIONOIIQO) 666666666 — — Se (ppm) o O to n E 3 z 8 CL E o in L GM=2-36 (g) 6 D =1-62 n = l6 GM=0-49 (h) GD = l-84 n = l6 in Oi X) fc z 1 Ld 21 EE o 4- ID in o - rooo Ji-foowoaicp cvi 6 — — ^ oil 10 10 * <b Se (ppm, dry weight) o><o<oo)(0Oe4(0ir> 666660 — — <\] Se (ppm) Figure 23. Histograms of Se content of wheat and C horizon soil, Rosetown area (bar interval logarithmic, GM»geometric mean,GD-geometric deviation). 109 Table XXVIII Se content of wheat (dry weight basis) and C horizon soil, and soil pH values, Rosetown area. Parent Number of Wheat Soil C Horizons Material Samplest Se* Se* pH** (ppm) (ppm) Lacustrine 16:16 2.18 0.37 8.3 clay 1.02-5.40 0.24-1.92 8.1-8.6 Lacustrine 15:15 1.08 0.28 8.3 silt and sand 0.38-3.60 0.18-0.63 6.9-8.9 Glacial till 15:15 1.54 0.26 8.3 0.85-11.2 0.08-1.50 7.5-8.9 Aeolian sand 16:15 0.64 0.12 7.8 0.42-4.00 0.07-0.26 6.5-8.9 1~Number of wheat samples: number of soil samples. * a) Median and true range. b) Individual sample values listed in Appendix C(2). ** Arithmetic mean; true range. 108° 00' 106° 43' 110 Tp34 TP32 RI4 RI2 SOIL PARENT MATERIAL [?-~H Lacustrine clay | | Lacustrine silt and sand RIO 1 | Glacial till f>" ° "Q| Alluvium Aeolian sand R 8 Wheat Se Concentration (ppm) • <IOO • 100-2-99 ©3-00-6-00 •>600 Figure 24. Se content, wheat material (dry weight), Rosetown area. 111 medians for both soil parent material and wheat samples are probably (99% confidence level) drawn from different populations (Table XXIX). Furthermore, although linear correlation co efficients show the relationship between individual overburden and wheat concentrations to be poor (Table XXX), there is a high correlation (+0.9 0) when medians are compared, which is significant at the 90% confidence level. Correlations between individual wheat Se and soil pH values are weak (Table XXX). Median pH values were not com pared with corresponding wheat data because median test results indicated that differences among median pH values associated with various parent material types are not significant. F. DISCUSSION - SELENIUM 1. BEDROCK Se concentrations measured in the uppermost two-thirds of the Bearpaw Formation range between 0.12 and 1.12 ppm. These values are much lower than those reported for black shale bed rock units (up to 100 ppm) associated with the distribution of accumulator plants (including A. bisulcatus and A. pectinatus) in the United States (Lakin, 1961). They are, however, con sistent with results of Williams et al. (1941) who found an average of 1.6 ppm in a limited number of surface Bearpaw Formation samples from Saskatchewan. TOurtelot (1962) attributed high concentrations in the Table XXIX Results of application of Median test to wheat and C horizon soil Se values, Rosetown area. Number of Values Above and Below Parent • Overall Group Medians* Chi-square Material TT, . _ •, -* Wheat Soil Classification Observed Expected Observed Expected Wheat Soil Lacustrine clay Above 14 8.0 14 8.1 Below 2 8.0 2 7.9 Lacustrine silt Above 6 7.5 9 7.6 and sand Below 9 7.5 6 7.4 Glacial till Above 7 7.5 7 7.6 Below 8 7.5 8 7.4 Aeolian sand Above 4 8.0 0 7.6 Below 12 8.0 15 7.4 ft ft Chi-square significantly greater than zero at P = 0.01, * Wheat median 1.53 ppm: soil median 0.26 ppm. 113 Table XXX Correlation coefficients relating log 10 Se concentrations in wheat to those of associated C horizon soil and arithmetic soil pH values, Rosetown area. Correlation Coefficients Data Type Parent Wheat Se Wheat Se Degrees Material and and of Soil Se Soil pH Freedom .". . rr. (n-2) . Individual Lacustrine 0.245 -0.320 13 data clay values Lacustrine 0.237 -0.186 13 silt and sand Glacial till -0.013 -0.123 13 Aeolian sand -0.574* 0.388 14 All parent 0.222 0.190 59 materials Parent Material 0.901 2 medians * Coefficient significantly greater than zero at P = 0.05. 114 Pierre Shale, the stratigraphic equivalent of the Bearpaw Formation in South Dakota, to adsorption of Se from seawater by clay and organic matter in relatively low energy far-shore environments. The Bearpaw Formation, in contrast, was deposited comparatively rapidly in a high energy littoral setting .(Caldwell, 1968), which probably allowed little time for adsorption proces ses to be effective. Furthermore this formation contains a high proportion of sand and silt size material (Caldwell, 1968), which would be expected to have relatively limited adsorption capacities. 2. C HORIZON SOIL Soil Se concentrations (range 0.07 to 1.92 ppm) are similar to those reported for the Bearpaw Formation, and are therefore compatible with the hypothesis that soil parent materials were derived, at least to some extent, from this bedrock unit (Scott, 1960) . Median test results (Table XXTX) suggest that soil parent material is a significant factor in determining regional soil Se distribution patterns. Furthermore, as for the other trace elements examined, Se concentrations appear to be closely re lated to textural variations, with median values tending to increase with clay contient. This trend is consistent with that noted in the Bearpaw Formation (Table XXVII), from which it may be, to some degree, inherited. 115 3. PLANTS Median test results for plant data suggest that soil parent material is also a significant factor in determining regional Se distribution patterns in wheat. The particular trend apparent in Table XXVIII toward highest plant Se con centrations associated with finest grained parent material, has been noted by other workers in Saskatchewan. Thorvaldson and Johnson (1940), for example, investigating Se levels in Saskatchewan wheat grain, observed that materials derived from areas of lacustrine clay soil tended to contain higher Se con centrations than those from other areas. Similarly, Owen (1972), in controlled field trials, reported somewhat enhanced Se con tents for forage crops grown on Saskatchewan lacustrine clay soils relative to those grown on glacial till derived materials. Low correlations between individual plant and soil Se values suggest that within parent material compositional variability for plants is controlled to a large extent by such factors as local soil pH and Eh, and secondary iron oxide con tent, which affect the form and hence availability of soil Se (Gerring et al., 1968). Gupta and Winter (1975) have reported similarly low, typically non-significant correlations between individual soil and plant Se values in Prince Edward, Island. The strong positive correlation between wheat and soil median values (0.90), on the other hand, implies that the among parent material plant Se distribution pattern is, to some degree at least, influenced by variations in total parent material 116 concentrations. Kubota and Allaway (1972) have likewise noted that broad geographic variations in Se levels in plant materials in the United States tend to reflect variations in the Se content of soil parent material. The strength of the median correlation, relative to coefficients for individual data values, is interpreted as being, in large measure, an effect of the decrease in data variability associated with the use of medians (Dixon and Massey, 1969). This effect is analo gous to those described previously (pp.98 andlOO) for coeffi cients relating data means. With regard to the possible health significance of wheat Se concentrations (Table XXVIII, Fig 24), it is interesting to note that approximately one-third of the wheat samples from both till and lacustrine clay contain concentrations equal to or greater than the maximum level of about 3-4 ppm recommended for animals by Underwood (1962). BecauseSe is concentrated in the wheat grain relative to the leaves and stems (Rosenfeld and Beath, 1964), an even higher proportion of wheat grain would be expected to contain concentrations above this limit. These results contrast with the relatively low values (^2.0 ppm) previously reported by both Bolton (19 38) and Thorvaldson and Johnson (1940) for composite wheat grain samples from Saskatchewan. 117 G. CONCLUSION Regional variations in the trace element content of Rose town area soils are controlled, to a large degree, by changes in parent material type. Concentrations associated with a particular surficial deposit appear, in turn, to be largely determined by its textural characteristics. Low values characterize soil developed on relatively coarse grained deposits such as aeolian sands, whereas high concentrations typically occur in soil assoc iated with fine grained materials such as lacustrine clay. Soil compositional patterns can be conveniently described by applying Duncan's New Muptiple Range test to mean values for individual parent materials and summarizing test results in map form, distinguishing only compositionally unique parent mat erials or parent material groups. Similar map patterns are obtained regardless of whether A, 30-46 cm (12-18 in) or C hor izons are used. Because of relatively large differences among parent material means, very few samples are required (< 5 per deposit) to produce stable maps. Depending upon the element being considered, close relat ionships may exist between mean concentrations for soils and plants associated with the same parent material. These relationshi suggest that soil compositional maps based on among mean differ ences could be of considerable value in identifying areas where trace element imbalances in crops and livestock are particul arly likely to occur. 117a CHAPTER IV RED DEER AREA 118 A. DESCRIPTION OF STUDY AREA 1. GENERAL 2 The Red Deer area covers approximately 6,100 km (2,400 sq mi) of south-central Alberta (inset map; Fig 2 5). Climatic conditions vary considerably (Chapman and Brown, 1966), from marginally semi-arid in the east near Sullivan Lake (mean an nual precipitation 35 cm or 14 in) to sub-humid in the extreme west (mean annual precipitation 50 cm or 20 in). The area occurs within the Alberta Plain physiographic subdivision of the Canadian Interior Plain (Fig 3). The land surface rises gradually in a westerly direction, from a minimum of 810 m (2,7 00 ft) on the nearly level lowlands near Gough and Sullivan Lakes to over 1,140 m (3,800 ft) along the western mar gin adjacent to the foothills of the Rocky Mountains (Fig 25). Topography on the central and western upland is generally un dulating to rolling, with local relief reaching a maximum of 45 m (150 ft). Drainage in the eastern lowland is controlled by numerous closed basins such as Gough Lake, which discharge mainly by evaporation (Fig 25). The Red Deer River and its tributaries drain the remainder of the area. As in the Rosetown area tribu tary streams suitable for reconnaissance stream sediment sampl ing purposes are rare. II4°46' ^Cdlgaryj AREA OF STUDY R27 R25 R23 R2I RI9 RI7 RI5 n2° 00' -3000— Topographic contours (interval 200ft). "~>— River, stream. Highway Township (Tp) - Range (R) boundaries. 9 City, town. Figure 25. Topography and drainage, Red Deer area. M VO 120 2. BEDROCK Bedrock, which dips to the west and southwest, comprises a succession of sandstones, siltstones and mudstones ranging in age from Upper Cretaceous to Tertiary. The four separate map units recognized (Fig 26), have been described in detail by Irish (1970) and Carrigy (1971). The Horseshoe Canyon Formation, which is the oldest rock unit, underlies the eastern lowland. It is composed of approxi mately 225 m (750 ft) of bentonitic feldspathic sandstone and silty bentonitic shale, as well as coal seams and beds of car bonaceous shale. This unit is overlain by from 2 to 6 m (6 to 2 0 ft) of white weathering sand, silt and clay belonging to the Whitemud Formation. The Battle Formation, which succeeds the Whitemud, consists of from 8 to 9 m (25 to 30 ft) of mauve weathering shale. Together these three formations constitute the Upper Crevtaceous Edmonton Group as defined by Irish (1970). The Paskapoo Formation, of Upper Cretaceous to Tertiary age, underlies the central and western portions of the area. Its thickness increases westward reaching a maximum of 900 m (3,000 ft). This unit, which is lithologically similar to the Horseshoe Canyon Formation, includes massive medium to coarse grained sandstone, fine grained sandstone and silty shale. Limestone and lenses of woody coal and pebble conglomerate are also present. !I4°46' T OJ tf> , 113° 52 SRed Deer Tp38 Tp37 n Tp36 Tp35 R7 R5 R3 ,2 Rl Ml MILES I KM 20 R27 R25 R23 R2I RI9 RI7 Tp34 (From Gfreen,l972) ^og^ R'5 ||2° 00* BEDROCK FORMATIONS TERTIARY AND CRETACEOUS CRETACEOUS Poska pOO : nonmarine sands tone, siltstone and muds tone; minor conglomerate, limestone, coal and tuff beds Whitemud and Battle-, nonmari ne bentonitic sandstone and muds tone; -Includes siliceous tuff beds Horseshoe Canyon: mainly nonmarine bentonitic sandstone, mudstone and carbonaceous shale; includes concretionary ironstone , cool and bentonite Figure 26. Bedrock geology, Red Deer area. I—1 122 3. SOIL PARENT MATERIAL The distribution of soil parent materials shown in Fig 27 was compiled from several surficial geological maps (Boydell, 1973; Craig, 1957; MacS. Stalker, 1956 and 1960). Only four major units are recognized - ground moraine, hummocky moraine, lacustrine and alluvium-outwash deposits. Moraines (Fig 28a and b)cover most of the area and are composed mainly of till derived from local bedrock (Gravenor and Bayrock, 1961; MacS. Stalker, 1960). Till thickness varies from only a few meters for ground moraine to over 15 m (50 ft) for hummocky moraine. Although textures are normally in the loam to clay-loam range, hummocky moraine tends to be somewhat coarser than ground moraine because of removal of fine material as outwash during deposition (MacS. Stalker, 1960). Mineral-ogical examination of till associated with both the Paskapbo and Horseshoe Canyon Formations north of the study area indicates that montmorillonite is the main crystaline component of the clay size fraction (Twardy et al., 1974). Up to 15 m (50 ft) of glaciolacustrine deposits (Fig 28c) locally overlie till. Although the largest of these are shown in Fig 27, numerous smaller deposits are also present. Because these sediments exhibit considerable textural heterogeneity over short distances, it was not possible to divide them into mapable units based on grain size. Alluvium and outwash de posits (Fig 28 d), which contain a relatively large proportion of sands and gravels, are associated mainly with the Red Deer R27 R25 SOIL PARENT MATERIAL Ground moraine I I Hummocky moraine I--—I Lacustrine deposits Alluvial-outwash deposits Figure 27. Soil parent material, Red Deer area. IsJ 124 c) Lacustrine deposits d) Mluvium-outwash Figure 28. Characteristic surface morphologies associated with individual parent materials, Red Deer area. 125 River and its tributaries. Gravels are chiefly of exotic origin, and include chert, quartzite and granitic rock frag ments (MacS. Stalker, 1960). 4. SOIL Soils in the Red Deer area have been described by Bowser et al. (1951) and Peters and Bowser (1960). As indicated previously in Fig 5 three major soil zones are recognized -from east to west Dark Brown, Black and Greywooded. Most soils in the Black and approximately one-half in the Dark Brown Zone belong to the Chernozemic Order. Solonetzic soils are also widespread in the Dark Brown Zone, whereas Luvisols are characteristic of the Greywooded Zone. Although detailed physical and chemical data are not gen erally available, soil survey information indicates that A horizon pH values are in the slightly acid to neutral range (6.1 - 7.3), and C horizon values are normally mildly alkaline (7.4 - 7.8). Depth to C (usually Cca) horizons increases west ward from 65 cm (25 in) in the Dark Brown Zone to over 90 cm (36 in) in the Greywooded Zone. 5. AGRICULTURAL LAND USE AND TRACE ELEMENT IMBALANCES Climatic conditions in the central Black Soil Zone are ideally suited to grain crops, principally wheat, whereas early frost in the Greywooded Zone and low rainfall in the Dark Brown Zone favour use of these regions for pastureland or hay produc tion. Se responsive white muscle disease is recognized as a 126 serious problem for cattle producers in the western half of the area (Godkin, 1973) where Se injections are now more or less routinely administered after calf birth. B. SAMPLE COLLECTION AND ANALYSIS 1. COLLECTION Only soil was sampled in the Red Deer area. Procedures for choosing sites and sample collection were generally similar to those previously described for soil in the Rosetown area (p. 59 ). However besides two sample, sites selected randomly within each township, a limited number of additional sites were located on alluvium-outwash to ensure adequate representation of this material. Also, duplicate samples were not collected, and B horizon soil was taken in place of the 30-46cm (12-18 in) depth sample. The majority of A horizons were collected from the plough layer, and those C horizons obtained were normally taken from the zone of carbonate enrichment immediately below the B horizon. Either because of excessive rockiness or depth of sola (> 1 m) C horizons were not obtained at over one-quarter of the sample sites. U.T.M. coordinates for individual sample sites are given in Appendix C(4). 2. ANALYSIS All C horizons, as well as selected A and B horizon samples were analysed for nitric-perchloric acid extractable Cu, Fe, Mn and Zn by atomic absorption using soil digestion Procedure 1. Soil reaction was measured for a limited number of both A horizon and C horizon samples. Procedures employed for sample preparation and analysis are described in detail in Chapter II. C. RESULTS As in the Rosetown area, soil trace element data are de scribed in terms of among and within parent material variations. Because B horizons are not present everywhere, and therefore cannot be used for regional mapping, concentrations in these materials are considered only briefly in relation to the effects of pedogenic processes. 1. AMONG PARENT MATERIAL SOIL COMPOSITIONAL VARIATIONS In view of the local derivation of till deposits, moraines were subdivided into those associated with either the Horseshoe Canyon or Paskapoo Formations. Geometric mean trace element concentrations for C horizon soil from both hummocky and ground moraines associated with each of these bedrock units are given in Table XXXI. Two distinct compositional trends are apparent -on the one hand, means for Horseshoe Canyon till are somewhat higher than corresponding means for Paskapoo till., and on the other, for a given bedrock type concentrations in ground moraine are generally higher than those of hummocky moraine. For example, Horseshoe Canyon mean Cu values for hummocky and ground moraine are 15.7 and 18.9 ppm respectively, whereas 128 Table XXXI Trace element content of C horizon soil from individual morainal types, Red Deer area. Trace Element Content* Bedrock Morainal Cu Fe Mn Zn Number Formation Type (ppm) (%) (ppm) (ppm) of Analyses Horseshoe Hummocky 15 . 7 1. ,35 22 1 40 .7 Canyon (1. 16) (1. ,15) (1. 42) (1. 15) Ground 18 .9 1. ,47 29 4 48 .8 (1. 40) (1. .28) d- 26) (1. 22) Paskapoo Hummocky 12 .8 1. .20 20 8 34 .9 (1. 58) (1. . 33) (1. 41) (1. 41) Ground 14 .9 1. .49 280 42 .1 (1. 40) (1. .22) (1- 37) (1. 24) a) Geometric mean (GM); geometric deviation (GD) in parentheses. b) Individual sample values listed in Appendix C(4). 129 Paskapoo Formation means are 12.8 ppm for hummocky moraine and 14.9 ppm for ground moraine. Application of Duncan's New Multiple Range test to these values however (Table XXXII), failed to detect any significant differences among Cu, Fe and Zn means. Data for each of these elements for all morainal types were therefore grouped together for the purpose of further statistical analysis. Results for Mn were exceptional in that means for hummocky moraine (2 08 and 221 ppm) were found to be significantly lower than those for ground moraine (280 and 294 ppm). Mean concentrations for both A and C horizons associated with major Red Deer area parent materials are given in Table XXXIII. Examination of C horizon data indicates that values for glacial till and lacustrine deposits are generally similar, whereas those for alluvium-outwash are relatively low. Duncan's test confirms the significance of this trend for Cu and Zn (Table XXXIV), Results for Fe differ in that the mean for lacus trine deposits is identified as being significantly greater than that for till. In the case of Mn, two distinctive data subsets are defined comprising alluvium-outwash and hummocky moraine on the one hand, and lacustrine deposits and ground moraine on the other. These test results are summarized in map form in Figs 29 to 31. As in the Rosetown area weighted means were calculated when compositional categories included more than one parent material. An analysis of variance procedure (see Appendix B) was 130 Table XXXII Results of application of Duncan's New Multiple Range test to log 10 C horizon soil data for individual morainal types, Red Deer area. Element Geometric Mean Concentrations' (ppm) 12.8 14.9 15.7 18.9 Cu Horseshoe Paskapoo Paskapoo Horseshoe hummocky ground Canyon Canyon moraine moraine hummocky ground moraine moraine Fe (%) 1.20 1.35 1.47 1.49 Paskapoo Horseshoe Horseshoe Paskapoo hummocky Canyon Canyon ground moraine hummocky ground moraine moraine moraine (ppm) 208 221 280 294 Mn Paskapoo Horseshoe Paskapoo Horseshoe hummocky Canyon ground Canyon moraine hummocky moraine ground moraine moraine Zn (ppm) 34.9 40.7 42.1 48.8 Paskapoo Horseshoe Paskapoo Horseshoe hummocky Canyon ground Canyon moraine hummocky moraine ground moraine moraine Means not underscored by the same or overlapping lines are significantly different at P = 0.05. 131 Table XXXIII Trace element content and pH of A and C horizon soil associated with major parent materials, Red Deer area. Soil Parent Number Trace Element Content* of Horizon Material Mn Cu Fe Zh.. pH** Element (ppm) (ppm) (%) (ppm) Analyses A Ground moraine Hummocky moraine 437 (1.25) 335 (1.40) 12.8 (1.25) 1.43 (1.23) 62.2 (1.21) 6.0 5.4-8.0 27 Lacustrine deposits 375 13.0 1.46 60.7 7.1 (1.20) (1.34) (1.25) (1.21) 6.1-8.0 10 Ground moraine Hummocky moraine 272 (1.25) 218 (1.41) 15.4 (1.39) 1.35 (1.25) 40.6 (1.28) 7.9 5.1-9.0 57 Lacustrine deposits 270 (1.33) 17.2 (1.49) 1.54 (1.29) 46.8 (1.36) 8.0 7.8-8.1 22 Alluvium- 201 8.9 1.00 24.4 7.4 outwash deposits (1.65) (1.40) (1.42) (1.75) 5.9-8.0 a) Geometric mean (GM); geometric deviation in parentheses. b) Individual sample values listed in Appendix C (4) . ** Arithmetic mean and true range. 132 Table XXXIV Results of application of Duncan's New Multiple Range test to log 10 C horizon soil data for major parent materials, Red Deer area. Element Geometric Mean Concentrations* Cu (ppm) Fe (%) Mn (ppm) Zn (ppm) 8.9 Alluvium-outwash deposits 1.00 Alluvium-outwash deposits 201 218 Alluvium- Hummocky outwash deposits moraine 24.4 Alluvium-outwash deposits 15.0 Moraines 1. 35 Moraines 270 Lacustrine deposits 40.6 Moraines 17.2 Lacustrine deposits 1.54 Lacustrine deposits 272 Ground moraine 46.8 Lacustrine deposits Means not underscored by the same or overlapping lines are significantly different at P = 0.05. 113° 52 I14°46' R27 R25 pH R23 R2I RI9 TRACE ELEMENT CONTENT* Cu (ppm) Zn (ppm) 7-9 5-1-9-0 7-4 5-9-8-0 15-6 (7-7-31-4) 8-89 (45-17-4) 42-3 (24-6-72 6) 24-4 (8-0-74-7) RI7 Number of analyses 79 8 Tp36 Tp35 Tp34 5I°53 RI5 ||2° QO1 * Geometric mean (GM):range=GfVRGD?GMxGDz ** Arithmetic mean-, true range Figure 29. Cu and Zn content and pH, C horizon soil, Red Deer area. (l=ground and hummocky moraines and lacustrine deposits>2=alluvium-outwash deposits) H LO 00 52°I9-113° 52 II4°46' pH R23 R2I RI9 TRACE ELEMENT CONTENT * Fe (%) 5-1-9-0 7-4 5-9-8-0 80 r^== 1-54 7.8-8l WI1M (0-93-2-56) 7-9 r-r-r-i 1-35 (0-87-210) 1-00 (0-50-2-02) * Geometric mean (GM):range=GM+GD*GMxGD8 **Arithmetic mean,true range Figure 30. Fe content and pH, C horizon soil, Red Deer area. (Hacustrine depositS52=ground and hummocky moraines;3=alluvium-outwash deposits). RI7 Number of analyses 22 57 8 RI5 -5I°53' 112° 00' * Geometric mean (GM):range=GM+GD*GMxGD2 ** Arithmetic mean-.true range Figure 31. Mn content and pH, C horizon soil, Red Deer area. (l=groundmoraine and lacustrine deposits;2=hummocky moraine and alluvium-outwash deposits). OJ on 136 used to estimate the relative magnitudes of among and within parent material compositional variations in C horizon soil. Results, given in Table XXXV, show that a relatively small proportion (14-42%) of the total C horizon data variability can be attributed to differences among parent material means. 2. WITHIN PARENT MATERIAL SOIL COMPOSITIONAL VARIATIONS a) Vertical Correlation coefficients relating individual log 10 con centrations in A and C horizons for moraines and lacustrine deposits are given in Table XXXVI. In agreement with results reported in the preceding chapter values for moraines are generally low and non-significant, whereas those for lacustrine deposits are somewhat higher. The strength of between horizon relationships, however, is not appreciably increased by com bining the two data sets. Because A horizon values were measured for only two parent materials, it was not possible to compute coefficients relating.A and C horizon means. Also consistent with Rosetown area trends, both Mn and Zn are enriched in A horizons ; The mean Zn content of A horizon glacial till for example (62.2 ppm) is about 50% greater than the mean for corresponding C horizon material (40.6 ppm). Examination of compositional data for a limited number of Chernozemic B horizons (Table XXXVII) indicates a tendency for this material to be enriched in iron. 137 Table XXXV Comparison of estimated within and among parent material C horizon logarithmic variance components, Red Deer area. Partitioned Variance Estimated Element Total log 10 Among Within Variance Parent Materials Parent Materials Component % Component % of total of total Cu 0.0326 Fe 0.0153 Mn 0.0221 Zn 0.0295 0.0100* 31.7 0.0043* 28.1 0.0031* 14.0 0.0125* 42.4 0.0226 68.3 0.0110 71.9 0.0190 86.0 0.0170 57.6 Significantly greater than zero at P = 0.05. 138 TABLE XXXVI Correlation coefficients relating log 10 trace element concentrations for A and C horizons, Red Deer area. Soil Parent Material Correlation Coeff1c1ent Cu Fe Mn Zn Degrees of Freedom (n-2) Moraines 0.245 0.368 0.495* 0.269 20 Lacustrine Deposits 0.762 0.958** -0.086 0.919** Both Parent Materials 0.316 0.532** 0.389* 0.432* 26 •k Coefficient significantly greater than zero at P = 0.05. Coefficient significantly greater than zero at P = 0.01. 139 Table XXXVII Trace element content of selected Black and Dark Brown Chermozemic soil profiles, Red Deer area. So11 Trace Element Content Great Parent Site Depth Horizon Group Material No. (cm) Cu Fe Mn Zn (ppm) (%) (ppm) (ppm) Black Ground 9 .'nbraine 11 22 Lacustrine 110 deposits Dark Hummocky 75 Brown moraine 79, 94 Ground 81 moraine 86 92 Lacustrine 147 deposits 0-15 A 12.0 30-46 B 9.7 76-91 C 11.6 0-15 A 12.9 46-61 B 12.5 76-81 C 9.8 0-15 A 10.4 30-46 B 4.8 76-91 C 17.5 0-15 A 16.0 35-51 B 15.5 76-91 C 16.7 0-10 A 12.9 23-38 B 11.6 46-61 C 17.2 0-10 A 12.0 15-30 B 9.7 30-46 C 15.7 0-10 A 8.8 30-46 B 14.5 61-66 C 19.4 0-10 A 30.3 30-46 B 21.3 76-91 C 18.5 0-10 A 10.4 15-30 B 9.7 56-71 C 12.0 0-10 A 12.8 15-30 B 7.. 8 76-91 C 38.9 0-10 A 10.0 15-30 B 5.0 76-91 C 6.9 1.35 . 380 51.5 2.06 749 36.9 1.15 315 37.0 1.48 499 52.8 1.81 292 48.6 1.00 190 31.0 0.99 366 56.9 1.51 212 28.8 1.37 172 43.0 1.51 486 66.7 1.67 264 44.9 1.54 283 45.9 1.44 413 66.4 1.81 311 48.5 1.41 324 42.9 1.23 518 69.4 1.67 297 61.0 1.42 266 41.0 1.56 343 54.7 1.58 109 59.2 1.45 184 41.5 2.54 486 74.7 2.14 406 71.8 1.49 342 50.3 2.05 680 64.0 1.37 344 68.2 1.86 311 51.7 1.40 518 65.4 1.11 231 37.7 2.10 393 69.2 0.93 347 51.6 0.81 110 23.1 0.86 122 19.2 140 b) Geographic Comparison of geometric deviations for A and C horizons associated with till and lacustrine deposits (Table XXXIII) suggests that A horizons tend to be more compositionally homo genous than C horizons. Considering Cu data, for example, A horizon geometric deviation values are 1.2 5 for till and 1.34 for lacustrine deposits, whereas corresponding C horizon values are 1.39 and 1.49 respectively. The relative magnitudes of among and witnin township C horizon data variability for till were estimated using an analysis of variance technique ( see Appendix B). Results, in Table XXXVIII show that among township compositional variations are negligible. D. , DISCUSSION 1. C HORIZON SOIL Differences between means for C horizon till associated with Horseshoe Canyon and Paskapoo Formations (Table XXXI) are consistent with the results of Pawluk.' and Bayrock (19 69) who noted that regional variations in the trace element con tent of Alberta till are closely related to changes in bedrock type. Lack of statistical significance for these compositional differences (Table XXXII) reflects, to a large extent, the lithological and chemical similarity of the two bedrock formations. 141 Table- XXXVIII Comparison of logarithmic within and among township variance components for C horizon glacial till, Red Deer area. „ J_. A , Partitioned Variance Estimated : Number of Flpmpnt «w.al loa Townships Ji-LemenT: ^ ^^Z^ Among Township Within Township Component of ^tal Component of ^tal 17 Cu 0.0140 0.0 0.0 0.0140 100.0 Fe 0.0080 0.0 0.0 0.0080 100.0 Mn 0.0170 0.0 0.0 0.0170 100.0 Zn 0.0093 0.0 0.0 0.0093 100.0 142 As was noted in Chapter III, textural characteristics appear to be of considerable importance in determining among parent material compositional trends. Thus low mean values for alluvium-outwash deposits (Table XXXIII) are consistent with the relatively high proportion of sand and gravel in samples from this parent material. Likewise, the occurrence of significantly lower mean Mn concentrations in hummocky relative to ground moraine(Table XXXII) can be related to the relatively coarse grained nature of the former deposits. The comparatively small proportion of the total log 10 c horizon data variability attributable to among parent material sources (14-42%) reflects the relatively narrow range of parent material means. Mean Mn concentrations, for example, range from only 201 to 27 2 ppm, whereas in the Rosetown area, where 54-69% of C horizon compositional variations can be explained in terms of among parent material mean differences, Mn means range between 133 and 319 ppm. Extreme Rosetown mean values are associated with comparatively coarse sands and fine clays, and small among parent material variance components . in the Red Deer area reflect the absence of similar textural units in this region. The lack of measurable among township compositional variations for C horizon till (Table XXXVIII) indicates that on a regional scale till may be considered to be essentially homogeneous. These results are consistent with those of Duncan's New Multiple Range test for Cu, Fe and Zn (TableXXXII) but ap pear to contradict results for Mn for which significant dif ferences were noted between means for hummocky and ground 143 l moraines. Explaination of these seemingly contradictory find ings lies, in part at least, in the fact that the analysis of variance was based on a subset only of till data, and furthermore both hummocky and ground moraines were represented in the sample pairs from some townships. 2. A AND B HORIZON SOIL As discussed previously in relation to Rosetown results, the apparent homogeneity of A relative to C horizons (Table XXXIII) is probably a partial effect of local mixing associated with ploughing, as well as the composite nature of A horizon samples. Subsurface variability would also, however, be expected to be relatively enhanced by the fact that, in some of the deeper soil profiles, the B-Cca contact was very close to the maximum sampling depth of the equipment used, and as a result variable amounts of B horizon material were inadvertently included in C horizon samples. Relatively low correlations between trace element values for individual A and C horizon samples for till (Table XXXVI) suggest that for this parent material compositional variations in A horizons are not strongly influenced by C horizon concent rations. The reverse would appear to be true for lacustrine dep osits, although more data is required to confirm this. As was pointed out in Chapter III, enhanced Mn and Zn con centrations in A horizons are likely attributable to the 144 influence of biocycling (Mills and Zwarich, 1975). Fe enrich ment in B horizons, (Table XXXVII) on the other hand, reflects the effects of surface leaching and subsequent fixation processes. 3. GEOCHEMICAL MAPS Map patterns in Figs 29 to 31 are based on results of ap plication of Duncan's New Multiple Range test to C horizon soil data (Table XXXIV). They are considerably less complex than those for C horizon Rosetown area soil (Figs 16 and 17), in part because among parent material mean differences are smaller, but also because fewer parent material types are recognized. The adjustable variance ratio (see Chapter I, p.12 ) was used to estimate the number of samples required per parent material to ensure map stability. Results in Table XXXIX, indicate that depending on whether a Vm value of 1.0 or 5.0 is taken as the accepted standard, as few as 6 or as many as 30 samples are required from each parent material. These values represent a considerable increase over corresponding numbers required from individual surficial deposits in the Rosetown area (maximum 5), principally because of the comparatively small differences in parent material mean concentrations. In view of the fact that a Vm value of 1.0 is considered adequate for the description of general map patterns, and in this study at least 8 C horizon samples were obtained from each parent material examined, it is concluded that the map patterns presented should be fairly stable. 145 Table XXXIX Numbers of randomly selected C horizon soil samples (n) required from each Red Deer area parent material to give adjustable variance ratio (Vm) values of 1.0 and 5.0. n Element Vm = 1.0* Vm = 5.0* Cu Fe Mn Zn 2.3 2. 8 6.1 1.4 11.5 14.0 30.0 7.0 2 2-2 Vm = Sex /s , where S<* = among parent material m 2 variance from TableXXXV,and S = within parent material m variance from TableXXXV-r H . 146 E. CONCLUSION The influence of parent material on regional compositional variations in Red Deer area soil is considerably less than that observed in the Rosetown area. This situation reflects the absence of texturally extreme surficial deposits (ie. relatively coarse sands and fine clays) and thus the small differences among mean concentrations for individual parent materials. Because of these relatively small among mean differences a greater number of samples are required per parent material to produce stable geochemical maps. 146a CHAPTER V SWAN RIVER - DAUPHIN AREA 147 A. DESCRIPTION OF STUDY AREA 1. GENERAL 2 The Swan River-Dauphin area covers approximately 15,000 km (6,000 sq mi) of western Manitoba and adjacent Saskatchewan (Fig 32). The climate, as in the western portion of the Red Deer area, is sub-humid. Mean July and January temperatures in agriculturally settled areas are about 18 and -19° C (65 and -2 ° F) respectively, and precipitation ranges from approximately 45 to 50 cm (18-20 in) annually (Ehrlich et al., 1959 and 1962). Elements of both the Manitoba Plain and Saskatchewan Plain physiographic regions are recognized within the area. The Saskatchewan Plain is represented by the Duck and Porcupine Mountains and Kenville and Valley River Plains: the Manitoba Plain includes both the Lowland and Swan River Plains (Fig 32). The break in slope between Saskatchewan and Manitoba Plains, locally referred to as the Manitoba Escarpment, is particularly well developed along the eastern margin of Duck Mountain. Topography in plain areas (elevations less than 510 m or 1700 ft) is generally smooth to gently sloping. The plateau-like sur face of the central upland, on the other hand, is characterized by numerous irregularly shaped morainic hills. v Because of the relatively high rainfall and cooler tempera tures, rivers and tributary streams are abundant throughout the region. Most streams, which begin in small upland lakes, are either dry by mid-summer or are occupied by discontinuous 148 101° 48' 100° 00' 52° 20' Tp38 Tp36 Tp34 Tp 32 Tp30 Tp28 Tp26 Tp 24 l0l°48' R24 R22 Figure 32. Topography and drainage, Swan River-Dauphin area. R20 5I°00' 100° 00' 149 bodies of stagnant water. Some of the river and larger stream channels have been eroded to bedrock, particularly in the area southwest of Dauphin where overburden is thin. 2. BEDROCK The region is underlain by a succession of carbonates, shales and sandstones which dip very gently in a southwesterly direction, and range from Devonian to Upper Cretaceous in age. Information on the distribution of bedrock units, indicated in Fig 33, was obtained from Cherry and Whitaker (1969), Klassen et al.(1970), Little (1973) and Moran and Whitaker (1969). Lithologic and stratigraphic descriptions were taken mainly from Wickenden (1945). Devonian limestones and dolomites (Unit 1) underlie the Lowland Plain in the northeast. Similar Paleozoic carbonates are widespread beneath the Manitoba Plain north and east of the study area. These rocks are overlain unconformably by a relatively thick ( 120 m or 400 ft) sequence of Jurassic to Lower Cretaceous marine and non-marine shale and sandstone, with minor limestone and evaporites (Units 2 and 3). Units 4, 5 and 6 which underlie the eastern slopes of Duck Mountain and large portions of both the Swan and Valley River basins, correspond respectively to the Cretaceous Ashville, Favel and Vermillion River organic-rich shale Formations. Greenish grey to grey shales of the most recent Upper Cretaceous Riding Mountain Formation (Unit 7), occur beneath most of the upland regions. 150 101° 48' CRETACEOUS ERiding Mountain: greenish grey, non-calcareous shale carbonaceous shale Favel: grey to black calcareous shale, minor limestone and bentonite Ashville: grey to black non-calcareous shale; minor sand and silt Swan River-.sandstone with shale and minor lignite JURASSIC 12 I Amaranth, Reston, Melita and Waskade: shale L=J sandstone, limestone, evaporites DEVONIAN tn Dawson Bay and Sourls River, limestone, dolomite, minor shale 100° 00' 52° 20' Tp38 Tp36 Tp34 Tp 32 Tp30 Tp28 Tp26 Tp 24 ^•SPOO" 100° 00' 101° 48' R24 Figure 33. Bedrock geology, Swan River-Dauphin area. R22 R20 Mo levels have been measured in rock material from some of these units. Delavault (1972) found only background Mo concentrations (<3ppm) in a limited number of samples of Riding Mountain Formation shale. Oddy (1966) however has reported enhanced Mo concentrations ( up to 14 0 ppm) in Ashville, Favel and Vermillion River Formations (Table XXXX). The Ashville Formation comprises a sequence of dark grey to black, locally bentonitic shales, which increase in thickness from about 30 m (100 ft) in the southern part of the area to approximately 105 m (350 ft) in the north. The Favel Formation, which is somewhat thinner (maximum thickness 36 m or 120 ft), consists of a grey to dark grey calcareous shale with minor limestone and bentonite. Vermillion River Formation strata (maximum thickness 72 m or 240 ft) have been divided into Morden, Boyne and Pembina Members. Basal Morden beds are composed of approximately 12 m (40 ft) of grey to black non-calcareous shale. Grey calcareous shales, from 12 to 24 m (40 to 80 ft) in thickness, characterize the overlying Boyne Member, which according to Wickenden (1945) correlates with Niobrara Formation shale in the United States. The uppermost Pembina Member ranges in thickness from 18 to 36 m (60 to 120 ft) and includes mainly grey to black non-calcareous shale. 3. SOIL PARENT MATERIAL Bedrock in the Swan River - Dauphin area is overlain by a 152 Table XXXX Mo content of Manitoba, bedrock units, Formation Lithology Mo Content* (ppm) Number of Analyses Riding Mountain non-calcareous shale 2.0 < 0.5-6.0 Vermillion River non-calcareous shale 19.4 3.0-120 22 Favel calcareous shale 49.4 13.0-140 31 Ashville non-calcareous shale 8.2 2.5-75.0 16 Swan River shale sand 2.5 2.5 6 1 Geometric mean and true range: Riding Mountain Formation data from Delavault ( 1972 ) ;. other data from Oddy (1966) . 153 variable thickness of unconsolidated Pleistocene surficial deposits, primarily of glacial origin (Fig 34). Drift thick ness ranges from less than one meter on the southeastern portion of the Valley River Plain where bedrock exposures are most common, to more than 100 m (300 ft) on Duck Mountain (Klassen et al., 1970). Deposits in plain areas consist for the most part of exotic strongly calcareous ground moraine, derived from Paleozoic carbonate, and to a lesser extent Precambrian granitic rocks to the northeast. Duck and Porcupine Mountains are characterized by somewhat less calcareous end moraines, which contain variable amounts of shale (Ehrlich et al., 1959). Ground moraine in the Valley and Swan River basins and eastern lowland is locally mantled by calcareous sand, silt, clay and to a lesser extent gravel deposits. These sediments, which were laid down in deltaic environments in former glacial Lake Agassiz (Ehrlich et al., 1959 and 1962), were probably derived from glacial drift to the west. Recent alluvial deposits, many of which are too local in extent to distinguish in Fig 34 are widespread in plain areas. Southwest of Dauphin, where stream-cut bedrock exposures are common, these deposits may locally contain significant amounts of shale. A limited number of geographically restricted, essentially residual surficial deposits have developed directly on shale. A few small bodies of Keld Soil Association "shale-till" occur on the southeastern portion of the Valley River Plain. Deep 154 IO0° 00* j I Calcareous ground moralne:source mainly limestone | 2 j Calcareous end morafne:source shale, limestone and granitic rock | | Calcareous lacustrine silt and clay Calcareous lacustrine sand | 1 Beach deposits | | Noncalcareous shale-till and shale-clay \S='o\ Recent alluvium LI Peat deposits RIVER JilM Tp30 Tp28 Tp26 Tp 24 f5l°00' 100° 00' 101" 48' R24 R22 Figure 34. Soil parent materials, Swan River-Dauphin area. R20 155 parent material samples obtained with the aid of a cobra drill (Fig 35), indicate that this shale-till grades at a depth of about one meter into non-calcareous bentonitic, presumably Vermillion River shale. A similar body of Favel Soil Series "shale-clay" is located on the Swan River Plain (Fig 36). Although soil survey information indicates that this deposit is underlain at shallow depth by calcareous till (Ehrlich et al., 1962), cobra drill investigations have shown that, at least locally, this material also grades into underlying shale, likely belonging in this case to the Ashville Formation. 4. SOIL Although most of the Swan River-Dauphin area occurs with in the Greywooded Soil Zone (Fig 5), Lowland and Swan River Plain soil belongs to the."High-lime" or Rendziria Zone. Upland areas are characterized by Luvisols, whereas on the Swan and Valley River Plains and eastern Lowland Regosolic, Chernozemic and Luvisolic Orders are all represented. These soils have been described in detail by Ehrlich et al. (1959 and 1962). Soil profile development in the eastern Lowland, as well as over wide regions in the river basins, has been retarded by both high calcium carbonate content of soil parent materials and generally poor internal drainage. Ground moraine in the Valley River basin and adjacent portions of the eastern Lowland is particularly carbonate-rich, and generally supports Orthic or Gleyed Regosols. Gleyed Black Chernozems predominate on lacustrine deposits in these areas, although Orthic Black 156 SOIL PARENT MATERIAL ONon-calcoreous shale -till (Keld Soil Assoc) , Calcareous till and •J sond BEDROCK Vermi Formation js^l Vermillion River —1300—Topographic contours (feet) ® Cobra drill sample site Tp24 Tp23 R2I R20 Figure 35. Soil parent material and bedrock, Keld oreo. Tp 36 me unit, if 7^ • /' /I Tp 35 R 25 SOIL PARENT MATERIAL ONoncalcareous shale-clay (Favel soil series) Calcareous till and Lacustrine deposits 0^) Cobra drill sample site *isoo—Topographic contours (feet) R24 BEDROCK FORMATIONS Y7A Swan River Ashville fTTffl Favel Vermillion River Figure 36. Soil parent maierial and bedrock, Favel area. soils occur locally on coarser textured sediments. Soils developed on till deposits in the Swan River basin and northern Lowland Plain are characteristically either Orthic or Gleyed Grey Wooded Luvisols, whereas lacustrine deposits in the Swan River basin typically support Gleyed Rego Black Chernozems. Chemical properties of some representative soil profiles are given in Table XXXXI. Soil pH values for C horizons are generally in the mildly to moderately alkaline range (7.4 - 8.4). Shale-derived Keld and Favel soils are exceptional in that their parent materials are acidic. Strongly acidic Keld Association soil is characteristically fine textured and poorly drained. Surface material is typically reddish, indicating the presence of abundant secondary iron oxides. Although it does not, strictly speaking, fit into the Canadian Soil Classification System, Keld soil has been clas sified by Ehrlich et al. (1959) as a Black Chernozem on the basis of A horizon characteristics. The Favel Series is also fine textured and poorly drained, but is generally grey and only slightly acidic. Salt concentrations are relatively high and Favel soils belong to the Solonetzic Order. 5. AGRICULTURAL LAND USE AND TRACE ELEMENT IMBALANCES Agricultural activity, chiefly small-scale mixed farming, is carried out most intensively on the Kenville, Swan River, Valley River and southern Lowland Plains. Wheat, barley and oats are the principal grain crops, whereas dairy and beef Table XXXXI Chemical properties of some representative Swan River-Dauphin area soil profiles (from Ehrlich et al., 1959 and 1962). 158 CaCO * • • „ • ^Pth J9^C ^i0n Equivalent pH Parent Sub- Association Horizon Carbon Exchange Material Group or series 1 ' (%) Capacity (%) (meq/lOOg) Calcareous Orthic Meharry L-H 3-0 17.9 - - 6.8 Till Regosol Ah 0-25 3.9 — 8.8 7.2 AC 25-30 1.7 - 17.6 7.6 C 30-90 0.6 — 43.9 8.1 Orthic ' Garison L-H 5-0 27.3 - - 6.9 Gray Ae 0-5 0.9 11.8 - 6.8 Wooded Bt 5-13 0.7 38.0 - 6.6 BC 13-35 0.4 15.7 40.1 7.6 C 35-71 0.3 50.5 7.9 Lacustrine Orthic Gilbert Ah 0-30 2.0 15.6 0.2 7.0 sand Black Bm 30-58 0.7 6.0 6.6 7.3 Ck 58-74 0.7 5.1 26.6 8.2 Cg 74+ 0.5 3.9 19.0 7.0 Lacustrine Gleyed Plainview L-H 5-0 - - - -silt and Rego Ah 0-15 6.7 54.9 0.6 7.5 clay Black AC 15-30 1.7 35.8 2.4 7.7 Ckg 30-50 0.2 24.6 25.3 8.3 Cg 50-90 0.3 23.7 24.2 8.3 Orthic Kenville L-H 3-0 12.3 - - 6.4 Dark (locally Ahe 0-33 4.6 - - 6.1 Gray Mo-toxic) Bt 33-53 1.4 - - 6.3 BC 53-61 1.1 - 5.2 7.4 C 61-102 1.1 — 14.5 7.8 Residual Gleyed Keld L-H 5-0 19.0 - nd 7.0 Shale Orthic Ah 0-20 8.1 - nd 5.5 Black Bm 20-64 1.0 - nd 4.1 Cg 64-102 1.1 — nd 3.5 Gleyed Favel Ahe 0-5 10.2 42.1 nd 5.8 Black Ae 5-10 4.0 25.3 nd 5.2 Solonetz Bnt 10-25 1.5 44.2 nd 6.0 BC 25-30 0.6 46.9 nd 6.2 Csg 30-69 0.5 36.9 8.8 6.1 * nd = not detected. 159 cattle, and swine are the major forms of livestock. The typically coarse textured and poorly drained soils of the cen tral and northern Lowland are utilized primarily for livestock production. Duck and Porcupine Mountains, characterized by steeply sloping and locally peaty soils, are maintained for the most part as forest reserves. The small areas of residual soil developed on shale are of only limited agricultural value. Keld Association shale-till soils are used mainly for mixed farming, although poor drainage and low pH values render these areas marginally productive. Similarly, poor drainage and high salt concentrations make Favel Series shale-clay soil suitable only for pasture. Mo-induced Cu deficiency (also referred to as Mo toxicity) was first reported in cattle by Cunningham et al. (1953) within a small area on the Kenville Plain (Fig 34). Subsequent det ailed investigations by Smith (1955) indicated Mo concentrations of up to 12 ppm in soils (Kenville Series) and 20 ppm in plants from the affected area. Typical symptoms included diarrhoea, anemia, fading of hair color and often death. Toxicity was over come by daily administration of two grams of copper sulphate either as a drench or salt lick. In recent years symptoms of Cu deficiency have been rec ognized in cattle throughout the Swan River-Dauphin area, assoc iated with a variety of highly calcareous soils. Blood Cu concentrations of affected animals are typically below normal 160 (Drysdale, 1975). Preliminary results of Cu supplementation studies indicate that the financial benefit which would accrue to the region from routine administration of additional Cu to all herds would be nearly 2 million 1974 dollars per annum (Drysdale, 1975). B. SAMPLE COLLECTION AND ANALYSIS 1. COLLECTION a) Bedrock Sixty-six bedrock samples were obtained from stream-cut exposures of Vermillion River, Favel, Ashville and Swan River Formations. The majority of samples were collected within the area of thin drift cover southwest of Dauphin (see Appendix C(6) for U.T.M. coordinates of sample sites). Only relatively unweathered material was taken, wherever possible as composite chip samples perpendicular to bedding. b) Stream Sediment Stream sediments were collected on a regional basis in the basins of both the Swan and Valley Rivers and along the eastern slope of Duck Mountain, in a manner similar to that recommended by Hawkes and Webb (1962). Over 200 samples were 2 taken at an average density of about one per 25 km (10 sq mi). Additional detailed stream sediment and bank soil sampling was carried out within the Mo-toxic area of Cunningham et al. (1953). Sampling localities for the regional survey were selected 161 a short distance upstream of road intersections with tribu tary streams. U.T.M. coordinates of site locations are given in Appendix C(5). Fine, organic-free material was obtained where possible from active stream channels and stored in kraft paper bags. c) Soil C horizons were collected at approximately 50 sites south west of Dauphin, during follow-up investigations of stream sediment anomalies. In part as a check on stream sediment sur vey results, A and C horizon soil was also obtained from about 7 5 sites throughout the Swan River Valley. Finally detailed A and C horizon sampling was carried out within three relatively small areas, two of which are centered on bodies of residual soil developed on shale bedrock., and the other being defined by the Mo-toxic area of Cunningham et al. (1953). For detailed studies sample sites were located at more or less regular intervals along grid roads at densities ranging 2 from about one per 2.5 to 5.0 km (1 to 2 sq mi). For regional 2 investigations 2.6 km areas (ie. 1 sq mi sections) for sampl ing were selected randomly over each major soil parent material. One sample site was located within each designated section to 2 give an average density of roughly one per 31 km (12 sq mi). Criteria governing the choice of sample site locations within selected sections, and procedures for A and C horizon collection were generally similar to those previously described in Chapter III (p. 60) . 162 Deep soil parent material samples were also obtained from residual shale (2 sites) and Mo-toxic Kenville soil (3 sites), using an Atlas Copco "Cobra Super" drill equipped with probing and soil sampling attachments. From 5 to 7 25 x 150 mm core samples were obtained at each site, at intervals of from 0.3 to 1.0 m (1-3 ft), to a maximum depth of about 5m (16 ft). d) Plants Although most plant sampling was undertaken within the three areas of detailed soil compositional investigations, a limited number of additional samples were obtained from random localities within the Swan River Valley. In total about 70 mixed grass samples and 40 samples of alfalfa (Medicago sativa L.) hay were collected. Although pasture grasses were preferred, in many cases samples were taken from uncultivated margins of either summerfallow or grain fields. A few samples of red clover (Trifolium pratense L.) were also obtained from some pastures. Sampling was undertaken for the most part, during a two week period in late June and early July 1974. The majority of grasses were either in or had passed the boot stage of development, and legumes were typically in the late bud or early flowering stages. Each sample was a composite of the above ground portions of several plants within a 30m X 30m (100 ft x 100 ft) quadrat centered on.a soil sample hole. Within a day or two of collec tion samples, stored in brown paper bags, were shipped to the laboratories of the Manitoba Department of Agriculture in 163 Winnipeg where they were air dried and ground. 2. ANALYSIS Approximate numbers and types of analyses performed are summarized in Table XXXXII. Procedures for sample preparation and analysis are described in detail in Chapter II. 3. ADDITIONAL INVESTIGATIONS Beginning in 1974, in part in conjunction with this study, the Manitoba Department of Agriculture undertook a large-scale soil and forage sampling program within the Swan River-Dauphin region and adjacent areas in west-central Manitoba. About 500 grass and 100 legume samples, as well as approximately 12 0 surficial and shallow depth soil samples, were obtained from pastures throughout the area. Dried and milled forage and unground soil material were sent to the University of British Columbia for trace element analysis according to the procedures described in Chapter II. Results of Manitoba Department of Agriculture investigations, were made available to the author (Fletcher, 1976), and are discussed in Section D in relation to the findings of this study. C. RESULTS - MOLYBDENUM AND COPPER 1. BEDROCK Nitric-perchloric acid extractable Mo concentrations in a limited number of samples from the Vermillion River, Ashville 164 Table XXXXII Approximate numbers, and types of analyses performed on Swan River - Dauphin area samples. Sample type Number of Analyses Mo Nitric-perchloric extraction Ammonium oxalate extraction Cu Se pH Bedrock Stream Sediment Soil: A horizon C horizon 66 215 125 225 36 16 10 125 125 Deep parent material Vegetation 29 110 110 27 and Favel Formations are given in Table XXXXIII. Mean values for Vermillion River and Favel shale are high - 13.0 and 14.0 ppm respectively. Individual shale samples from these forma tions may contain up to 40 ppm Mo and none contain less than 3 ppm. Although Ashville Formation shale may also be enriched in Mo (maximum concentration 15 ppm), nearly one-third of Ashville rock samples analysed contained only background con centrations (<3 ppm). Enhanced Mo concentrations were also detected in Favel Formation limestone (mean 5.1 ppm) and in gypsum, iron oxide and sulfur precipitates associated with Ashville shale. Mean values for Favel Formation bentonite and Swan River Formation sandstone and shale are low (<3 ppm). 2. STREAM SEDIMENT The distribution of Mo in minus 8 0-mesh stream sediment is shown in Fig 37. Individual sample values and U.T.M. co ordinates are listed in Appendix C(5). In contrast to the case for bedrock, stream sediment throughout most of the region, in cluding material obtained within the Mo-toxic area defined by Cunningham et al. (1953), characteristically contains less than 3 ppm molybdenum. Detailed stream sediment and associated bank soil sampling subsequently confirmed low concentrations within the area where Mo toxicity had been recognized (Fig 38). A limited number of relatively Mo-rich samples were how ever collected southwest of the town of Dauphin where drift 166 Table: .XXXXIII Mo content of Cretaceous bedrock, west-central Manitoba. Mo Content* Number Formation Lithology (ppm) of Analyses Vermillion River soft, black non-calcareous shale 13.0 4.0-30.0 14 Favel grey to black 14.0 calcareous shale; 3.0-40.0 minor limestone 23 Ashville limestone bentonite grey to black non-calcareous shale intermixed iron oxide and gypsum 5.1 2.0-30.0 2.5 2.0-4.0 4.6 < 1.0-15.0 5.0 5 3 13 Swan River sulfur white to orange unconsolidated sand 8.0 - 0.6 <1.0-1.0 1 4 brown siltstone and black non-calcareous shale 0.5 a) Geometric mean; true range. b) Individual data values, lithological descriptions and sample site locations given in Appendix C(6). c) Samples with less than detectable concentrations (1.0 ppm) assigned the value 0.5 ppm for mean calculations. 167 100° 00' 101° 4S" R24 R22 R20 Figure 37. Mo content of minus 80-mesh stream sediment, Swan River — Dauphin area. 100° 00' 168 SOIL PARENT MATERIAL pzi—1 Lacustrine clay I I Lacustrine silty clay I 1 (Kenville Series) Lacustrine sand 1 Glacial till Cunningham et al (I953)'s Mo-toxic area Molybdenum concentration PPm <2 Figure 38. Mo content of minus80-rnesh stream sediment (•) and A horizon bank soil (•), Mo-toxic area, Swan River Valley. 169 cover is thin. Locations of these anomalous samples relative to the distribution of associated bedrock formations and soil parent materials are shown in detail in Fig 39. Somewhat en hanced Mo levels (3-5 ppm) in both Wilson River and Edwards Creek sediment occur immediately downstream from exposures of Mo-rich Favel shale. Highest sediment Mo concentrations (up to 14 ppm) are associated with a small unnamed tributary of the Vermillion River in Township (Tp) 24 - Ranges (R) 20 and 21. Two small bodies of semi-residual till, derived from Mo-rich shale, are included within the catchment of this tributary one overlying Vermillion River and the other Ashville Formation bedrock. 3. SOIL AND PLANTS a) Nitric-Perchloric Acid Extraction Nitric-perchloric extractable Mo levels in C horizon soil associated with anomalous stream sediments are shown in Fig 40. Highest Mo values occur in material from the Vermillion River shale-derived till body (Keld Soil Association) at Keld Junction. Concentrations for C horizon soil, associated with similar Keld Association shale-tillH underlain by the Ashville Formation a few miles to the northeast, are somewhat lower (range 2.4 to 5.6 ppm). Samples from both lacustrine silty clay (Dutton Soil Association) and alluvium (Edwards Soil Association) situated near shale-till also tend to contain high Mo levels (>5 ppm). In contrast, Edwards Association alluvium along both Edwards Creek and the Vermillion River, Gilbert Association sands and ni9 \ V- -/ ooO c,° RJ DAUPHIN-\-v-SOIL PARENT MATERIALS Lacustrine clay Lacustrine silty clay .2 Mile* pMHr Km STREAM SEDIMENT Mo CONCENTRATION (ppm) >5 k ^e-mqr>ft.iodTfled from Fhrlich or al, 1959 (indKlassan etal,!970) Tp 25 Tp 24 Tp23 t;X;.;-X-J Lacustrine sand [ | Calcareous till:source mainly limestone | 1 Shale-till (Keld Soil Assoc) |o°„°o j Alluvium Figure 39. Mo content of minus 80-mesh stream sediment southwest of Dauphin. 3-5 <3 BEDROCK Riding Mountain Fm. @ Vermillion River Fm. <3) Favel Fm. © Ashville Fm. © Swan River Fm. X Outcrop Bedrock contact O R 21 R20 RI9 J„° o ° ° o ° ° o Jf> io BOO oj modified from Ehrlich et at.V 1959 ondKlassen etal.1970) Tp25 Tp24 Tp23 SOIL PARENT MATERIAL/SOIL ASSOCIATIONS L—_-| Lacustrine clay/mainly Dauphin Lacustrine silty clay/Dutton i'-lvXvj Lacustrine sand/Gilbert | | Calcareous till/Meharry and Isafold I I Shale-till/Keld SOIL MOLYBDENUM CONCENTRATION (ppm) >5 3-5 <3 BEDROCK (§) Riding Mountain Fm. @ Vermillion River Fm. (f) Favel Fm. (D Ashville Fm. © Swan River Fm. Bedrock contact l—1 H f0 ° ° 1 Alluvium/Edwards Figure 40. Mo content of selected C horizon soil samples, southwest of Dauphin. 172 Meharry and Isafold Association tills typically contain less than 3 ppm molybdenum. Results of detailed soil and plant compositional investiga tions in the vicinity of Keld Junction (Keld area) are summarized in Fig 41 and Tables XXXXIV to XXXXVI. Strongly acidic (pH 5.3) Keld Association C horizon soil in this area contains an average of about 7 and up to 20 ppm Mo (Fig 41 and Table XXXXIV). Alka line soils developed on associated calcareous till and lacustrine deposits, on the other hand, are comparatively Mo-poor. Analyses of cobra drill samples (Table XXXXV) suggest that Mo concentra tions in the parent bedrock may be higher (by a factor of about 2.0) than levels in overlying soil. In contrast to the case for soil, Mo levels in plants from this area exhibit little among parent material variability (Table XXXXVI). Concentrations in grasses associated with shale-till are low (mean 1.3 ppm) and comparable to those for material from other surficial deposits, whereas values for alfalfa samples are uniformly high (>6 ppm). Plant Cu concentra tions are within the normal range for forage. Like Mo, plant Cu data appear to be most strongly influenced by variations in plant type, alfalfa tending to be somewhat enriched in this element relative to grasses. Nitric-perchloric extractable Mo concentrations in Swan River Valley soil, including material from the Mo-toxic area of Cunningham et al. (1953), are indicated in Fig 42 and Tables XXXXVII and XXXXVIII. Consistent with stream sediment survey Figure 4 I Mo content of C horizon soil, Keld area. Table ..XXXXIV Mo content and pH of A and C horizon soil associated with individual soil parent materials, Keld area. Parent Number Horizon Material Mo Content* pH** of (ppm) Analyses Shale-till 3.4 7.6 9 (Keld Assoc.)<0.8-16.0 7.2-8.3 Calcareous 0.8 7.9 18 till <0.8-3.2 7.6-8.5 Lacustrine 0.4 7.8 9 sand - 7.6-7.9 Shale-till 6.7 5.1 9 (Keld Assoc.) 2.4-20.0 3.4-7.1 Calcareous 1.1 8.1 17 till <0.8-6.0 7.2-8.4 Lacustrine 0.7 8.3 9 sand <0.8-8.0 7.7-8.8 a) Geometric mean; true range: samples with less than detectable concentrations (0.8 ppm) assigned the value of 0.4 ppm. b) Individual data values listed in Appendix C (7). ** Arithmetic mean; true range. 175 Table. XXXXV Mo content of shale-till parent material and underlying bedrock, Keld area. Cobra Drillhole Sample Mo Content (ppm) Location* Approximate Description depth (m) SW5-24-20W1 0.7 clay:mottled grey, 12.0 non-calcareous, bentonitic 1.0 clay:mottled grey, 14.0 non-calcareous, bentonitic 1.3 shale:soft, dark, 20.0 non-calcareous, bentonitic 1.6 shale:soft, dark, 24.0 non-calcareous, bentonitic 1.9 shale:soft, dark, 20.0 non-calcareous, bentonitic 2.2 shale:soft, dark, 32.0 non-calcareous, bentonitic 2.5 shale:soft, dark, 14.0 non-calcareous, bentonitic * Section - township - range 176 Table'XXXXVI Mo and Cu content of vegetation (dry weight basis) associated with individual soil parent materials, Keld area. Plant Type Parent Material Trace Element* Content (ppm)  Mo Cu Percentage of samples with Cu:Mo ratios <4 . 0 Number of Analyses Grass Shale-till 1.3 8.3 (Keld Assoc.) 0.6-2.4 6.5-10.1 13 8 Calcareous till 1.1 0.4-3.4 8.6 6.5-12.1 13 Lacustrine sand 1.0 0.4-2.0 7.2 4.1-9.8 13 Alfalfa Shale-till (Keld Assoc.) 7.0 12.2 100 Calcareous till 7.8 6.0-10.0 10.5 8.9-13.0 100 Lacustrine sand 7.0 10.6 100 * a) Geometric mean; true range. b) Individual data values listed in Appendix C( 7). 177 R26 Tp36 B2<H. Tp34 Tp32 Mo CONCENTRATION ppm © 3-5 • < 3 Cunningnom et ol (I953)'s Mo-toxic area SOIL PARENT MATERIAL [ | Calcareous till: contains some shale along southern margin Lacustrine silt and clay |':|V:':V:': Lacustrine sand I Shale-clay (Favel Soil Series) Figure 42. Mo content of C horizon soil, Swan River Valley. 178 Table XXXXVII Mo content and pH of A and C horizon soil associated with major soil parent materials, Swan River Valley. Parent Mo Content* Number Horizon Material (ppm) pH** of Analyses A Mo-toxic 0.7 7.0 19 lacustrine silt <0.8-1.6 6.4-7.8 (Kenville Series) Lacustrine 0.4 7.5 17 silt and clay <0.8-0.8 6.2-8.2 Calcareous till+ 0.8 7.6 9 <0.8-2.4 7.1-7.9 Lacustrine 0.6 7.6 10 sand < 0.8-2.4 6.8-8.0 C Mo-toxic 0.9 7.6 25 lacustrine silt < 0.8-3.2 5.9-8.2 (Kenville Series) Lacustrine 0.6 8.1 38 silt and clay <. 0.8-4.0 7.7-8.5 Calcareous till t 0.8 7.9 19 < 0.8-3.2 7.7-8.2 Lacustrine 0.7 8.1 18 sand < 0.8-2.4 7.9-8.5 TLocally contains some shale. * a) Geometric mean; true range: samples with less than detectable concentrations (0.8ppm) assigned the value 0.4ppm. b) Individual data values listed in Appendix C(8)~ . ** Arithmetic mean; true range. 179 results neutral to mildly alkaline Swan River Valley soil, includ ing material associated with locally shale-bearing calcareous till along the southern margin of the valley, typically contain less than 3 ppm molybdenum. Despite concentrations of up to 12 ppm reported by Smith (1955) for Kenville Series soil from the Mo-toxic area of Cunningham et al. (1953), only background concentra tions were detected in these soils. Deep Kenville soil parent ma terial samples (Table XXXXVIII) were similarly found to be relatively Mo-poor. Mo and Cu concentrations for plants growing within the Mo-toxic area are compared to values for material collected elsewhere in the Swan River Valley in Table XXXXIX. In contrast to the case for soils, grass from the affected area tends to be somewhat enrich ed in molybdenum. One sample of pasture grass from within this area contained 20 ppm Mo, and symptoms of Cu deficiency were evident in cattle grazing this material. Mean values for both toxic and background area legumes are similar, and are somewhat elevated relative to those for grasses. Although Cu concentrations in grasses from the Mo-toxic area are not exceptional (range 3-11 ppm), legumes from this area contain relatively low amounts of Cu in comparison with legumes from other regions. Results of detailed soil and plant compositional investi gations in the vicinity of the body of Favel Series shale-clay east of Swan River (Favel area) are shown in Fig 43 and Tables L to LII. Consistent with stream sediment data, Mo concentrations for this residual shale-clay soil (Table L) and the underlying presumably Ashville Formation shale (Table LI) are low «3 ppm). Similarly 180 Table XXXXVIIIMo content of Mo-toxic area Kenville Soil Series parent material. Sample  Cobra Drillhole Approximate Description Mo Location* Depth (m) Content (ppm) SE32 - 34 - 29W1 0.5 1.5 2.3 3.5 4.1 calcareous fine sand and silt; small iron oxide concretions calcareous sand with small iron oxide concretions as above as above slightly calcareous silt, orange staining 2.4 0.8 < 0 1 8 6 4.0 SE17 - 35 - 29W1 NW11 - 35 - 29W1 1.1 calcareous find sand and silt; small iron oxide concretions < 0.8 1.7 as above 0.8 2.3 as above 0.8 2.9 as above 1.6 4.1 as above 1.0. calcareous silt to fine < 0.8 sand; orange steining 1.4 as above 0.8 1.7 calcareous silt and clay: 0.8 orange stoining 2.3 as above 0.8 2.8 as above 1.6 3.2 as above; no staining 2.4 3.7 as above; no staining 0.8 * Section - township - range. 181 Table XXXXIX Mo and Cu content of vegetation, (dry weight basis), Swan River Valley. Plant .Type Area Trace Element Content (ppm) * Percentage of samples with Cu:Mo ,ratios<4.0 Mo Cu Number of Analyses Grasses Mo-toxic area 3.0* 0.6-12.0 5.7 3.0-10.7 89 19 Other areas 1.6 0.8-2.8 6.0 4.7-11.9 38 Legumes** Mo-toxic 3.6 6.8 area 1.0-6.0 6.5-8.7 83 Other areas 4.5 1.0-8.0 10.5 5.0-15.7 88 16 a) Geometric mean; true range. b) individual data values listed in Appendix C (8) . ** Includes both alfalfa and red clover. f One sample containing 20ppm molybdenum rejected as being unrepresentative of target population. R 25 R 24 SOIL PARENT MATERIAL | | Shale-clay (Favel Series) Lacustrine silt and clay Lacustrine sand [ I Calcareous till: contoins some shale MOLYBDENUM CONCENTRATION ppm % 3-5 • <3 i—1 co to Figure 43. Mo content of C horizon soil, Favel area. 183 Table L Mo content and pH of A and C horizon soil associated with individual soil parent materials, Favel area. Parent Mo Content* Number Horizon Material (ppm) pH** of Analyses Shale-clay 0.6 7.1 9 (Favel Series) < 0.8-5.6 6.5-8.2 Lacustrine 0.9 7.5 10 silt and clay < 0.8-2.4 6.6-8.0 Calcareous"]" 0.5 7.3 8 till < 0.8-0.8 6.4-8.1 Lacustrine 0.4 7.7 6 sand - 7.1-8.7 Shale-clay 0.6 6.8 10 (Favel Series) < 0.8-1.6 4.7-7.7 Lacustrine 1.0 7.5 11 silt and clay < 0.8-3.2 6.4-8.2 Calcareous"! 0.5 7.4 8 till < 0.8-0.8 6.2-8.2 Lacustrine 0.5 8.1 5 sand < 0.8-0.8 8.0-8.1 "J" Locally contains some shale. a) Geometric mean, true range: samples containing less than detectable concentrations (0.8ppm) assigned the value of 0.4 ppm. b) Individual data values listed in Appendix C(9). * * Arithmetic mean; true range. 184 Table LI Mo content of Favel Series shale-clay and underlying shale, Favel area. Sample Cobra Drillhole Approximate Location* Depth(m) Description Mo Content (ppm) SW11-36-25W1 0. 5 clay: grey, non-calcareous 1 .6 1. 0 silty shale:soft,grey,non- <0 .8 calcareous 1. 4 as above with minor bentonite<0 .8 1. 9 shale:soft, black non- <o .8 calcareous, bentonitic 2. 3 as above <0 .8 * Section - township - range. 185 Table LII Mo. and Cu content of vegetation (dry weight basis) associated with individual soil parent materials, Favel area. Plant Type Parent Material Trace Element* Content (ppm) Mo Cu Percentage Number of samples of with Cu:Mo Analyses: "ratios<4.0 Grass Shale-clay (Favel Series) Lacustrine silt and clay Calcareous till t 1.4 0.6-4.0 1.1 0.6-1.8 2.7 1.0-5.0 7.7 4.4-11.5 7.6 6.0-8.7 6.0 4. 4.-10.7 25 13 86 Lacustrine sand 1.6 0.4-4.0 9.3 6.4-13.7 50 Legumes** Shale-clay (Favel Series) Lacustrine silt and clay Calcareous till Lacustrine sand t 15.2 6.0-28.0 10.0 6.2 3.4-12.0 7.6 4.0-12.0 9.6 5.7-14.1 7.4 7.0 5.4-9.4 9.3 8.1-12.0 100 100 100 100 ~ Locally contains some shale. * a) Geometric mean; true range. b) Individual values listed in Appendix C(9). ** Includes both alfalfa and red clover. 186 low values are associated with other soil parent materials, including calcareous till which locally contains some shale (Ehrlich et al., 1962). Although grasses associated with soil of the Favel Series are not enriched in Mo (Table LII), samples obtained over shale-bearing calcareous till contain slightly more Mo (mean 2.7ppm) and less Cu (mean 6.0 ppm) than grasses associated with other parent materials. Consistent with previous observations legumes contain larger amounts of Mo than grasses, but in this area a similar trend is not apparent for copper. b) Acid Ammonium Oxalate Extraction Acid ammonium oxalate extractable soil Mo has been related by Grigg (1953 a, b) to the Mo status of associated plants. The effectiveness of this extractant in assessing plant-available Mo levels in Swan River-Dauphin area soil was therefore investigated. Oxalate extractable Mo concentrations were determined for selected C horizon soil samples associated with both Mo-rich (> 5 ppm) and background (< 3 ppm) grasses. Because a relatively large number of analyses were performed on material from the Mo-toxic area outlined by Cunningham et al. (1953), data from this reg ion are considered separately. Soils associated with Mo-rich grasses outside of Cunningham et al. (1953) 's Mo-toxic area were obtained in part from Manitoba Department of Agriculture collections. Ammonium oxalate extraction results are summarized in Table LIII. Within the Mo-toxic area this extractant removed 187 Table LIII Acid ammonium oxalate extratable Mo content of selected C horizon soils associated with both Mo-rich and Mo-poor grass samples. Oxalate Grass Extractable Number Soil Type Mo-status** Molybdenum* of (ppm) Analyses .n. _ . Anomalous 1.4 4 Kenville Series Q Cj_-^ g Mo-toxic area Background 0.5 8 0.2-2.0 ^ ., Anomalous 0.4 Assorted n i o Q Q calcareous lacustrine and till soils Background 0.2 13 < 0.1-4.0 a) Geometric mean; true range. b) Samples containing undetectable amounts of molybdenum «0.1 ppm) assigned a value of 0.05 ppm. Anomalous ^ 5.0 ppm; background<C3.0 ppm. 188 nearly three times as much Mo from samples associated with Mo-rich grasses as from samples supporting grass with only back ground Mo levels. Despite the small number of observations, the difference between anomalous and background mean values is significant at about the 90% confidence level. Throughout the remainder of the Swan River-Dauphin area oxalate extractable soil Mo levels do not appear to be closely related to concentra tions in associated plants. D. DISCUSSION - MOLYBDENUM AND COPPER 1. BEDROCK Mean nitric-perchloric extractable Mo concentrations in Vermillion River, Favel and Ashville Formation grey to black shales (13.0,14.0 and 4.6 ppm respectively) are high relative to Turekian and Wedepohl (1961)'s estimated average for shale (2.6 ppm), but are comparable to the median value of 10 ppm given by Vine and Tourtelot (1970) for North American black shale. In Kansas, organic-rich Niobrara Formation shale, the stratigraphic equivalent of the Boyne' Member of the Vermillion River Formation, is also reportedly enriched in Mo (Vine and Tourtelot, 1970). Oddy (1966) found means of 19.4, 49.4 and 8.2 ppm Mo in Vermillion River, Favel and Ashville Formation shales respec tively. His values, particularly for the Favel Formation, are considerably higher than those reported in this study. The apparent discrepancy is attributable, in large measure, to 18 9< differences in sample digestion procedures. Oddy (1966) used a total hydrofluoric-perchloric attack, whereas in this study a nitric-perchloric procedure was employed. As noted previously (p. 37), the nitric-perchloric attack used releases only about 40% of the Mo liberated by a hydro fluoric acid based attack. Elevated Mo concentrations in organic-rich shales are usually attributed to removal of this element from sea water by sediment collecting in anaerobic marine basins. This is generally considered to occur either by direct adsorption of Mo by decaying organic matter (LeRiche, 1959; Tourtelot, 1964) or by coprecipitation with iron sulfide (Korolev, 1958). Although the phase associations of Mo were not specifically examined for Maintoba shales, Vine and Tourtelot (1970) concluded that Mo in similar shales in the mid-western United States is more associated with organic matter than with sulfides. 2. SOIL Enhanced concentrations of nitric-perchloric extractable Mo (> 5 ppm) in soil within the area of thin drift cover south west of Dauphin (Fig 4 0) reflect the incorporation of variable amounts of Mo-rich shale into local parent materials. Anoma lous Keld Association soil near Keld Junction, for example, has developed almost exclusively on highly weathered Mo-rich Vermillion River shale. Similarly high Mo concentrations in Edwards Association alluvium are probably a result of downstream transport of shale-derived Keld Association material, as well 190 as Favel shale from stream-cut exposures. Elevated Mo con centrations in soil associated with Mo-rich shale have been reported in the United States by Massey and Lowe (1961) and in Canada by Doyle et al. (1973). Mo levels for Keld Association soil developed on the Ashville Formation (Fig 40) are considerably lower than values for Vermillion River shale-derived soil. This is consistent with low concentrations (<2 ppm) in many of the Ashville Formation samples analysed (Table XXXXIII) and with low Mo concentrations in Favel Series shale-clay east of Swan River (Tables L and LI). Reduced Mo concentrations in A relative to C horizon Keld Association soil developed on Vermillion River shale (Table XXXXIV), suggest that extensive surface leaching has taken place. This is somewhat surprising because clay-rich Keld soil is typically poorly drained, and its strongly acidic character and high Fe content would be expected to severely limit the mobility of Mo (Jones, 1957; Reisenaur et al., 1962). Further evidence of the removal_of Mo from this soil is how ever apparent in the low concentrations in weathered shale-clay parent material relative to the underlying fresh shale (Table XXXXV). Generally low Mo values for soils developed on both cal careous till and lacustrine deposits in the Swan River Valley (Fig 42) and southwest of Dauphin (Fig 40) indicate that rela tively little Mo-rich shale has been incorporated into these 191 deposits. In view of the generally close relationship between stream sediment and upstream soil composition (Thornton and Webb, 1970), low Mo values in sediment throughout the Valley River Plain and along the eastern margin of the Lowland Plain suggest that the associated soils are also Mo-poor. This is consistent with the observation of Ehrlich et al. (1959) that tills in these areas are derived mainly from exotic limestone and granitic rock. Concentrations for Kenville Series soil from the Mo-toxic area of Cunningham et al. (1953) are considerably below the enhanced values of up to 12 ppm. reported in this area by Smith (1955). As in the case of bedrock data this inconsistency is in part a consequence of differences in sample digestion pro cedures. Smith (1955), like Oddy (1966), used a hydrofluoric acid based attack which would be expected to liberate more Mo than the nitric-perchloric acid mixture used for this study. However, analysis of a representative suite of Kenville soils for total Mo using a sequential ammonium oxalate/hydrofluoric-nitric-perchloric acid extraction indicated a maximum Mo con centration of only 5 ppm, and an average of 2.2 ppm. Further more, low total Mo values (< 2 ppm) for selected Kenville Series samples were confirmed by a separate semiquantitative emission spectrographic procedure (Marshall, 1973) . These results sug gest that the accuracy of the anomalous soil concentrations reported by Smith (1955) is questionable. 192 3. PLANTS Enhanced Mo values (> 5 ppm) in grasses from the Mo-toxic area are consistent with high concentrations previously noted by Smith (1955). Excluding these results, Mo values for grasses are generally within the normal range for forage (<3 ppm), where as those for legumes are relatively high. Because of limited sampling, however, a large proportion of non-toxic area grasses, and to a lesser extent legumes, were obtained within two rela tively restricted areas centered on shale-derived soil bodies (Keld and Favel areas). A more complete regional picture of the distribution of Mo in forage is provided by results of Manitoba Department of Agriculture investigations. In agree ment with findings of this study, their data show enhanced values for Mo in legumes compared to grasses, with concentrations equal to or greater than 5 ppm ( and up to 7 0 ppm ) noted in over 40% of the legumes (Fletcher, 1976). Although values for the majority of grasses were less than 3 ppm, nearly 25%, most of which were collected outside the Mo-toxic area of Cunningham et al. (1953), contained 5 ppm or more Mo (Fletcher, 1976). Plant Mo concentrations, like those of other elements, are influenced by a variety of plant and soil variables. Plant factors of importance include the genotype,age and part of plants sampled (Sauchelli, 1969; Barshad, 1951a). Of these the effects of plant genotype are particularly apparent in this study. As indicated in Tables XXXXVI, XXXXIX, and LII, Mo concentrations in legumes are invariably higher than concentrations for grasses 193 growing in the same soil. In the Favel area (Table LII) legumes may be enriched by as much as a factor of 10 relative to grasses. Similar grass-legume compositional differences have been reported by other workers in the United States (Barshad, 1948; Jensen and Lesperance, 1971) as well as in the British Isles (Webb et-al., 1968). The tendency for legumes to con centrate relatively large amounts of Mo is probably related to the presence, on their roots, of bacteria which require Mo in the process of nitrogen fixation. With regard to soil factors influencing Mo uptake, varia tions in soil parent material appear, at least locally, to be of significance. Thus in the Favel area legumes growing on shale-clay (Favel Soil Series) contain exceptionally high Mo levels (mean 15.2 ppm), whereas.grasses associated with cal careous till, which contains variable amounts of shale, are also slightly enriched in this element (mean 2.7 ppm). Further more, regional maps of Manitoba Department of Agriculture data (Fletcher, 197 6) show that Mo-rich grasses are particularly common over calcareous shale-bearing till deposits (Unit 2, Fig 34), which are widespread in the central and western portions of the area. These plots also show that, although anomalous grasses are associated with a variety of parent materials located west of the contact between Mo-rich shale and underlying Mo-poor bedrock (Units 3 and 4, Fig 33), enhanced Mo concentra tions do not occur in grasses east of this line. Variations in plant Mo content are not, however, directly 194 relatable to nitric-perchloric extractable soil Mo levels. For example, although high Mo levels occur in soils developed on Keld Association shale-till, grasses growing in this soil contain relatively small amounts of molybdenum. Furthermore, both anomalous and background concentrations occur in grasses growing in a variety of similarly Mo-poor soils. Lack of increased Mo uptake by grasses associated with Keld soil is probably related to its strongly acidic character (C horizon pH 5.3). Greenhouse experiments by Barshad (1951a) have shown that as soil pH decreases through the range 8.0 to 5.0, Mo concentrations in both grasses and legumes fall by a factor of at least 2.0. Jones (1957) and Reisenaur et al. (1962) have demonstrated experimentally that this pH effect is related to the ability of soil clays and hydrous iron oxides to adsorb progressively larger amounts of Mo, as the molybdate anion, from aqueous solution as pH levels decrease. The absence of a relationship between plant and soil Mo values for Mo-poor soils probably, in part, reflects the relative ly high detection limit and poor precision of the routine ana lytical method. In an attempt to overcome this problem the method of estimating available Mo using an acid ammonium oxalate extrac tion, recommended by Grigg (1953 a, b), was employed. This re agent would be expected to release Mo combined with secondary iron oxides, which it selectively dissolves (Rose, 1975), as well as exchangeable Mo associated with other soil phases. Since originally proposed, this procedure has been used to 19 5 measure plant available Mo by a number of investigators, with variable degrees of success' (Gupta and MacKay, 1966; Pathak et al., 1969; Walker et al., 1954). Results of applying Grigg (1953 a,b)'s procedure to Swan River-Dauphin area soils (Table LIII) are inconclusive. Oxalate extractable Mo for Kenville Series material within the Mo-toxic area defined by Cunningham et al. (1953) appears to be closely related to associated grass Mo concentrations, with soils sup porting Mo-rich forage containing relatively high extractable Mo values. Elsewhere, however, values for a variety of differ ent non-toxic area soils display relatively little relationship to grass contents. Takahashi (1972) reported poor correlation between plant and oxalate extractable Mo unless data for individual soil types were considered separately. This likely reflects the effects of changes in soil environmental conditions on the availability of molybdenum. The Mo content of plants is known to be influenced by such soil factors as pH, drainage, organic matter content, sulphate and phosphate levels (Barshad, 1951 a,b; Kubota et al., 1963; Stout et al., 1951). The bedrock source, which determines the original form of the Mo is also important. High Mo concentrations in vegetation associated with Mo-poor soils indicate that locally these factors combine to render a large proportion of the total soil Mo available for uptake by plants. Alkaline conditions in many Mo-poor soils would favour increased Mo uptake, but this cannot be the only factor of importance because alkaline soils also give rise to 196 forage with normal Mo levels. Fertilization practices could also be significant, because as Stout et al. (1951) have noted, plant Mo content tends to increase in the presence of phosphate. The importance of bedrock type is suggested by the fact that Mo-rich grasses occur almost exclusively in areas underlain by either Ashville, Favel, Vermillion River or Riding Mountain Formations. The precise nature of the relationship between bedrock and plant Mo.content is not at present clear however. Detailed investigations of the factors responsible for elevated plant Mo concentrations associated with Kenville and Favel Series soils were not undertaken. Mineralogical analyses of selected Kenville soils by Smith (1955), however, indicated the presence of abundant shale fragments and hydrated ferric oxides. He suggested that Mo in these soils is a constituent of the ferric oxides. If so, this would help to explain ano malous grass concentrations, because under the prevalent neutral to moderately alkaline soil conditions Mo would be expected to be relatively loosely bound to these oxides and hence would be comparatively available to plants. In the case of Favel Series soil, enhanced Mo levels in legumes may be related to poor drainage conditions, which according to Kubota et al. (1963) and Jensen and Lesperance (1971), tend to promote Mo uptake. 4. AGRICULTURAL SIGNIFICANCE OF THE DATA The ingestion of large amounts of Mo is known to inhibit the ability of ruminants to utilize dietary Cu supplies 197 (Underwood, 1962). Although the strength of this effect is influenced by such factors as inorganic sulfate and protein, as well as Zn and Pb intakes (Underwood, 1976), the Cu adequacy of animal diets is, in practice, generally assessed in relation to associated Mo concentrations only. Miltimore and Mason (1971) suggest, on the basis of experience in British Columbia, that Cu deficiency is likely to occur in areas where feeds are characterized by Cu:Mo ratios of less than 2.0. As Underwood (1976) however points out, other workers have noted symptoms of Cu deficiency in livestock associated with Cu:Mo ratios of closer to 4.0. In Manitoba, provincial agricultural scientists have defined 4.0 as the minimum acceptable Cu:Mo ratio . for cattle (Drysdale, 1975). Deficiencies resulting from consump tion of feeds with ratios of less than 4.0 are called "conditioned" or "Mo-induced". "Simple" Cu deficiency, on the other hand, may be caused by the ingestion of inadequate absolute amounts of Cu in the presence of very low Mo concentrations. In Manitoba, forage Cu concentrations of at least 10 ppm are considered essential for cattle (Drysdale, 1975). As indicated in Tables XXXXVT, XXXXIX and LH almost all legumes analysed in this study (most of which were alfalfa hay), because of their relatively high Mo content, are characterized by Cu:Mo ratios of less than 4.0. Furthermore, nearly half of these legumes contain less than 10 ppm Cu, with values for material from the Mo-toxic area of Cunningham et al. (1953) being 198 particularly low. Most grasses are absolutely deficient in Cu, and Cu:Mo ratios for about 43% of the samples analysed are below 4.0. Although low ratios occur in grasses associated with a wide variety of parent materials, they are especially common in Mo-rich samples obtained within the Mo-toxic area (Table XXXXIxy and in material collected over Favel area cal careous shale-bearing till (Table LII). A similar pattern is apparent in the" Manitoba Department of Agriculture plant data. Cu concentrations of less than 10 ppm occur in nearly all of the grasses and about 9 0% of the pasture legumes, whereas Cu:Mo ratios of below 4.0 characterize about 66% of the grasses and 84% of the legumes (Fletcher, 1976). In agreement with results of this study, low grass ratios are as sociated with a variety of soil types, but are particularly common in material obtained over calcareous shale-bearing till deposits (Unit 2, Fig 34). Consistent with these data Manitoba Department of Agri culture personnel have diagnosed both .simple and conditioned Cu deficiency in cattle throughout the study area (Drysdale, 1975). Pasture grasses are probably a major factor in this problem since they appear to be regionally deficient in Cu and are locally enriched in molybdenum. Deficiency conditions may be further aggravated by the presence of Mo-rich legumes in some pastures, as well as enhanced Mo levels in alfalfa hay, although as Stiles (1946) has noted Mo in hay is considerably less toxic than in fresh forage. 199 E. RESULTS - SELENIUM Results of Se analyses of bedrock, C horizon soils and plants are summarized in Tables LIV, LV and LVI respectively. As indicated in Table LIV Se concentrations in selected Mo-rich shales range between 1.3 and 24.8 ppm. Values for the Vermillion River Formation (mean 12.2 ppm) are characteristically high relative to those for the Favel (mean 3.3 ppm) and Ashville (mean 4.8 ppm) Formations. Se, like Mo, does not appear to be enriched in C horizons of either the Favel or, in the Mo-toxic area of Cunningham et al. (1953), Kenville soils (Table LV). Mo-rich Keld Association soil contains an average of 4.3 and up to 7.4 ppm selenium. In view of the apparent association between enhanced Mo and Se concentrations in both bedrock and soil, a limited number of Mo-rich and Mo-poor plants were analysed for selenium. As indicated in Table LVI, concentrations are generally low (<1 ppm). Values of over 3 ppm were detected in only two samples, one a grass growing on Mo-toxic Kenville Series soil, and the other a clover associated with the Favel Soil Series, east of Swan River. F. DISCUSSION - SELENIUM 1. BEDROCK Se concentrations in Mo-rich Vermillion River, Favel and Ashville Formation shale are well above Goldschmidt (1954)'s 200 Table LIV Se content of selected Mo-rich bedrock samples, west-central Manitoba. Formation Lithology Se Content* Number (ppm) of Analyses Vermillion River soft, black 12.2 non-calcareous shale 6.8-24.8 Favel grey to black calcareous shale 3.3 1.3-4.9 Ashville grey to black 4 . 8 non-calcareous shale 3.1-6.1 a) Geometric mean; true range. b) Individual concentrations and brief lithological descriptions listed in Appendix C(6). 201 Table LV Se content of selected C horizon soil samples, west-central Manitoba. Soil Se Content* (ppm) Number of Analyses Keld Association shale-till 4.28 2.18-7.36 Favel Series shale-clay 0.50 0.37-0.92 Kenville Series Mo-toxic area 0.50 0.24-0.76 a) Geometric mean; true range. b) Individual data values listed in Appendix C(7-9) 202 Table LVI Se content of selected plant samples (dry weight basis), west-central Manitoba. Plant Type Number ClassT Se Content* of (ppm) Analyses Grasses Mo-poor 0.48 0.12-0.84 Mo-rich 0.64 0.26-4.32 Legumes** Mo-poor 0.58 0.22-1.06 Mo-rich 0.6 0 0.09-4.00 a) Geometric mean; true range. b) Individual data values listed in Appendix C(8-10). Alfalfa and red clover. tMo-rich > 5 ppm Mo-poor < 5 ppm 203 estimated crustal abundance of 0.09 ppm and Turekian and Wedepohl (1961) *s average for shale of 0.6 ppm. High concentra tions in Vermillion River shale are consistent with enhanced Se values found by Lakin (1961) in stratigraphically equivalent Niobrara Formation shale from Colorado and Kansas. The associa tion of anomalous amounts of Mo and Se in organic-rich shale has also been reported by Fletcher et al. (1973), Tourtelot (1962) and Webb et al. (1966). It should be noted, however, that the digestion procedure for Se was only partially effective in destroying the highly resistant organic fraction of these shales, and therefore the accuracy of values reported in Table LIV is questionable. Nevertheless, the fact that data are consistent with results reported by other investigators for similar rocks suggests that they can at least be taken as reliable indications of above average concentrations. As with Mo, enhanced levels of Se in organic-rich shales are commonly attributed to adsorption from sea water by both organic matter and clay minerals (Tourtelot, 1964) . 2. SOIL According to Swaine (1955) Se levels in soil typically range between 0.1 and 2.0 ppm. Concentrations in C horizon Keld Association soil (mean 4.3 ppm) are therefore anomalously high, whereas those in Favel and Kenville Series samples (means 0.5 ppm) are not exceptional. High values in Mo-rich Keld soils are not 204 surprising in view of the elevated Se concentrations noted in Vermillion River shale (Table LIV) on which this soil has developed. Enhanced Se concentrations in soil derived from Se-rich shale have also been reported in the United Kingdom by Webb et al. (1966) and in the United States by Jackson (1964). Background concentrations in Favel and Kenville soils are consistent with their previously noted low Mo content. 3. PLANTS In contrast to the case for bedrock and soil, Se levels in plants do not appear to be related to Mo contents (Table LVI). The mean Se content of Mo-rich legumes, for example, 0.60 ppm, is only 0.02 ppm greater than that for Mo-poor ma terial. Also, unlike the pattern for Mo, Se concentrations in sampled legumes (alfalfa and clover) are not generally elevated compared to those of grasses. Miltimore et al. (1975) have likewise observed similar Se levels in grass and legume forage in British Columbia. The overall average Se content for both grasses and legumes, 0.58 ppm, is considerably higher than concentrations reported for forage from other parts of Canada. Miltimore et al. (197 5), for example, found an average of only about 0.20 ppm in grass-legume forage throughout British Columbia, whereas Lessard et al. (1968) noted typical concentrations of less than 0.1 ppm in grasses in Northern Ontario. Relatively enhanced plant concentrations in the Swan River-Dauphin area are probably, 205 in part, a result of the prevalent alkaline soil conditions, because as Lakin (1972) has pointed out, high pH values tend to favour the availability of Se to plants by promoting its oxidation to the highly soluble selenate form. With regard to the health implications of these data, nearly all concentrations are above the 0.10 ppm minimum dietary intake recommended for cattle (National Academy of Sciences-National Research Council, 1971) and below the generally accept ed minimum toxic limit of 3-4 ppm suggested by Underwood (1962). Consistent with these findings, neither Se responsive white muscle disease nor Se toxicity are, at present, considered major problems in the Swan River-Dauphin area. G. APPLICATION OF REGIONAL GEOCHEMICAL RECONNAISSANCE TECHNIQUES 1. SOIL Although in the Rosetown area close relationships were noted between nitric-perchloric extractable Cu, Fe, Mn and Se data for plants and soils when expressed on a parent material basis, a similar relationship is not apparent for Mo in Manitoba. For example only background Mo concentrations occur in grasses growing on Mo-rich Keld Association shale-till (Table XXXXVI) whereas grasses associated with Mo-poor calcareous till east of Swan River are somewhat enriched in molybdenum (Table LII). The relationship between ammonium oxalate extractable Mo and plant concentrations is also weak. In the Swan River-Dauphin 206 area, therefore, regional soil Mo data appears to be of little use in predicting plant compositional trends. 2. STREAM SEDIMENT' As stated in Chapter I, stream sediment may be regarded as an approximation to a composite sample of upstream rock, overburden and soil, and as such it generally constitutes an ideal sampling medium for regional geochemical reconnaissance studies (Hawkes and Webb, 1962). Furthermore in the United Kingdom Webb and his associates have been notably successful in relating enhanced stream sediment Mo concentrations (> 3 ppm) , to similarly elevated concentrations in associated bedrock, soil and forage, and to the distribution of both clinical and pre viously unrecognized subclinical Mo-induced Cu deficiency in cattle (Thornton et al., 1972 a, b; Webb et al., 1968; Thornton and Webb, 1970). As indicated by the generally low Mo concentrations in sediment collected over Mo-rich shale units (Fig 37), Swan River-Dauphin area sediment values are normally not related to Mo levels in associated bedrock. Anomalous sediment concentrations (>5 ppm) over molybdeniferous shale southwest of Dauphin are exceptional, and reflect the presence of stream-cut bedrock exposures in this area of relatively thin drift cover. Sediment Mo concentrations, on the other hand, do reflect the Mo status of soil. For example, values for both soil and sediment through out the Swan River Valley are generally low (<3 ppm), whereas anomalous sediments southwest of Dauphin are related to upstream 207 occurrences of Mo-rich soil units (Fig 40). However because of typically poor soil-plant compositional relationships Mo levels in stream sediment, like those in soils, are not reflected in associated plants. For example, only background Mo values were noted in stream sediment obtained within the Mo toxic area of Cunningham et al. (1953), whereas grasses from this area are relatively Mo-rich (Fig 3 8; Table XXXXIX). Consequently, in contrast to the experience of other workers, in Manitoba, reconnaissance data on the Mo content of stream sediment are of little value in outlining areas where elevated Mo concentrations in vegetation are likely to give rise to animal disorders. H. CONCLUSION Grasses throughout the Swan River-Dauphin area are locally enriched in Mo, whereas concentrations in legumes are regionally enhanced. Soils, however, typically contain relatively little Mo ( < 3 ppm) . Elevated values in legumes reflect the ability of these plants to concentrate relatively large amounts of molybdenum. Locally enhanced Mo uptake by grasses, on the other hand, appears to be a consequence of changes in soil environ mental conditions such as drainage and pH, which tend to increase the availability of molybdenum. Widespread Cu deficiency in the Swan River-Dauphin area is attributable, in part, to the consumption of Mo-rich feeds. However because of poor soil-plant compositional relationships, 208 neither regional soil nor stream sediment survey data are useful in predicting areas where excessive Mo levels are mo likely to occur in vegetation. CHAPTER VI CONCLUSION A. STATEMENT OF THE PROBLEM 209 The purpose of this study was to examine the distribution of trace elements in earth surface materials on the Southern Canadian Interior Plain with a view to recommending appropriate methods of collecting and presenting regional geochemical data in this area-. Although stream sediment sampling has been used extensively for reconnaissance survey purposes elsewhere, on the Canadian prairies tributary streams are too scarce to permit routine application of this technique. Because soil can be collected everywhere with relatively little effort at tention was focused on obtaining information on compositional variations in this material. Studies were undertaken in three separate areas selected to represent a range of prairie environmental conditions. In two of these, Rosetown and Red Deer, the nature of both re gional and local variations in soil trace element content were examined. In the Rosetown area soil compositional variations were related to the distribution of trace elements in associated wheat plants. In the third area, around Swan River and Dauphin, tributary streams are relatively common, and emphasis was placed on investigating regional patterns of Mo distribution in both soil and stream sediment. The agricultural significance of this data was evaluated in terms of information on the Mo con tent of forage plants and the distribution of Mo-induced Cu deficiency in cattle. 210 •B. SUMMARY OF RESULTS 1. ROSETOWN AND RED DEER AREAS Regional variations in the Cu, Fe, Mn, Zn and Se content of soils are influenced to a considerable extent by changes in soil parent material. This parent material effect appears in turn to be largely controlled by textural variations. Thus in the Rosetown area lowest concentrations are associated with comparatively coarse grained aeolian sands, intermediate with alluvium, glacial till and lacustrine silt and sand, and high est values with fine grained lacustrine clay. In the Red Deer area compositional differences between hummocky and ground moraines likewise reflect textural differences in these two materials. Red Deer data further suggest that changes in bedrock type can also influence till trace element content. Approximately 60% of the variability in Rosetown Cu, Fe, Mn and Zn data for C horizon soil, and over 7 0% of the A horizon and 30-46 cm (12-18 in) depth soil variability is attributable to differences among parent material means. .In the Red Deer area, on the other hand, only 14 to 42% of the C horizon data variations can be assigned to among parent material sources. Comparatively large percentages for the Saskatchewan study reflect the presence of relatively coarse sand and fine clay deposits, and the resultant large differences between extreme mean values. Cu, Fe, Mn and Zn concentrations in individual A horizon 211 and 30 - 46 cm (12-18 in) depth material collected around Rosetown are generally fairly closely related (r>0.50) to levels in associated C horizons. Much stronger relationships (r>0.90), however, were noted when mean values for individual parent materials were compared. Effects of pedogenic processes are most apparent in the characteristically enhanced Mn and Zn concentrations in A horizons. Analysis of variance results for Rosetown data indicate that among sample site compositional differences for C horizons are statistically significant for all parent materials with the exception of glacial till. Among township variance com ponents for Rosetown area parent materials as well as moraines in the Red Deer area are typically non-significant. In both areas, estimated total variance for a given parent material is lower for A than C horizons. Significant among parent material variations for soil means were identified using Duncan's New Multiple Range test, and results summarized in map form distinguishing only composi-tionally distinctive parent materials or parent material groups. For the Saskatchewan study, because of close relationships be tween A, 30-46 cm (12-18 in) and C horizon sample means, map patterns for these three materials are very similar. Applica tion of Tidball (1970)'s adjustable variance ratio (Vm = 5.0) indicates that stable maps could have been produced for . C horizons by collecting as few as 5 samples per parent material, 212 whereas for A horizons 2 samples would have been adequate. In the Red Deer area as many as 30 C horizon samples would be required from each surficial deposit. Correlation coefficients relating Cu, Fe, Mn, Zn and Se concentrations in individual wheat and soil samples in the Rosetown area are generally relatively weak. Strong positive coefficients (r>0.70), however, were observed when Cu, Fe and Mn means and Se medians for separate parent materials were compared. Zn data is exceptional in that mean plant and soil values were found to be negatively related. Application of Duncan (1955)'s test to Cu, Fe and Mn means for wheat gave results consistent with those for soil. Thus means for both Mn and Fe associated with lacustrine clay were indicated to be , significantly higher, whereas Cu and Mn means for material grow ing on aeolian sand were shown to be significantly lower than other mean values. 2. SWAN RIVER-DAUPHIN AREA Agriculturally settled portions of the Swan River-Dauphin area are underlain, in part, by a sequence of Mo and Se en riched dark grey to black shales belonging to the Vermillion River, Favel and Ashville Formations. These bedrock units are overlain by a variable thickness of exotic glacial till and glacio lacustrine deposits. Data from a reconnaissance stream sediment survey and follow-up soil sampling indicate that soils developed on these deposits in general contain uniformly low Mo levels (<3 ppm). Enhanced sediment Mo concentrations within a small 213 area southwest of Dauphin, however, lead to the identification of a limited number of locally Mo-rich soil units. Drift cover in this area is thin, and highest concentrations (up to 20 ppm) were detected in an essentially residual soil (Keld Association) developed on Vermillion River shale. Se levels in this soil body were also anomalously high. Enhanced Mo concentrations (up to 42 ppm) occur locally in grasses associated with a variety of alkaline Mo-poor soils west of the contact between the Swan River and overlying Ashville Formations (Units 3 and 4, Fig 33). The Mo content of legumes collected throughout the region is generally high (> 5 ppm). In part because of elevated Mo values, Cu:Mo ratios in forage are commonly below the minimum acceptable value of 4.0. Further more Cu concentrations in both grasses and legumes are formally below the absolute minimum of 10 ppm recommended for cattle. Con sistent with these findings, both simple (Cu<10 ppm) and Mo-induced (Cu:Mo<4.0) Cu deficiency have been noted in cattle throughout the region. Se levels measured for a limited number of forage samples are within the generally accepted safe range (0.1 - 4.0 ppm) and Se-related nutritional disorders are not at present recognized in livestock. There appears to be little relationship between the Mo content of plants and soils either when data for individual samples or means for parent materials are compared. Mo con centrations in stream sediment generally reflect levels in as sociated soils and consequently regional patterns of Mo 214 distribution in stream sediment are also unrelated to variations in plant Mo content. C. RECONNAISSANCE GEOCHEMICAL SURVEYS 1. INTRODUCTION Although in this investigation attention was concentrated on assessing the feasibility of producing regional geochemical maps based on soil analyses, and on examining the potential agricultural value of such maps, in Manitoba it was possible to evaluate the usefulness of established reconnaissance stream sediment sampling procedures. Regional data on nitric-per chloric extractable Mo in stream sediment, however, were found to be unrelated to variations in the Mo content of forage or information on the distribution of Mo-induced Cu deficiency in cattle. Thus, in addition to being impractical for general use because of the absence of well developed tributary drainage systems, it appears that on the Canadian prairies stream sed iment data for Mo at least, have relatively little agricultural value. Results of soil investigations, on the other hand, indicate that broad-scale soil compositional patterns, based on differences among mean concentrations for individual soil parent materials, are related to compositional variations in associated crops for several nutritionally important trace elements. In the following section, therefore, parent mat erial based soil sampling procedures patternedtto a large extent 215 on those developed by Miesch (19 76) and his associates, are recommended for application on the Canadian prairies. Various aspects of these procedures are then discussed in detail. 2. RECOMMENDED PROCEDURES The area to be surveyed is first divided into several subareas for sampling on the basis of information on the distribution of soil parent materials. Composite A horizon samples are then collected at an equal number of randomly chosen sites over each major parent material. The decision as to how many samples to initially collect is necessarily some what arbitrary. Results of this study suggest that, for the elements examined, if among parent material compositional vari ations are expected to be large, for example because of the presence of coarse sand and fine clay deposits, as few as 5 samples per deposit are required. If, on the other hand, the influence of parent material is expected to be small, up to 30 samples should be taken from each deposit. After sieving.samples to minus 10-mesh and grinding to minus 100-mesh, trace element concentrations are measured using appropriate techniques. Compositional data are then log-transformed (base 10), and geometric means (GM) and geometric deviations(GD) calculated for individual parent materials. Samples containing concentrations in excess 2 of the GM x GD value for any element are rejected as 216 probably being unrepresentative of the parent population. An analysis of variance procedure is applied to estimate the magnitudes of both within and among parent material variance components. Tidball (1970)'s adjustable variance.ratio (Vm = 5.0) is used to determine whether sufficient samples were collected to adequately describe among parent material compositional patterns. If necessary additional samples are collected and analysed and the procedure for rejecting anomalous samples reapplied. The significance of differences among means for individual parent materials is evaluated using Duncan (1955)'s New Multiple Range test. When differences for two or more means are shown to be non-significant data for the deposits involved are group ed together and weighted means calculated based on their relative sizes. Results are finally summarized in map form distinguishing only compositionally distinctive parent materials or parent material groups. 3. DISCUSSION a) Choice of Size of Area Effects of varying study area size on geochemical map patterns were not specifically examined. If relatively strong map trends are sought, however, one factor limiting the mini mum size would be the requirement that it be large enough to include a sufficient variety of compositionally distinctive parent materials. On the other hand study area boundaries 217 cannot be extended indefinitely because,(1) generalizations necessary for production of final-maps covering very large areas would greatly limit their usefulness,and (2), because within parent material compositional variability would be expected to increase with the size of the region examined, for very large areas the significance of among parent material trends would be considerably reduced. Survey procedures recommended were tested in two areas 2 ranging in size from about 6,000 to 10,000 km (2,000 to 4,000 sq mi). It is tentatively suggested that these procedures could be applied with similar results in areas of up to about 15,000 km (6,000 sq mi). This size is convenient because it corresponds to the area covered by the National Topographic Map System's 1:250,000 scale maps, as well as many published surface geolog ical and bedrock maps. b) Identification of Target Populations The area to be investigated should be divided into various subareas for sampling in such a manner as to maximize the ex pected differences among mean soil concentrations for individual subdivisions. Results of this investigation• indicate that subareas should be defined on the basis of changes in soil pa rent material type. For example, in the Rosetown area over 7 0% of the total data variability for A horizons is attributable to differences among means for individual parent materials. An additional advantage in the use of soil parent materials is that, because they tend to cover relatively large areas,a single mean value has considerable regional significance. 218 Unfortunately surficial geological maps showing the re quired detail are not available in many Canadian prairie regions. Soil maps ,however, have been published for most regions, and the required information can generally be obtained from these. When identifying individual parent materials for sampling an attempt should be made to distinguish deposits which differ either texturally or in probable bedrock source. In the case of lacustrine deposits, extensive bodies consisting predominantly of sand, silt or clay size material should be sampled separately. Because till tends to be locally derived, the trace element content of moraines overlying compositionally distinctive bed rock units should also be estimated separately. Differences in surface morphology of till deposits should be recognised in the initial sampling plan as well, if this does not result in an excessive increase in the total sampling load. In the Red Deer area, for example, ground and hummocky moraines were found to differ significantly in their mean Mn content. It should, however, be emphasized that, because surface geological maps are only generalized representations of the actual pattern of surficial deposits, individual map units which define the subareas to be sampled,contain variable amounts of"foreign"material which are not representative of the deposits indicated. The target populations for sampling, therefore, are in fact only those soils, within the various subareas recognized, which are associated with the deposit of interest. Defining target populations in this fashion, of 219 course, has the disadvantage that geo.chemic.ally anomalous soil bodies, too geographically restricted to distinguish on regional maps, could be overlooked. Although the effect of cultivation on soil trace element content was not specifically examined, generally close re lationships between data for A and C horizons suggest that it is relatively slight. Furthermore because cultivated and un cultivated soils were not differentiated in the present investi gation and meaningful soil patterns were obtained, it is tentatively proposed that for trace element map production the influence of cultivation on soil composition need not be con sidered. c) Selection of Soil Horizon Because soil is characteristically composed of at least three distinct genetic horizons, the question arises as to which, if any one of these is most suitable for sampling. In this study the relative merits of A and C horizons and a 30 - 46 cm (12-18 in) depth sample were compared. The useful ness of B horizons was not specifically examined because this horizon is not present in some soils such as Regosols and Rego Chernozems. Because in the Rosetown area.trace element concentrations in A, 30-46 cm (12-18 in) and C horizons are generally closely related, essentially similar compositional patterns could be obtained by sampling any of these materials. This close 220 relationship is likely attributable, to some degree, to the lack of profile development in the Chernozemic soils of the region. Somewhat weaker relationships would be expected, however, for soils of the Greywooded Zone where Luvisols pre dominate and the effects of surface leaching are more pro nounced. Nevertheless, Chernozemic soils like those around Rosetown occupy over 80% of the agriculturally settled Canadian prairie region. A horizon sampling has the advantage that, for a given parent material, error associated with estimation of mean concentrations is low relative to that for subsurface horizons. This characteristic is especially useful because, other factors being equal, a greater proportion of the total data variability is attributable to among mean differences on which final geo chemical maps are based. Furthermore A horizons can be collect ed with considerably less effort than subsurface soils. For reconnaissance mapping purposes, therefore, A horizon collec tion is recommended. d) Choice of Number and Distribution of Sample Sites Tidball (1970)'s adjustable variance ratio (Vm) is used to determine the minimum number of randomly collected samples required per deposit to adequately describe differences among parent material mean values. Application of this statistic in the Rosetown area, however, indicated that with Vm set equal to 1.0, for all elements examined less than one sample was required from each parent material. These unrealistically low 221 values are attributable to large among mean differences, which in turn reflect the presence of coarse sand and fine clay deposits in this area. Because with Vm set equal to 5.0 more acceptable results were obtained, it is suggested that this higher value generally be employed. The total sampling load can be greatly increased if the intention is to describe details of "within" as well as "among" parent material compositional variations. Results of this study, however, indicate that generally attention need be focused only on among parent material patterns. As noted previously, around Rosetown these patterns account for over 70% of the total A horizon data variability. Furthermore although close relation ships were noted between Cu, Fe and Mn mean and Se median con centrations for soils and plants associated with the same pa rent material, relationships between data for individual plant and soil samples from the same site were relatively weak. Thus only differences among soil means appear to be of value in predicting regional variations in the trace element content of plants. Miesch (1976) has likewise stressed the importance of concentrating on "among category" compositional trends when undertaking geochemical surveys of this type. Miesch(1976), however, does advocate the use of a "nested" sampling design such that "within category" (ie. in this study, within parent material) data variability can be partitioned into separate components corresponding to areas of differing geographic size. This information can be used to maximize 222 follow-up sampling efficiency when a large proportion of the within parent material data variability is found to occur in relatively small areas. That is, when Vm calculations indicate that additional samples are required, follow-up sampling can be concentrated in only a few such geographically restricted areas, thereby reducing the time and cost of sample collection (Tidball, 1976). Disadvantages associated with the use of a nested design, however, include an increase in the total number of samples for analysis, and complication of statistical handling of the data because many statistical tests require random sampling. In addition, the nested design proposed is based on the assum ption that geographic components of variability are the same for all map categories (parent materials) examined. Because the validity of this assumption is very doubtful when dealing with deposits as dissimilar as, for example, aeolian sand and alluvium, nesting of samples could lead,unnecessarily , to serious biasing of final mean and variance estimates. Therefore, until- the relative importance of these shortcomings has been evaluated, random sampling is recommended. e) Sample Preparation and Analysis As is standard agricultural practice, all soils in this study were initially sieved to minus 10-mesh and then ground to minus 100-mesh prior to digestion. This procedure, however, was found to have the disadvantage that the grinding stage is 223 comparatively time consuming, especially when large numbers of samples require processing. Sample preparation for mineral exploration surveys, on the other hand, consists simply in sieving soil directly to minus 80-mesh. In addition to de creasing the sample processing time, application of this sieving procedure could improve the relationship between plant and soil compositional data because a relatively large propor tion of the trace elements extracted from the minus 80-mesh fraction would probably be loosely bound,, in a plant-available form,on the finer soil particle surfaces. On the other hand, sieving in this fashion could reduce the observed differences among parent material means, because these differences appear to be largely texturally controlled. Until this question has been examined further, therefore, application of standard agricultural procedures is suggested. As Miesch (1976) has observed, for most reconnaissance geochemical surveys relatively rapid, low-cost analytical pro cedures are adequate, because analytical error generally represents a relatively small fraction of the total error in volved in estimating category means. Procedures for Cu, Fe, Mn and Zn analysis used in this study, involving simultaneous digestion of up to 240 samples and subsequent atomic absorption determinations, therefore are satisfactory. On the other hand methods for both Se and Mo require improvement because, the fluorimetric procedure for Se is relatively slow, whereas the colorimetric method for Mo, though rapid, is not sufficiently precise. 224 f) Data Presentation The scale of final map production is limited only by the detail of information on the distribution of individual parent materials. Scales therefore may be varied depending upon the purpose for which maps are to be used. For example, where the intention is to describe only broad variations in the geo-chemical"background" against which the magnitude of the effects of pollution can be assessed, relatively small scale maps such as those presented in Chapters III and IV would be satisfactory. However, for veterinarians and other agricultural scientists, concerned with the occurrence, of trace element imbalances on individual farms, considerably more detailed maps, with scales of not less than about 1:250,000, would be required. Finally it should be noted that Duncan (1955)'s New Multiple Range test, which is used as the basis for map production, dis tinguishes only statistically, as opposed to "practically", significant among mean differences. That is, statistical sig nificance does not necessarily imply significance in terms of plant composition. It is possible, for example, that on the Canadian prairies, for among parent material compositional vari ations to be reflected in associated plants, means must differ by at least a factor of 1.5. The problem of using such mini mum proportional differences to distinguish between means has been treated briefly by Miesch (1976). 225 •D. . GENERAL CONCLUSIONS Although in the British Isles Webb and his associates (Webb and Atkinson, 1965; Thornton and Webb, 197 0) have been successful in relating regional stream sediment data to a variety of nutritional imbalances in crops and livestock, on the Southern Canadian Interior Plain stream density is gen erally inadequate for routine application of stream sediment sampling techniques. Furthermore results of this investigation indicate that information on the distribution of Mo in stream sediment in west-central Manitoba is of little value in identi fying areas where enhanced forage Mo concentrations and as sociated Mo-induced Cu deficiency in cattle are most likely to occur. Because soil is available nearly everywhere, reconnaissance geochemical surveys based on soil sampling, on the other hand, can be applied throughout the Canadian prairies. More impor tantly, however, although relationships between plant and soil data are weak when values for individual samples collected at the same site are compared, when data are summarized on the basis of mean concentrations associated with various parent materials relatively strong soil-plant relationships exist for several nutritionally significant trace elements. It appears therefore that soil survey data, when expressed in an appro priate fashion, can be used to predict regional variations in the trace element content of associated plants. It is suggested that reconnaissance soil surveys focus on describing differences among mean concentrations associated with individual soil parent materials. Briefly the procedure recommended involves collection of A horizon samples from the various surficial deposits within the area of study and estima tion of mean and variance values for each deposit. Duncan (1955)'s New Multiple Range test is used to identify signifi cant differences among means and results are summarized in map form distinguishing only compositionally unique parent materials or parent material groups. If the boundaries of individual survey areas are chosen to correspond to those of the National Topographic Map System's 1:250,000 scale maps, the agriculturally settled portion of the Southern Canadian Interior Plain could be conveniently 2 divided into about 40 separate 15,000 km (6,000 sq mi) quadrangles. Assuming that, on the average, 20 samples are obtained per parent material and 5 surficial deposits are recognized within each quadrangle, geochemical maps could be produced for the entire prairie region by collecting only about 4,000 samples. This number is not large when it is con sidered that over 2,000 soil samples were taken for the present investigation alone. Maps so produced could be used to predict areas where trace element imbalances in crops and livestock are most likely to occur. They could also be of value to medical scientists concerned with the distribution of trace element related 227 disease states in man. Furthermore, they would provide basic data on variations in the geochemical "background" on the Canadian prairies. Such information is of fundamental value to both ecologists and earth scientists. In addition it provides a"base-line" against which the magnitude of the environmental impact of man's activities can be assessed. With the growing public concern for environmental quality and the awareness of the need to maximize agricultural pro ductivity, the demand for basic geochemical survey information is expected to increase on a global scale. Because well developed tributary drainage systems are lacking over large portions of the earth's surface, parent material based soil sampling procedures such as those recommended could play a major role in supplying the required data. E. SUGGESTIONS FOR FURTHER WORK Follow-up investigations are required to test the usefulness of the survey procedures proposed in other Canadian prairie environments, expanding the range of elements and plant species examined. In particular the strength of relationships between parent material based mean concentrations for soil and plants should be investigated in areas where compositionally extreme parent materials (coarse sands and fine clays) are not represented. Also, because it was not possible to do so in the present study, a special effort should be made 228 to relate soil compositional variations to information on the distribution of trace element imbalances in either crops or livestock. Around Red Deer, for example, regional patterns for Se in A horizon soil could be compared with data on the incidence of Se responsive white muscle disease in cattle. In addition, there is considerable scope for refinement of the suggested survey procedures. Several possibilities for improvement were considered in Section C of this Shapter. These include, (1) use of a nested sample design to reduce the cost of sample collection, (2) sieving soil directly to minus 80-mesh to minimize sample processing time and (3) replacement of Duncan (1955)'s New Multiple Range test with a more suitable procedure. Basic investigations into the nature of compositional relationships between bedrock, soil parent material, soils and plants in the Canadian prairie environment could also provide much useful information. For example, although till is gen erally considered to be derived mainly from local bedrock, to date no attempt has been made to quantify the extent to which this is true. Similarly little specific data are available on the provenance of material in other types of surficial de posits. Results of studies of this type could have been used in Manitoba, for example, to identifying the probable bedrock source of Mo in soils supporting Mo-rich plants. Furthermore, information from such investigations would be of considerable value.when initially dividing areas to be surveyed into 229 parent material based subareas for sampling. The influences of both pedogenic processes and cultiva tion on soil composition should be examined more closely. A nested sampling design similar to that used by Tidball (1976) could be employed to investigate the influence of soil type on within parent material compositional variations in A horizons. Study areas should be chosen to include Luvisolic soils because the effects of pedogenic processes would be expected to be par ticularly apparent in soils belonging to this Order. The in fluence of cultivation could be assessed, on the other hand, by comparing average ratios of trace element concentrations in A and C horizons for both cultivated and uncultivated soil'developed on the same parent material. Related to these studies, an at tempt should be made to determine whether pedogenic factors, cultivation or sampling procedures are primarily responsible for the reduced error in mean estimation for A horizons relative to subsurface horizons associated with a particular surficial deposit. Information is also required on how the form in which trace elements occur in prairie soil (ie. in solution, adsorbed onto clays etc.) affects their availability, to plants. Such data could be used to design partial extraction procedures which would more accurately reflect plant available soil concentrations than the nitric-perchloric attack used in this study. Green house experiments could also be undertaken to evaluate the relative importance of such factors as soil Eh, pH arid organic 230 matter content in trace element uptake by plants. In\ this manner it should be possible, for example, to identify factors responsible for the weak relationships between data on the Mo and Zn content of soils and plants noted in this invest igation. In addition to these studies, a survey of trace element concentrations in the Cretaceous and younger sediments which underlie the Canadian Interior Plain would be very valuable. Information obtained could be used, for example, to identify bedrock units containing anomalously high or low levels of nutritionally significant trace elements, as well as to predict the influence of changes in bedrock type on soil composition. 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Bull. 758, pp. 46-55. 243 APPENDIX A PROCEDURE FOR THE FLUOROMETRIC DETERMINATION OF SELENIUM IN BOTH PLANT AND GEOLOGICAL MATERIALS SPECIAL APPARATUS Turner Model 111 fluorometer equipped with #7-60 primary filter, a combination of #58 and #2A-15 secondary filters, a 1% neutral density filter and 12 x 100 mm glass cuvettes. REAGENTS a) Ammonium hydroxide - dilute 400 ml of concentrated NH^OH to 1 L with distilled water. b) Arsenic solution - dissolve 250 mg of arsenic trioxide and 2 g of sodium hydroxide in 200 ml of water.. c) DAN solution - dissolve 0.25 g of 2,3-diaminonapthalene (Aldrich Chemical Company) in 25 ml of concentrated HCl and dilute to 250 ml with distilled water. Extract solution with 10 ml hexanes, shaking in a separatory funnel 4 times only, and allowing 3 to 4 minutes for the mixture to separate. Repeat extrac tion 3 additional times. Store solution under about 0.5 cm of hexanes in a brown bottle in a refrigerator -it should be stable for several weeks. d) EDTA solution - 0.04M - dissolve 7.445 g Na2H2 EDTA.2H20 along with 50 g hydroxylamine hydrochloride in 500 ml of distilled water. e) Formic acid solution - add 250 ml 91% formic acid to 250 ml distilled water. f) Indicator solution - dissolve 100 mg of the sodium salt of m-cresol purple in 100 ml of distilled water. g) Selenium standard solution - 100 yg/ml - dissolve 100 mg elemental Se in 5 ml concentrated HNO_ and 2 ml con centrated HCl and dilute to 1 L with distilled water. This solution should be stable for up to two.months. Prepare a fresh 1yg/ml solution from this stock solution before each determination. h) Hydrochloric acid - 0.1 M - add 10 ml concentrated HCl to 990 ml distilled water. - 6 M - add 600 ml concentrated HCl to 400 ml of distilled water. 244 3. PROCEDURE a) Samples (i) Digestion: Plant Materials: Weigh an appropriate amount (usually 0.500 g) of ground sample into a 12 5 ml erlyhmyer flask. Add 15 ml of 4:1 nitric-perchloric acid, cover flask with watch-glass and place on warm hot plate overnight. The following morning remove watch-glass and raise hot plate temperature until solution boils gently. Evaporate to about 5 ml and remove from heat. If undissolved fatty material is visible on the surface of cooled solution, place a small glass funnel in flask mouth and reflux gently on hot plate until fats are dis solved, if necessary adding a few milliliters of concentrated nitric acid. Remove funnel, raise hot plate temperature and evaporate to the first appearance of white perchloric acid fumes. Con tinue fuming for approximately 15 minutes, being careful not to allow solution to approach dryness. Geological Materials: Place a suitable weight (usu ally 0.500 g) ground sample in a 100 ml beaker. Add 15 ml of 4:1 nitric-perchloric acid, cover with watch-glass and heat on warm hot plate overnight. The following morning remove watch-glass and raise hot plate temperature until solution boils gently. Evaporate directly to perchloric acid fumes, and then fume for about 15 minutes as described above. (ii) Arsenic coprecipitation: Cool solution-, add 10 ml 6 M HCI and bring to a rapid boil. Filter warm solution through Watman #541 paper into a tapered 40 ml glass centrifuge tube. Rinse either flask or beaker with 5 ml 6 M HCI and transfer to centrifuge tube. Add 2 ml arsenic solution and 5 ml hypo-phosphorous acid and mix contents. Place tube in a hot water bath at 90°C for at least one hour. When precipitation is complete centrifuge at high speed for 10 to 15 minutes. Draw off supernatant liquid through a fine-tipped glass tube attached to an aspirator, being careful.. to avoid removing pre  cipitated arsenic. Wash precipitate in 10 ml dis tilled water, recentrifuge for 10 minutes and draw off liquid phase as before. (iii) Reaction with DAN: Dissolve precipitate in 1 ml concentrated nitric acid. Add 5 ml 0.1 M HCI, mix and transfer solution to 100 ml beaker. Rinse tube with 5 ml 0.1 M HCI and add to beaker. Bring solution rapidly to a boil on hot plate, remove and cool. 245 Add 10 ml 0.1 M HCI, 5 ml EDTA solution, 5 ml formic acid solution and two drops of indica tor solution to beaker. Titrate with NH.OH solu tion until sample color is orange indicating that the pH is approximately 1.8 (for more precise results pH should be checked with a meter). Place beaker in hot water bath at 70°C and cover with a watch-glass. After about 15 minutes remove from bath, add 2 ml DAN solution, mix and replace cover ed beaker in bath for exactly 30 minutes. Remove and cool beaker for 30 to 40 minutes. Transfer beaker contents to 60 ml separatory funnel and add 8 ml hexanes. Stopper and shake 4 times only. Allow a minimum of 3 to 4 minutes for phases to separate and drain off aqueous layer. Pipette 5 ml hexanes into a cuvette for fluoresence measurement being careful to avoid formation of water droplets on the inside of cuvette walls. b) Blank and Standards Determinations are carried out in batches of 16. Each bath includes one blank, one 0.4 yg and one 1.5 yg Se standard. Blanks and standards are taken through the entire procedure including the digestion step. c) Operation of Fluorometer Using the combination of filters described in the section on Special Apparatus the Se-DAN complex is irradiated at approximately 365 my and the resultant fluoresence measured at about 535 my. With the range selector set at 3.x zero the fluoresence dial with a dummy cuvette. Measure blank fluoresence and reset instrument to zero on blank sample. Measure the fluoresence of the 0.4yg Se standard and establish a callibration curve. Measure sample fluoresence values and record those giving a scale deflection less than that of the 0.4yg standard. Adjust range selector to lx. Reraeasure blank fluoresence and zero instrument as described previously. Establish a callibration curve using both the 0.4 and 1.5yg Se standards and measure fluoresence of samples containing more than 0.4 yg Se. For samples containing in excess of 1.5 yg Se a new callibration curve can be determined with range selector at 3x and a 1% neutral density filter inserted between the ultraviolet source and sample cuvette. The fluoresence - concentration relationship is approximately linear up to about 3.0 yg Se. Samples containing larger amounts of Se should be reanalysed using a smaller sample weight. Typical blank and 246 standard fluoresence measurements for 3x and lx range selector settings are given below. Se Fluoresence Reading* Added 3x lx Blank 0.4 yg 1.5 yg 25.5 9.0 22-28 7.5-11.0 (10) (13) 80.0 27.5 63-93 24-30 (10) (12) 99.0 90-107 (13) Mean and range; number of measurements in parentheses. 4. NOTES a) The entire procedure is carried out under normal laboratory illumination. b) Major items of glassware are rinsed in tap and dis tilled water between each batch, except for cuvettes which are cleaned with alcohol and dried in acetone. c) Separatory funnels are equipped with teflon stopcocks to avoid contamination from glass stopcock grease. d) The procedure takes two full days to complete with samples typically being stored overnight after the arsenic coprecipitation stage. e) The method described combines aspects of several pre viously published procedures. The original sources are cited in Chapter II, p. 37. APPENDIX B COMPUTATIONAL PROCEDURES FOR STATISTICAL TREATMENT OF THE DATA DATA TRANSFORMATION x = log 10 y, where y represents an individual data value expressed either in ppm or percent. ESTIMATION OF POPULATION PARAMATERS a) Geometric Mean (GM) GM = 10X, where x is calculated as: n x = 1=1 , n and n represents the number of samples in the population of interest. b) Geometric Deviation (GD) s GD = 10 X , where s„ is calculated as: n _ 2 E (x.-x) i=l 1 n-1 IDENTIFICATION OF OUTLIERS A sample was rejected as probably unrepresentative of the parent population if for any element, xy x + 2 s . 248 4. TESTS OF SIGNIFICANCE a) Linear Correlation Coefficient (r) i=l (xli " Xl} (x2i ~ X2) r = n _ 2 n - 2 E (XlJ - xn) E (x2i - x2.) 1=1 where x^ and x2 typically represent values for the same element in two different sample types and n is the number of data pairs. The probability that r is not in fact equal to zero is determined using the "t" statistic calculated as: t = r NJ(n-2)//'(l-r2) The calculated "t" value is then compared to values in standard "t" tables for n-2 degrees of freedom (Snedecor, 1946). b) Analysis of Variance Computational procedures for partitioning data variance into among and within group sources are sum marized in Table B-l. In the case where there were an unequal number of observations within separate groups the value of "b" in Table B-l is calculated as: a b =. -. n. f. , i=l l i where n. represents the number of observations in the ith data group. is given by: • _1 _ 1 f. = n. N a-l where N is the total number of observations (Kozak, 1976). 249 Table B-l Method of estimating within and among group components of variance. Source of Variation Sum of Degrees Mean Mean Square Squares of Freedom Square is estimate of. • . Among Group SS. = Z a rE X.. ) a-1 SS-a-1 • 2 -2 "B ot a b o - (z z xii^ • i j ab Within SS2 = I I (Xij)2 a(b-l) SS2 ^ Group a - E i (bX..)2 a(b-l) Adopted from Connor and Ebens (1970): X . is the log 10 trace element content of the jth sample in the ith group, a is the number of groups, b is the number of samples within each group, :a/ is the within group variance component and -a* isPthe among group variance component. 250 The significance of among group mean differences is assessed by comparing the ratio, SS-, /ss0 a-l/ a(b-l) with values in standard "F" tables for a-l and a(b-l) degrees of freedom. c) Duncan's New Multiple Range Test Firstly the standard error of the estimated means is calculated as: s-x i ss. £(b-l) where SS2» a and b are defined as in Table B-l. Then a-l "significant studentized ranges" are extracted from a table given by Duncan (1955) for the 5% confidence level and a(b-l) degrees of freedom. A separate range value is obtained depending upon the number of means to be involved in a single comparison: that is one value is taken for the case where there are only two means, another for the case where the two means being compared are separated by a third mean, and so forth to the case where a-2 means separate the two means of interest. These range values are then multiplied by s- to give a set of "least significant ranges". Means are arranged in numeric order and differences between them tested in the following manner: largest minus smallest, largest minus second smallest,..., largest minus second largest, second largest minus smallest, second largest minus, second smallest and so on to the second smallest minus the smallest. Generally a difference is declared significant if it exceeds the "least significant range" corresponding to the number of means involved in the comparison. An exception however occurs in that no difference between two means can be declared significant if the two means are contained in a larger subset with a nonsignificant range. d) Median Test The chi-square formula used for this test can be expressed as follows: 251 = E i=l E j = l (fij F . .) ID F. . ID where k represents the total number of data sets, f. . represents the number of observations in the itft set either above (j=l) or below (j=2) the overall group median and F.. represents the corresponding expected number of observations obtained using contingency tables. The null hypothesis, that samples were drawn from populations having the same median, is tested by comparing the calcu lated chi-square values with those of standard statistical tables for k-1 degrees of freedom. 5. ESTIMATION OF ANALYTICAL PRECISION (P) a) Among Batches Among batch precision is estimated on the basis of analyses for a single laboratory standard sample which was included within each analytical batch. The formula used is, P = 1.98 E i=.l <y. - Y)2 L-l 100 % , where y. is the measured concentration (in ppm or %) of a particular element_in the laboratory standard for the ith analytical batch, y is the overall average concentration for all of the batches, and L is the total number of batches. b) Within Batches Within batch precision is estimated on the basis of results of analyses for one randomly selected sample within each analytical batch. P = 100 where y . and y„. are the measured concentrations for the seleited samjle in the ith analytical batch and L is the total number of batches. 253 APPENDIX C LISTING OF INDIVIDUAL DATA VALUES USED POR MEAN (OR MEDIAN) AND VARIABILITY ESTIMATES 1. ROSETOWN AREA SOIL (TABLES XIV AND XVI) SAMPLE DESCRIPTION SITE U.T.M. SAMPLE CU FE MN ZN SE NO. COORDINATES NO. (PPM) (%) (PPM) (PPM) (PPM) E N PH A HORIZON LAC. SOIL CLAY 4 2996 6955 720246 26.968 2. 7 05 376.674 8 6. 049 8. 0 9 2957 6737 720261 26.639 2. 943 390.497 88.605 8. 0 16 3113 6963 72C282 24.666 2. 625 469.978 90.309 7. 4 20 3063 6777 72C294 13.813 1. 9 09 259.179 51.118 6. 8 27 32 07 7019 720316 27.626 2 . 864 425.054 81.789 7. 8 40 3292 6926 720355 19.404 1 . 989 400.864 73.269 7. 8 62 3479 7052 720421 17.333 1. 724 456.641 73.583 7. 2 93 3698 6706 720514 16.333 1 . 564 298 .573 59.037 7. 7 97 3736 7075 720526 14.000 1. 4 84 344.237 64. 171 7. 0 126 3043 7237 730067 18.229 1. 927 420.591 84.670 6. 4 129 3172 7123 73GC76 26.515 2 .690 424 .096 92.526 7. 5 143 3261 7358 730136 18.209 1. 7 00 421.193 82.509 5. 9 149 3363 712 9 730157 13.778 1. 464 364.056 63.158 7. 0 199 2949 6 890 73C355 28.889 3. 033 401.320 9 0.00 0 7. 5 208 2949 6970 730382 28. 889 2. 966 364.356 85. 000 7. 9 221 2997 6362 73C467 2 8.000 2. 9 48 390.55 1 92.000 7. 5 222 3121 6768 ' 730473 25. 778 2. 715 377.953 90.000 7 . 7 223 3221 69 18 730479 28.889 2. 793 390.55 1 95. 000 7. 8 224 3337 7029 73 04 85 23.111 2. 172 453.543 85.000 7. 7 225 3120 7127 730491 24.000 2. 2 50 491.339 85.000 7. 7 226 3055 7162 730497 24.984 2 . 488 410.915 70.000 7. 9 227 3507 7059 730503 16.239 2. 0C6 372.392 70.000 6. 9 IAC. 112 2957 7321 730010 14.938 SILT 135 3180 74 50 73C097 18.560 AND 137 3222 7562 730109 22.929 SAND 140 3284 7583 730121 19.220 156 3388 7469 730184 15. Ill 159 3488 7546 730196 15.556 160 3500 7500 73C199 11.111 161 3527 7487 73C205 11.111 172 3524 7273 730250 7.556 178 3560 7523 730274 14.222 187 3635 7170 730307 13.333 1 .674 316. 483 65.033 7.9 2.168 417.086 82.924 6.7 2.226 385.499 36.762 8.1 1.943 421.193 82.509 6.2 1.685 364.356 72.000 6.7 1.685 356.436 65.000 7.4 1.247 285.148 52.000 7.2 1.264 303.631 58.000 6.0 0.977 227.063 36.000 7.7 1.449 382.838 75.000 6.4 1.533 330.033 60. 000 6.5 GLACIAL <+i TILL 52 * 59 78 3307 3350 3324 3542 6366 6957 6596 6885 720358 72C391 72C412 720469 17.102 15.457 23.022 16.000 1. 750 1.710 2. 1 48 1.604 359.395 331.750 449.244 372.338 61. 342 58.786 69.862 66.738 7.8 7.0 8.0 7.7 * Sanple rejected for containing exceptionally high concentrations of the underlined element (s) + Blank = concentration not measured. 254 SAMPLE DESCRIPTION SITE U.T.M. NO. COORDINATES A HORIZON GLAC-SOIL IAL TILL SAMPLE NO. CU (PPM) E N 90 3710 6876 720505 14.333 91 3620 6737 720503 15.667 98 3790 7010 720529 14.000 101 3747 6891 72C538 14.333 116 2961 7511 730025 20. 581 117 3011 7541 730031 17.593 210 3088 7542 730391 13.333 *211 3102 7506 73 039 7 17.778 214 3309 6810 73C420 16.000 216 32 3 6 6700 730429 12.889 217 3253 6672 730435 12.444 218 3219 6610 73 0441 16.000 220 3152 6637 730455 14.222 228 3398 6693 730512 13.741 229 3470 6691 73C515 15.823 230 3489 6725 730521 14.990 231 3538 6789 730527 13.325 233 3495 6984 730536 11.659 235 3742 7011 730546 14.574 FE (%) 1 .684 1.305 1.684 1.684 1.993 1.333 1. 483 2. 2 24 1 .550 1.415 1.241 1.629 1. 590 1.485 1.725 1.725 1.525 1.3 64 1. 926 MN (PPM) 372.338 358.288 365.313 375.851 464.176 351 .648 303.631 396.040 337.954 290.429 428.346 503.937 340.157 423.756 410.915 487.961 359.55 I 333.868 290.208 ZN (PPM) 65.027 65. 882 70. 160 68.449 81.960 73.051 55.000 65. 000 45.000 3 6.000 55.000 73.000 55.000 62.000 60.000 65.000 55.000 50.000 60. 000 SE (PPM) PH 7.7 7.7 6. 8 7.8 7.7 7. 6 7.6 7.5 8.0 8.1 6.9 6.0 7.7 7.2 7.9 7. 6 7.2 7.5 7.9 ALLUVIUM 29 50 92 122 132 136 170 191 198 3128 3357 3682 3083 3 145 3219 3601 3768 3775 6893 7111 6748 7452 7309 7451 7200 7252 7545 720322 720385 720511 730049 730C63 730103 730241 730322 730349 27. 955 13.484 15.333 11.286 1 1 .932 20. 906 4. 889 5.333 13.333 943 392 6 84 1 96 767 226 1.247 0. 343 1. 529 425. 362, 428 260, 315 399 316 221 284 054 851 540 220 ,44 3 ,777 .832 , 782 ,913 87. 753 55. 378 77.005 56.125 61,102 90.165 4 8.00 0 30.000 70. 175 7. 6 6.7 7.9 AEOLIAN SAND * 123 141 155 166 169 173 174 182 197 3110 3237 3349 3438 3603 3557 3540 3716 3738 73 ei 7472 7436 7252 7147 7322 7345 7398 7500 730055 730127 73C178 730223 730235 730253 730259 730289 730343 ,286 0.598 6.070 0.688 5.778 0.640 4.889 0.681 4.444 0.843 5. 333 0.775 4.889 0.674 4.000 0.758 4.444 0.781 115.663 232.013 121.452 171.617 195.380 142.574 134.654 174.258 166.200 25.052 2 7. 390 29.000 29. 000 20.00 0 28.000 28. 000 25.000 28. 070 6. 6. 6. 6. 7. 7. 6. 6. 6, 30-46 CM LAC. DEPTH CLAY SOIL 4 2996 6955 720247 9 2957 6737 720262 16 3113 6963 720283 20 3083 6777 720295 27 3207 7019 720317 40 3292 6926 720356 62 3479 7052 720422 93 3698 67C6 720515 97 3736 7075 720527 28.284 2.546 26.968 2.745 24.008 2. 585 12.826 1.432 30.536 3.023 24. 666 2. 705 17.667 2.326 16.667 1.684 13. 333 1.604 380.129 362.851 449.244 2 03.88 8 459.611 317.927 351.262 252.909 344.237 92.865 84.345 76.677 35.783 9 1.161 85. 197 85.562 47.914 62.460 8.0 8. 1 7.9 3.2 7.7 7.4 8. 0 8.1 7.3 * Sanple rejected for containing anomalously high concentrations of the underlined element (s) + Blank = concentration not measured. 255 SAMPLE DESCRIPTION SITE U.T.M. SAMPLE CU FE MN ZN SE+ PH NO. COORDINATES NO. (PPM) (%) (PPM) (PPM) (PPM) 30-46 CM LAC. DEPTH CLAY SOIL 126 3043 7237 730068 17.275 1. 8 29 364.169 64.961 7. 4 I 29 3172 7123 73CC77 26.735 2. 514 349.746 78.309 7. 9 143 3261 7358 730137 15.219 1. 981 338.929 62.291 6. 9 149 3363 7129 730158 11.556 1. 562 250.618 43. 860 7. 1 199 2949 6890 73C356 28. 000 2. 870 365.354 92.000 7. 9 208 2949 6970 730383 30.222 2. 9 09 340. 157 82. 000 8. 0 221 2997 6862 730468 28.889 2. 7 15 365.354 92.000 7. 8 222 3121 6768 730474 26.667 2. 5 60 332 .598 82.000 7. 8 223 3221 6918 730480 29.564 3. 210 398.074 90.000 8. 0 *224 3337 7029 730486 18.738 2. 327 539.326 85.000 8. 2 225 3120 7127 73C492 22.902 1. 926 333.868 60.000 8. 0 226 3055 7152 730498 24.151 2. 403 385.233 70.000 8. 0 227 3507 7 059 73C504 2 0.8 20 2.006 333.868 60.000 3. 6 LAC. 1 12 2957 7321 730011 16.452 1.5 24 223.549 53.393 8. 1 SILT 135 3130 7450 730098 20.566 1.638 306.479 56.062 8. 1 AND 137 3222 7562 73C110 22.622 2. 133 331.718 72. 970 8.4 SAND 140 3284 7583 730122 13.162 1.867 331.718 55.172 6.3 156 3388 7469 73C185 15. 556 1. 855 448.475 78. 947 6.6 159 3488 7546 730197 9. 333 1.269 242.704 39.474 3. 3 16C 3500 75C0 730200 12.444 1. 757 290.190 6 1.403 6.8 161 3527 7487 730206 8.444 1. 1 39 197.857 35. 068 7.8 172 3524 7273 730251 8. 889 1. 139 197.857 30.702 3. 1 17R 3560 7523 73C275 12.444 1. 643 197.857 68.421 7. 1 187 3635 7170 730308 17.778 2.017 329.761 5 7.018 7.8 SLACIAL 41 3307 6366 720359 18.088 1. 432 255.724 36. 635 8.2 TILL 52 3350 6957 720392 20.391 1.511 221. 166 37.487 7. 9 59 3 32 4 6596 720413 24.333 2.2 06 449 .616 69.305 7.9 78 3 54 2 6885 720470 16.667 1. 764 3 51.262 59.037 7.8 90 3710 6976 720506 17.667 1 .845 298.573 64.17 1 7.8 91 3620 6737 720509 18.000 1 .684 252.909 49.626 3.1 98 37 90 7010 720530 16.000 2.326 256.421 91. 551 7. 1 101 3747 6891 720539 12.333 1.283 203.732 35.936 3.3 * 1 16 2961 7511 730026 22.211 1.981 566.084 105.006 6.8 117 3011 7541 730032 16.041 1.524 259.606 53.393 8. 4 210 3088 7542 730392 14.667 1. 7 84 277. 165 50.000 8.3 211 3102 7506 73C398 26.222 2.133 327.559 65. 000 8.3 214 3309 6810 730421 14.222 1.396 284.724 39.000 8.4 2 16 3236 67CC 730430 15.556 1.3 96 191.496 39.000 8.1 217 3253 6672 730436 9. 333 1. 164 272.126 36. 500 3.0 218 3219 6610 730442 13.778 1.745 352.756 62.000 6.4 2 20 3152 6637 73C456 15.556 1. 319 214. 173 45.000 8.4 228 33 9 8 6693 730513 I 2.49 2 1.645 359.55 1 65.000 7.4 229 3470 6691 730516 8. 744 0.903 243.981 23.000 8.5 230 3489 6725 730522 16.656 2.327 398.074 70.000 6.7 231 3538 6789 730528 10.410 1.525 269.663 50.COO 6.3 233 3495 6984 730537 10. 410 1. 043 192.616 27. 000 8.2 2 35 3742 7011 730547 14.990 1 .966 218.299 60. 000 8.3 * Sample rejected for containing anomalously high concentrations of the underlined element(s) . + Blank = concentration not measured. 256 SAMPLE DESCRIPTION SITE U.T.M. SAMPLE NO. COORDINATES NO. E N 30-40 CM ALLUVIUM 29 3128 6893 720323 DEPTH 50 3357 7111 72C386 SOIL 92 3682 6748 720512 122 3083 7452 730050 132 3145 7309 73CC89 136 3219 7451 730104 170 3601 7200 730242 191 3768 7252 730323 198 3775 7545 7303 50 AEOLIAN *123 3110 7381 730056 SAND 141 3237 7472 730128 155 3349 7436 73C179 166 3438 7252 730224 169 3603 7147 73C236 173 3557 7322 730254 174 3540 7345 730260 182 3716 7398 73C290 197 3738 7500 730344 CU FE MN ZN SE+ PH+ (PPM) (%) (PPM) (PPM) (PPM) 29.599 2.904 390.49 7 85.197 8.3 13.155 1. 3 52 228.078 46.858 8.6 18.000 2. 125 403.95 1 72.727 7.5 9.049 1.219 155.042 40.044 6.3 13.162 0. 990 191.099 32.036 8.5 18.098 1.714 281.240 60.512 8. 1 8.889 1.1 06 226.876 36.842 8.6 4. 000 0.716 179.390 16.667 7.2 8.889 1 .125 206.614 35.000 8. 0 8.226 0.930 227.155 42. 714 6.2 5.347 0.731 201.916 13.526 7.0 3. 556 0.5 86 92.333 17.105 7.0 4.444 0.765 133.223 22.307 7. 2 4. 444 0. 634 213.635 13.596 8.4 4.444 0. 683 109.43 1 19. 737 7.6 2.667 0.560 93.652 16.667 7. 1 2.222 0. 667 122.671 15.789 7.4 3. 556 0.781 131.904 20. 175 7. 0 C HORIZON SOIL LAC. CLAY 1 3005 7063 7200239 18.317 1. 509 331 .396 48.485 2 3033 7C66 7200242 29.974 2. 531 34 8.83 7 86.762 3 2967 7007 7200245 32.194 2. 3 36 286.046 80.333 4 2996 6955 7200243 2 7.754 2. 287 320.930 80.383 5 3027 6910 7200251 31. 63 9 2. 239 296.511 77.831 6 2938 684 1 7200254 31.639 2. 433 32 7.90 7 85. 486 7 2952 6829 72C0257 24.978 2.433 338.372 8 5. 486 8 2951 6800 7200260 16.652 1. 4 84 261.628 48.435 9 2957 6737 7200263 24.978 2. 433 324.413 82. 935 10 3022 67C7 7200266 22.203 2. 190 244.136 67.624 13 3053 7C90 720C275 31.639 2. 239 324.418 74.003 14 3070 7030 7200278 27.754 2. 336 300.000 81.659 15 3066 7010 72CC281 26.644 2. 2 87 376.744 8 2.93 5 16 3113 6963 7200284 27.754 2. 141 366.279 74.003 18 3040 6847 720C290 29.974 2. 579 313.953 89.314 19 3036 6813 7200293 17. 762 1. 4 84 296.511 54.864 20 3083 6777 7200296 12.767 0. 376 170.930 25. 51 8 21 3076 6708 7200299 2 6 . 08 8 2. 385 324.418 82.935 22 3 04 7 6679 7200302 33. 351 3. 3 50 307.692 81.250 25 3203 7039 7200312 27.026 2. 350 401.619 7 1.250 26 3198 7085 72CC315 21.851 2. 500 365.992 8 5.000 27 3207 7019 7200318 27.601 2. 600 340.081 75. 000 28 3174 6986 72CC321 10.350 1. 225 217.004 40.000 30 32 0 8 6873 7200327 3 1.051 2. 850 349.798 83.750 37 3287 7114 7200348 27.026 2. 100 333.603 62.500 39 3275 6926 72C0354 33.351 3. 150 304.453 9 1.250 40 3292 6926 7200357 18.976 1. 675 259. 109 43.750 42 3262 6858 7200363 25.876 2. 3 50 281.781 71.250 49 3329 7073 72CC384 18.772 1. 6 72 2 83.110 55.728 61 3497 7 102 7200420 29.331 2. 282 418.230 71.827 7.7 7.7 3.3 3.7 7.8 3. 1 * Sample rejected for containing anomalously high concentrations of the underlined element(s) . + Blank = value not measured. 257 SAMPLE DESCRIPTION SITE U.T.M. SAMPLE CU FE MN ZN SE+ PH+ NO. COORDINATES NO. (PPM) (%) (PPM) (PPM) (PPM) C HORIZON IAC. SOIL CLAY 62 3479 7052 7200423 25. 811 1.751 312.064 6 1.920 8.7 72 3452 6590 7200453 19.089 1.8 26 360.805 7 1. 429 75 3536 7082 7200462 11.665 1.040 225.503 35.065 76 3568 6918 7200465 24. 391 2. 079 373.691 74.026 84 3553 6558 7200489 24.921 2. 130 360.805 79.221 86 3703 7071 72 00495 14.847 1.445 251 .275 48.052 93 3698 6706 7200516 28.971 2. 247 328.317 117.224 8.1 95 36 78 6564 7200522 20.016 1.712 279.070 94.602 96 3661 6559 720C525 20. 016 1.712 311.902 94.602 97 3736 7075 72C0528 14.749 1. 498 252.804 67. 866 8.6 109 3007 7139 73CC03 24.000 2.206 309.111 70. 160 1 10 2965 7162 730006 23.333 2.2 06 3 12.623 65. 027 125 3033 7253 730066 21.875 1.887 371.522 68. 085 126 3043 7237 73C069 19.886 1.767 311.938 6 I.102 8.5 127 3112 7218 730072 24.858 1.887 364.512 6 5. 466 128 3122 7211 730075 30.823 2. 6 50 3 96.05 7 35.543 129 3172 7123 730C78 33. 143 3.011 364.512 89.907 8.0 131 3129 7236 73C087 24.858 2. 2 89 399.562 78. 560 134 3198 7387 73C096 14.915 1.606 280.394 56.738 142 3327 7427 730135 28. 325 2.024 378.360 70.601 143 3261 7353 730138 22.255 1. 822 260.569 6 1. 244 8.2 144 3312 7335 730144 17.534 2. 105 356.944 47.634 147 3249 72 12 730153 30. 049 2. 389 373.980 89.137 148 3315 7136 730156 26.249 2. 142 370.452 80.223 154 3339 7384 73C177 12.434 1 .277 261.080 41.003 189 383 5 7131 73C318 30.747 2.480 328.018 7 9.778 221 2997 6862 73C469 33.706 3. 120 346.903 95.164 8. 0 222 3121 6768 73C475 34.924 3.2 72 325 .664 93.385 7.7 223 3221 6918 730431 29.239 2. 663 279.646 88. 049 7.8 224 3337 7029 73G487 30.05 1 2.663 400.000 84.491 8.4 225 3120 7127 730493 23.147 1. 864 431.858 64.925 7.9 226 3055 7162 730499 2 3.553 1.7 50 297.345 7 1.15 1 8.0 2 27 3507 7C59 . 730505 30. 863 2.473 375.221 76.487 8.3 247 3737 7067 730606 27. 558 2.171 349.746 7C. 300 248 3747 7067 730612 23.445 2.019 270.422 66.741 249 3275 7405 730618 25. 501 1 .905 331.718 69. 410 LAC. SILT AND SAND 7 1 3440 6590 72C0450 26. 512 2.231 347.919 75.325 85 3673 7104 7200492 18.558 1.674 267.382 79.221 88 3667 6917 7200501 29.693 2.029 302.819 71.429 112 2957 7321 730012 1 7. 92 5 1 .514 295.385 58.797 8.4 113 2987 7327 730018 18.921 1. 833 253.187 58. 797 124 3118 7353 730063 10.274 0.976 189.266 30.551 135 3180 74 5 C 73C099 26.515 2. 369 403.067 80.306 8.4 137 3222 7562 73011 1 2 3.604 2. 307 335.527 65.497 3.3 138 3187 7577 730117 31.359 2.7 12 381.929 85.061 1 39 32 86 7598 730120 12.813 I. 498 199.888 39. 128 140 32 84 7583 730123 21.91 8 2.226 267.708 63. 796 8.5 149 3363 7129 730159 21.414 I .689 314.002 62.396 8.6 151 3372 7265 730168 5. 181 0.659 114.664 22.284 153 3391 7349 73C174 6.908 0.692 105.843 22.462 156 3388 7469 730186 12.C89 1.8 53 275. 193 47.242 8. 1 + Blank = value not measured. 258 + + SAMPLE DESCRIPTION SITE U.T.M. SAMPLE CU FE MN ZN SE PH NO. COORDINATES NO. (PPM) (%) (PPM) (PPM) (PPM) SOIL LAC. 157 3348 75C9 730192 I 1.052 1.441 197.574 44. 568 SILT 158 3384 7564 730195 15.888 1.771 261 .080 59.721 AND 159 3483 7546 73C198 18. 996 1.894 306.946 65.070 8.6 SAND 160 3500 75C0 730201 11.052 1. 359 239.912 41. 003 8. 5 161 3527 7487 730207 10.707 1.236 218.743 39.220 8.2 162 3486 7468 730213 8.800 1. 140 211.454 36. 281 168 3490 7172 730234 14.553 1. 392 260.793 47.166 * 17 1 3539 7241 730249 18.614 1.720 655.507 67. 120 172 3524 7273 730252 9.476 1. 264 303.084 39.909 8.6 176 3557 7455 730270 12.184 1. 2 80 239.648 45.351 8. 5 177 3 540 7500 73C273 15.708 I .400 320.729 57.618 178 3560 7523 730276 18.715 1.400 306.150 54. 958 186 3686 7209 73 03 06 8.355 0.940 160.36 5 34.571 187 3635 7170 730309 22. 72 6 1.880 349.886 69.141 8.4 188 3663 7111 730315 8.639 0.940 156.720 32. 798 190 3729 7170 730321 9.358 0.960 164.009 39.003 2 39 3370 7557 730567 17.222 1. 458 256.285 60. 244 242 3288 7541 730582 18.42 3 1.650 256.285 59.358 243 3379 7563 73C588 17.275 1.371 277.634 63.181 GLACIAL TILL Ground Moraine 41 3307 6866 72CC360 13. 801 1.225 246.154 37. 500 43 3255 6824 7200366 15.526 1.425 278.542 43.750 * 48 32 7 7 6596 720C381 15.839 I .3 80 572.654 5 9.443 51 3359 6991 72C0390 16.425 1.539 308.847 45. 320 52 3350 6957 7200393 10.559 1 . 167 231.635 33.437 59 3324 6596 7200414 22.291 1.804 366.756 64.396 60 3382 6538 7200417 24.051 2.0 17 334.584 68. Ill 81 3605 6652 7200480 ' 13.786 1.217 2 15.839 41. 558 • 100 3745 6947 7200537 4. 214 3. 104 170.725 48. 946 8.3 8.2 Humitocky Moraine 31 3194 6734 720C330 14.376 1.3 50 233.199 36.250 32 3225 6 76 8 7200333 8.050 '0.375 139.271 22.500 33 3162 6695 7200336 28.176 2.300 349.798 6 7. 50 0 36 3183 6556 7200345 13. 226 1. 150 217.004 35.000 44 3278 6772 720C369 13.492 1.210 267.024 39.628 47 3240 6628 72C0378 24.638 1.6 72 305.630 59.443 53 3383 6880 720C396 1 I. 732 1.114 241.287 37.152 54 3386 6853 7200399 12.906 1.247 270.241 37.152 55 3345 6822 7200402 12.906 1.857 418.230 54.489 56 3413 6820 7200405 13.492 1. 592 312.064 53.251 57 3361 6660 7200408 14.079 1. 221 273.458 39.628 58 3403 6653 7200411 18. 772 1. 725 315.281 55.728 65 3422 6852 7200432 14.665 1. 380 299.196 43. 344 66 3457 68 51 72CC435 14.665 1.449 176.944 42.105 67 34 52 68C8 72C0438 23.861 2. 130 434.899 98.701 69 3433 6681 7200444 6.893 1.141 164.295 25.325 114 2941 7389 730020 27. 220 2.391 302.418 74.833 115 2957 7474 730024 17. 593 1. 793 316.483 65.033 116 2961 7511 73002 7 18.257 1.753 316.483 65.033 117 3011 7541 730033 18.589 1.873 393.846 65.924 8. I 8. 1 * Sample rejected for containing anomalously high concentrations of the underlined element (s) . + Blank = value not measured. 259 SAMPLE DESCRIPTION SITE U.T.M. SAMPLE CU FE MN ZN . SE PH NO. COORDINATES NO. (PPM) (%) (PPM) (PPM) (PPM) E N C HORIZON Humm-SOIL ocky Moraine Wash board Moraine Ridged End Moraine 118 2957 7612 73C039 24. 232 2. 271 369.231 119 3059 7591 730042 13.278 1.435 253.187 120 3C92 7568 73C045 7.303 0.510 140.659 214 3309 6810 7304 22 14.151 1. 752 327.840 216 3236 6700 730431 11.900 1.448 292.205 217 32 53 6672 73C437 5. 789 0.789 174.610 218 3219 6610 73C443 13.829 1.562 270.824 220 3152 6637 73C457 12.995 1.294 261.947 228 3398 6693 730511 12.995 1.2 18 254.867 229 3470 6691 730517 23.836 1.880 363.070 63 3461 6988 7200426 14.079 1 .343 257 . 37 3 64 3494 6926 7200429 14.079 1.4 59 267.024 77 3547 6911 72C0468 12.726 1. 166 206. 174 78 3542 6885 72C0471 1 7. 498 1. 521 273.825 79 3607 6814 7200473 15.907 1. 471 206.174 80 3552 6743 72CC477 16. 968 1.521 376.913 82 3518 6648 7200483 12.726 1.293 244.832 87 3680 6975 720C497 12.196 1.029 180.403 90 3710 6876 720C507 14.749 1.327 262.654 91 3620 6737 7200510 17.909 1 . 498 239.672 94 3641 6688 7200519 12.115 1.311 219.973 98 3790 70 10 720C531 15.802 1. 552 443.229 99 3803 6998 7200534 14.222 1.231 321.751 101 3747 6891 72CC540 16.856 1.391 275.786 102 3747 6872 72C0543 12.642 1. 177 249. 52 I 1 C3 3769 6808 72 C0545 15.802 1.472 311.902 104 3803 6750 720C549 14.222 1 .980 308.618 105 38C8 6697 7200552 13.169 1.498 262.654 230 3489 6725 730523 28.836 1.995 448.498 231 3538 6739 730529 18.023 1.650 281.201 2 33 3495 6984 730538 20.000 1.611 356. 142 235 3742 7011 730548 17.622 1 . 765 224.249 244 3470 7020 73C591 13.985 1.219 227.155 11 2948 6610 72C0269 22. 203 1 .6C6 320.930 12 2983 6550 720C272 14.432 1. 324 237.209 23 3076 6599 7200305 15.526 1 .650 187.854 24 3063 6628 7200309 23.001 2.100 259.109 121 3067 7509 730048 23.900 2.391 323.516 210 3088 7542 730393 15.802 1.976 244.248 211 3102 7506 730399 16.080 1.8 29 302.895 81.96 0 48.107 15.234 47. 802 46.900 22.548 50. 507 40.912 40.912 76. 191 39.628 47.059 34.416 51.948 48.052 64.935 36.364 35.065 67.866 90.488 61.697 88.432 67.866 82.262 58. 61 2 76.093 96.658 71. 979 83.278 5 3. 156 48.246 66.445 37. 37 5 61.244 40. 829 47.500 62.500 75.724 54.607 56. 82 1 8 . 3 8. 1 8.2 3. 1 3.4 7.9 8. 5 7.9 8.7 8.1 ALLUVIUM 17 3104 69C0 720C287 4.996 1 .046 327.907 20.415 29 3128 6893 7200324 20.701 1.900 272.065 53.750 38 3238 7 02 5 7200351 5.750 0.565 139.271 19.750 50 3357 7111 72CC387 8. 799 0. 876 154.424 26.625 70 3431 6658 7200446 8.484 1.471 241.61 1 29. 870 74 3588 7063 720C459 13.786 1.217 209.396 44.156 92 3682 6748 720C513 16.329 1. 605 361.149 82.262 • 111 3017 7281 730009 9.295 0.693 573.187 37.416 122 3083 7452 73CC51 9.62 7 1 .235 193.407 33.853 * Sample rejected for containing anomalous concentrations of the underlined element (s) + Blank = value not measured. 7. 8 8.5 7.8 8.3 260 C HORIZON ALLU-SOIL VTUM t SITE U.T .M. SAMPLE CU FE MN ' ZN SE+ PH+ NO. COORDINATES NO. (PPM) (% SOIL) (PPM) (PPM) (PPM) E ' N (PPM WHEAT) 132 3145 7309 73C090 13.920 1.486 269.879 48.009 8.5 136 3219 7451 730105 19.220 1.984 356.944 69.750 8.4 145 3297 7281 730147 13.488 1 .376 221 .305 35.726 8.6 150 3363 7177 730165 13.815 1.236 246.968 37.437 167 3443 7184 730230 14.215 1.220 239.648 56.236 170 3601 7200 73C243 11.846 1 .448 296.035 58.050 9.3 185 3682 7253 730303 10.026 1. 032 189.522 35.457 191 3768 7252 73 0324 7. 352 0.880 189 .522 3 1.025 8. 6 193 3776 7305 730333 4. 741 0. 801 201.770 21.479 195 3789 7429 730339 16.198 1. 4 54 261.947 56.428 198 3775 7545 73C351 13.432 1.267 191. 150 39.135 8.1 238 3604 6910 73C562 12.816 1.228 213.57 1 47.841 73 3 5 83 6992 7200456 8. 484 0.882 151.409 34.805 89 3630 6911 7200504 9. 544 1.090 199.732 42.857 106 3768 6627 7200555 3. 160 0. 546 91.929 26.324 123 3110 7381 73C057 5.634 0. 422 70.099 12. 220 6.6 133 3243 7343 73C093 3.314 0.474 80.613 15.887 141 3237 7472 730129 5. 058 0.4 05 123.500 14.886 8.4 146 3260 7280 73C150 3.454 0.478 70.562 22.284 152 3407 7278 730171 7.598 0.885 208. 159 24.067 155 3349 7436 730180 5. 526 0.482 67.034 15.688 8.5 163 3473 7379 7 30216 5.415 0. 800 137.445 31 .746 164 3455 7345 730219 10.153 1 .240 190.308 40.8 16 165 3446 7277 730222 5. 077 0.6 16 1 12.775 I 7.415 166 3438 7252 730225 5.077 0.720 126.872 22.313 7. 8 169 3603 7147 730237 4.73 8 0.648 193.833 15.420 7.9 173 3557 7322 730255 7. 784 1 .1 36 169.163 36. 28 1 8.3 174 35 40 7345 73C261 4. 06 1 0.5 80 86.696 22.404 3. 3 175 3609 743 1 7 30267 7. 446 0. 840 197.357 34.467 179 3658 7561 730282 8.689 1. 180 178.588 46.094 1 80 3678 7539 730285 6.016 0. 364 153.075 30.139 181 3648 7463 73C288 4. 679 0. 776 116.629 31. 02 5 182 3716 7 39 8 730291 4.010 0.756 123.918 22.515 8. 1 183 3687 7367 730297 4. 010 0.660 120.273 19.058 *184 3700 7302 730300 14.037 1. 380 280.638 52.299 194 3728 73 61 730336 5.136 0.846 176.99 1 19.386 196 3737 7451 730342 4. 741 0.865 134.513 21.843 197 3 73 8 7500 730345 5. 136 0. 883 141.593 24.755 7.4 240 36 23 7433 730573 I 1.214 1.266 245.606 41.639 2. ROSETOWN AREA WHEAT AND ASSOCIATED SOIL (TABLES XXIII AND XXVTII) LAC. 251 29 53 7152 740598 12.348 151.64 43 .845 21.432 2 .120 CLAY 2 52 3008 7156 740601 1 6. 582 187.32 37.481 18.845 253 3029 7040 740604 14.818 114.17 39.602 17.367 3 .880 263 3319 7417 740634 12.348 139. 15 26.873 22.818 1 .020 283 3280 7390 740694 I 7.471 100.46 30.280 19.738 2 .1 80 * Sample rejected for containing anomalously high concentrations of the underlined elemeent(s) . + Blank = value not measured. 261 SAMPLE DESCRIPTION SITE U.T.M. SAMPLE CU+ FE+ MN+ ' ZN+ SE + PH+ NO. COORDINATES NO. (PPM) (PPM) (PPM) (PPM) (PPM) WHEAT LAC. CLAY *284 3C70 7223 740697 10.696 159.09 33.032 33.201 285 2919 6998 740700 16.045 120.91 35.097 24.105 3 .160 286 2960 6997 740703 13.192 88.64 32.688 24.559 2 .1 80 287 2991 6860 740706 15.331 156.36 36.817 18. 192 *288 2932 6839 74C7C9 16.401 143.18 49.892 13.644 3 .560 289 2982 6770 740712 13.549 76.36 39.570 16.328 2 .5 80 290 3067 67C0 740715 14. 975 89. 54 32.688 2 1.831 2 .420 291 31 09 6797 740713 14.975 126.82 32.000 25. 014 292 3185 6800 74C721 13.549 65.00 26.151 26.651 293 3069 6928 740724 14.690 96. 34 41.695 26.132 294 3223 6961 740727 12.019 12 8.00 40.678 23.564 5 .400 295 3123 6995 740730 1 4. 02 2 96.78 41 .356 17.880 296 3C99 6988 740733 13.020 120.42 31.186 21.547 306 3135 7215 74C763 12.686 74.93 32.203 18.980 1 .940 307 3158 71 89 740766 14. 022 147.13 37 .28 3 22.189 322 3221 7182 740811 17.525 74.22 30.728 27. 518 1 .0 40 323 3240 7215 740814 17.850 80. 89 34.614 24.767 3 24 3327 7231 74C817 1 3. 631 59. 11 29.316 2 1.818 339 3750 7154 740862 14.280 80. 00 37.036 27.518 354 3613 656C 740907 16. 162 89.57 36.247 26.634 5 .160 359 3087 7 122 740922 13.899 64. 88 36.247 22. 388 1 .920 360 3003 7035 740925 13.576 61.95 29.850 19.976 1 .900 361 2956 6812 74C928 14.222 61 . 53 39.800 19.300 1 .600 LAC. SILT AND SAND *256 3558 7544 740613 13.760 131.57 25.459 24.480 1 .000 257 3482 7585 740616 12.701 8 0.. 28 34.652 24.296 2 58 3428 7595 740619 16.229 109.2 7 26.87 3 24.203 0 .96 0 260 3281 7537 740625 16. 93 5 100. 35 25.459 28.360 261 3287 7516 740628 17.641 87. 86 27.580 24. 665 1 .680 262 3 286 7500 74C631 16. 935 73.94 28.287 23.279 268 3 72 2 7 3 28 740649 1 1.290 77. 60 22.276 31.963 277 3383 7474 740676 16.401 90. 91 27.527 19.557 1 .0 80 278 3399 7 473 740679 17. 82 7 76.36 22.710 2 1.831 1 .020 279 3479 7444 740682 13.905 90. 91 32.000 23.286 2 80 3514 7435 74C685 16.758 92. 73 26.151 22.922 1 .600 281 3530 7397 740688 14.262 84. 09 23.398 19.829 282 3543 74C5 74C691 16.045 85. 00 23.903 2 1. 467 1 . 140 297 2940 7292 740736 15.023 91. 43 25.763 23.473 1 .700 298 3019 7323 74C739 14.022 91. 88 20.339 19.897 1 .000 299 3056 7322 740742 14.022 92. 32 32.542 22.464 301 3140 7379 740748 14.356 64.22 25.085 22.739 302 3217 7481 740751 1 7.360 98. 56 29.492 2 6.407 303 3192 7459 740754 16.025 99.46 23.390 26.957 304 3102 7477 740757 14.356 89.20 21 .017 19.713 305 3117 7433 740760 14.356 84. 29 21.017 28. 607 0 .440 325 3362 7132 740820 3 .600 326 3508 72 10 740823 12.333 81 . 78 32.49 4 27. 027 0.330 348 3172 7416 740389 13. 576 76. 60 33.404 24. 125 0. 380 355 3780 67C5 74C910 2 .600 358 3179 7433 740919 14.545 89. 16 33.048 26.345 1 .600 * Sample rejected for containing anomalously high concentrations of the underlined element (s) . + Blank = value not measured. 262 SAMPLE DESCRIPTION SITE NO. WHEAT GLACIAL TILL U.T.M. COORDINATES SAMPLE NO. CU (PPM) FE (PPM) E N , 308 3358 6967 740769 14.022 113.28 309 3376 6954 74G772 12.686 91.43 310 3409 6953 740775 14. 690 107.04 311 3424 6972 740778 13.354 82.96 312 3450 6912 740781 12.353 74. 04 313 3398 6888 740784 11.685 63. 33 314 3307 6803 740787 12.982 91. 11 315 3311 67E2 740790 11.359 69.33 *316 3283 6667 74C793 14.929 164.44 317 3300 66C5 74C796 14.929 98.67 318 3282 6590 740799 14. 929' 88.00 319 3261 6563 740802 15.578 80. 89 3 20 3218 6630 740805 15.254 132.00 321 3162 6722 740808 14.280 82. 22 341 3703 6973 740868 121.78 34 2 3731 6971 74C671 15.903 343 3731 6993 740874 14.280 66. 67 344 3775 7010 74C877 349 3350 6792 740892 77. 85 3 50 3410 6759 740895 14.869 351 3573 6861 740898 15. 192 64.46 353 3585 6690 740904 14.869 81. 20 356 3743 6871 740913 15.833 92. 09 357 3797 6916 74C916 MN (PPM) 28.136 27.797 21.017 21.695 25.763 16.949 31.082 32.848 42.031 40.618 35. 320 28.962 35.320 22.605 29.669 26.137 20.611 27.713 27.007 30.205 ZN (PPM) 23. 656 27.966 27. 140 30.716 18.155 18.338 20.344 21.622 22. 113 21.818 24. 177 28. 698 20.049 21.622 24.079 23.587 27.406 23.836 28.372 26.538 SE (PPM) PH" I .240 1 .280 1 .780 3 .700 0.380 9.500 1 .400 1 .040 11.200 6 .000 1.540 1 .000 1 .500 1.12 0 6.400 AEOLIAN SAND 254 3679 7587 740607 255 3608 7540 740610 2 59 33 54 7537 740622 264 3627 7460 740637 265 3549 7273 740640 267 3692 7297 740646 269 3728 7366 740652 270 3748 7425 740655 271 3729 7393 740658 272 31 83 7249 740661 274 3200 7248 740667 *275 3210 7343 74C670 276 3175 7350 740673 300 3102 7380 740745 327 3564 72 03 74C826 328 3347 7475 74C829 329 33 79 7509 74C332 330 33 41 7472 74C835 331 3324 7440 740838 *332 3319 7437 74C841 3 34 3623 7093 74C847 335 3615 7129 740850 336 3763 72C4 74C853 345 3453 72 4 8 74C880 346 3492 7327 74C383 13.407 13.407 13.407 11.996 13. 407 13.407 13.054 13.054 12.348 11.409 11.409 14.975 15.331 12.019 12.008 11.034 10.385 14.929 12.333 14.929 104.36 83. 85 100.79 118.19 100.35 73.59 99. 01 78.94 77 .60 108.64 7 4. 54 227.27 77. 27 72. 25 69.33 67. 56 73.33 82. 22 61. 33 142.22 11. 636 72. 83 26 .873 24.751 19.801 21.923 21.923 12.729 22.276 25.812 25.459 22.022 12.387 21 .677 19.613 11.525 21 .898 14.834 26.137 16.954 24.371 19.426 13.148 26.513 28. 1 76 21.801 29. 56 1 2 6. 513 23.095 27.714 34. 457 19.400 2 5.469 30.927 21 .831 30. 654 21.639 23.784 1 9. 459 19.165 30.467 24.767 23.096 24. 125 0.570 0.640 0.620 0 .540 0.760 0.640 0.560 0.480 0.420 1 .440 2 .580 2.730 3 .130 0.680 4 .000 * Sample rejected for containing anomalously high concentrations of the underlined element (s) + Blank = value not measured. 263 A HORIZON LAC. SOIL CLAY SITE U.T. M. SAMPLE CU FE MN ZN NO. COORDINATES NO. (PPM) (%) (PPM) (PPM) 251 29*53 7^52 740C596 25. 852 2. 4 82 454.586 94.144 252 3008 7156 7400599 28. 3 74 2. 177 350.783 72.928 2 53 302 9 7040 7400602 29.320 2. 635 400.895 92.818 263 3319 7417 740C632 13.631 1. 4 72 294.005 57. 174 283 3280 7390 74CC692 13.353 2. 081 391.546 75. 082 284 3070 7223 74CC695 15.261 1.890 420 .022 78.346 285 2919 69S8 740C698 23.845 2. 749 345.272 86.181 286 2960 6997 7400701 24.799 2. 215 295.439 73.776 287 2991 6860 74GC704 22.414 2. 8 64 377.308 9 1.404 288 2932 6 839 74CC707 26.230 2. 444 302.558 78.346 289 2 9 82 6770 7400710 23.368 2. 673 355.95 I 88.139 290 3067 67C0 7400713 25. 514 2. 864 355.951 97.933 291 3109 6797 7400716 17.407 2. 406 391.546 81. 610 292 3165 68C0 7400719 13.830 1. 947 402.225 67.900 293 3069 6928 740C722 27. 340 2. 568 417.548 86.557 294 3223 6961 7400725 28.893 2. 491 449.944 90.492 295 3123 6995 74CC728 29.204 2.721 424.747 85.246 296 3099 6988 7400731 30. 447 2. 549 352.756 8C.656 306 3135 7215 7400761 20.585 2. 153 417.391 80.465 3C7 3158. 7189 74CC764 19.649 1 . 958 428.375 77.930 322 3221 7182 74CC809 20.391 2. 117 437. 856 84. 599 323 3240 7215 74CC812 15.457 1. 683 369.44 1 69.63 1 3 24 3327 7231 740C815 1 5. 786 1. 791 355.758 65.076 339 3750 7154 7400860 15.683 1. 524 400.921 69.328 354 3613 6560 7400905 17.442 2. 088 386.207 72.414 359 3087 7122 740C920 22.877 2. 1 33 405.806 75.661 360 3 003 7035 7400923 31.560 2. 2 57 337.327 72.076 361 2956 6812 74CC926 30.059 2. 4 84 351.264 78.601 256 3558 7544 740061 1 15.133 1. 6 80 411.633 76.243 257 3432 7585 740C614 15.448 1. 757 422.371 82.21 0 '258 3428 7595 7400617 15.133 1. 757 386.577 517.127 260 32 81 7537 740C623 I 6.C79 1. 718 422 .371 84.199 261 3287 7516 740C626 15.133 1. 757 375.839 8C.884 262 3286 7500 74C0629 14.280 1. 4 92 344.202 68.346 268 3722 7328 74C0647 7. 140 1. 077 294.005 44.688 277 3383 7474 7400674 10.640 1. 796 346.816 7 9.0 34 278 3399 7473 7400677 11. 60 7 1. 739 339.665 64.544 279 3479 7444 740C680 9. 189 1. 455 346.816 79.034 280 3514 7435 7400683 10.156 1. 607 346.816 102.086 281 3530 7397 74CC686 8. 947 1. 493 311 .061 7 1.13 1 282 3543 7405 740C689 10. 156 1. 5 50 368.268 44. 127 297 2940 7292 74CC734 16.466 1. 8 40 316.760 68.852 298 3019 7328 74CC737 10.563 1. 226 241. 170 5 1.148 299 3056 7322 7400740 13.359 1. 456 287.964 61.639 301 3 140 7379 7400746 13.359 1.6 10 305.961 57.049 302 3217 7481 74CC749 19.262 1. 954 341.957 66.885 3 03 3192 7459 7400752 14.602 1. 6 10 313. 161 6G.984 '304 3102 7477 74C0755 24. 327 2. 2 84 411.899 74.129 305 3117 7433 7400753 16.218 1. 468 378.947 66.526 325 3362 7132 74CC818 19.253 1. 855 391.724 77.754 3 26 35C8 7210 740C821 12.282 1. 473 331.034 62.851 SE (PPM) PH 7.2 8.1 7.7 6.4 7.0 6.3 7.8 7.7 7.9 7.8 7. 7 7.8 7.3 7.1 7.9 7.8 8.2 7.1 7. 3 7.2 6.2 6.3 7.1 6.4 7.4 6.6 7.9 7.6 6.3 6.9 6. 9 6 .4 6.4 6.5 7.1 6.8 6.4 6.4 7.1 7.8 6. 5 7.9 6. 8 6.7 7.5 * Sample rejected for containing anomalously high concentrations of the underlined element (s) + Blank = value not measured. 264 NO. E N 348 3172 7416 355 3780 67C5 358 3179 7433 'SAMPLE DESCRIPTION SITE A HORIZON LAC. SOIL SAND AND SILT GLACIAL 308 3358 6967 TILL 309 3376 6954 310 3409 6953 311 3424 6972 312 3450 6912 313 3398 6888 314 3307 6303 315 3311 6782 316 3283 6667 317 3300 6605 318 3282 6590 319 3261 6563 *320 3218 6630 321 3162 6 722 341 3703 6973 342 3731 6971 343 3731 6993 344 3775 7010 349 3350 6792 350 3410 6759 351 3573 6861 352 3598 6752 353 3585 6690 356 3743 6371 357 3797 6916 SAMPLE NO. 740C887 74CC908 74CC917 7400767 740C770 740C773 74CC776 7400779 740C782 74CC785 7400788 740C79 1 74CC794 740C797 74CC800 7400803 74CC806 74CC866 7400869 740C872 74CC875 74C0890 740C893 7400896 74GC899 74C0902 7400911 74CC914 CU (PPM) 17.778 11.069 17.792 16.530 19.337 18.090 14.971 13.411 13.723 20.719 17. 102 20.391 19.075 17.102 19.733 24.337 16.444 12.013 16.017 14.682 14.348 15.765 11.740 14.423 14.088 16.101 12.459 10.157 FE (%) 1.925 1.492 1. 808 1.794 1.794 1.9 30 1. 615 1.631 1 .495 1. 710 1.683 2.117 2. 063 1.873 1.927 2.226 1 .683 1. 676 1.879 1.625 1.686 1.681 1. 323 1.398 1.725 1. 492 1.503 1 .123 MN (PPM) 419.310 297.931 385.023 351.487 392.677 373.455 417.391 307.552 3 76.201 323.392 509.008 424.173 405.017 451.540 448.803 541.847 383.124 290.322 320.737 345.622 331.797 441.379 275 .862 284.138 377.931 391.72 4 339.515 229.336 ZN ' (PPM) 80. 172 53.017 69.209 65.892 68.427 67.159 7 1. 594 53. 854 60.190 52.711 75.488 71.584 68. 330 71.584 65.076 78.091 63.774 58.190 62. 069 64.655 64.655 73.060 45.259 64.655 64.655 64.65 5 56.774 27.527 SE (PPM) PH 7.3 8.0 7.0 6.7 6.8 6.6 6.0 7.9 7.9 8.4 8. 1 8.0 3.0 7.9 8.0 4 , 5 ,9 . 8 .0 . 1 . 9 7.3 7.0 7.5 7.4 7.7 7.6 AEOLIAN 254 3679 7587 740C605 SAND *255 2 59 3608 7540 7400603 3354 7537 7400620 264 3627 74 6 0 74006 35 265 3549 7273 7400638 267 3692 7297 7400644 269 3728 7366 740C650 270 3748 7425 7400653 271 3729 7393 74CC656 272 3183 7249 7400659 2 74 3200 7248 7400665 27 5 32 10 7343 74CC668 276 3175 7350 74GC671 300 3102 7380 7400743 3 27 3564 7203 740C824 328 3347 7475 740C827 329 3379 75C9 74CG830 330 3341 74 72 74C0833 331 3324 7440 7400836 *332 3319 7437 74CC339 333 3623 7083 740C842 10.719 1 1.980 6.305 6. 81 5 5. 842 5.842 7.789 5.517 7. 140 5. 562 3. 869 5.320 7. 496 6.835 7.967 8.963 11.618 8.299 11.6 18 6.6 39 5. 643 1.2 60 1. 146 0. 894 0. 969 0. 891 0.930 1 .123 1.038 1.104 0. 862 0.567 0. 998 1. 134 0. 843 1.129 1.037 1.255 1. 146 1.2 00 .753 , 900 0. 0. 279. 195 304.250 178.97 1 179.272 179.272 179.272 268.907 218.711 276.078 185.922 114.413 160.894 332.514 165.579 248.276 206.896 286.896 187.586 237.241 377.931 137.931 51.713 6 9.613. 29.834 34.330 2 8.258 34.173 40.745 34.173 39.430 36. 883 25.027 32.931 44.786 32.787 37.581 40.821 58.315 43.413 49.892 23.974 29.158 6.1 6. 5 7.8 6.5 6. 8 7.8 6. 6 6.4 6.8 6. 6 6. 8 8.2 * Sample rejected for containing anomalously high concentrations of the underlined element (s) . + Blank = value not measured. 265 SAMPLE DESCRIPTION SITE U.T.M. SAMPLE CU FE m ZN SE PH NO. COORDINATES NO. (PPM) (%) (PPM) (PPM) (PPM) EN SOIL SAND 334 3623 7C93 7400845 7.967 1.004 v 146.207 33.693 8. 0 335 3615 7129 740C848 5.673 0.965 152.074 25. 862 8. 6 336 3763 72 04 7400851 7.341 1 .057 17 4. 19 4 42.026 7. 2 337 3768 7218 74CC854 9. 009 0.965 179.723 40.733 6. 8 338 3698 7208 74CC857 9.34 3 1.092 171.429 38. 793 7. 4 345 3453 7248 74CC878 9.009 1.016 248.848 43. 319 7. 2 346 3492 7327 740C881 10. 734 1.258 275.862 54.957 6. 8 347 3345 7422 7400884 6.373 0.949 146.207 32. 328 7. 2 C HORIZON SOIL LAC. CLAY 251 2953 7152 7400597 3 I. 527 2. 138 343.624 82.873 0. 32 8. 1 252 3008 7156 7400600 26. 483 1. 928 357.942 6 1.657 7.9 253 3029 7040 740C603 29.005 2.368 340.045 79. 558 0.64 3.2 2 63 3319 74 17 7400633 27.586 2. 189 333.445 65.717 0. 70 3. 6 283 3280 7390 740C693 17.407 2. 062 3 02 . 55 8 61.37 1 0. 36 8.4 284 3070 7223 7400696 16.215 1 .604 202.892 48.966 28 3. 1 285 2919 6998 7400699 26.945 2 .406 2 84.761 76.337 1 . 8.1 286 2960 6997 74CC7G2 24.799 2. 444 302.558 77.040 0. 35 8.3 287 2991 6860 7400705 24.560 2. 558 313.237 78.346 8. 2 288 2932 683 9 74C0708 32.429 2.177 224.249 65.288 1. 92 8.2 289 2982 6770 7400711 2 5. 2 76 2.406 259.844 78.346 0 . 3 4 8.3 290 3067 6700 740Q714 23.845 3. 131 320.356 99.238 0. 3 3 3. 2 29 1 3109 6797 74CC717 21.461 2 .368 266.963 71.817 8 . 2 292 3185 68C0 7400720 15.499 1.489 220.690 4 3. 743 3.6 293 3069 6928 740C723 37.282 2.223 295. 163 68.852 3.4 294 3223 6961 7400726 27.340 2. 529 4 10.349 88.525 0. ,74 3 .4 295 3123 6995 7400729 30.447 2.0 12 287.964 56.393 8.0 296 3C99 6988 7400732 27.340 2. 721 334.758 81.967 .24 8.6 306 3135 7215 74C0762 19.961 1.794 367.963 5 8. 923 0 . 3.5 3 07 3158 7189 7400765 24.016 2.066 340.503 65.892 3. 6 322 3221 7182 740C810 25.324 2.443 344.812 71.56 4 0 . .38 3.2 323 3240 7215 74CC813 14.800 1.7 37 301.026 49.458 7. 8 324 3327 7231 740C816 14.606 1.528 256.552 48.596 3.6 339 3750 7154 740C861 14.015 1. 829 276.498 51.724 3 . 1 340 3769 7102 7400864 19.020 2. 083 345.622 72.414 8.6 354 3613 6560 7400906 22.474 2.061 325.517 62.716 0 , .28 3.3 359 3087 7 122 7400921 24. 935 1. 764 299.391 60. 150 o, .26 8.2 36C 3C03 7035 740C924 29.976 2.070 297.003 67.205 0.27 8.4 361 2956 6812 74CC927 30.059 2.3 63 320.698 78.950 0 .57 8.5 LAC. 256 3558 7544 74006 12 11.665 1.713 268.456 45.083 0.18 6.9 SILT 257 . 3482 7585 7400615 14.502 2. 024 311.409 54.365 7.2 AND 258 3428 7595 7400618 16.709 1.642 268.456 72.928 0.46 8.6 SAND 260 3281 7537 740C624 13.241 1 .432 221.924 46.409 8.3 261 3287 7 516 7400627 15.578 1. 588 243.810 50. 602 0.26 8.2 262 3286 7500 74CC630 12.657 1 .588 207 .955 40.745 7. 1 268 3722 7328 74CC648 5. 517 0. 988 207.955 26.287 8.4 277 3383 7474 7400675 10.640 1.701 264.581 80.351 0.24 8. 4 278 3399 7473 74CC678 12.574 1.739 271.732 88.255 0.2 8 8.4 279 3479 7444 7400681 6.287 1.210 178.771 98.793 8.1 280 3514 7435 74CC684 7.254 1.285 207.374 82.327 0.20 8. 2 + Blank = value not measured. 266 SAMPLE DESCRIPTION SITE U.T.M SAMPLE CU FE' MN W SE+ PH NO. COORDINATES NO. (PPM) (%) (PPM) (PPM' (FM> C HORIZON SOIL LAC. SILT AND SAND 281 3530 7397 74C0687 282 3543 7405 7400690 297 2940 7292 7400735 298 3019 7328 74CC738 299 3056 73 22 74CC741 301 3 140 7379 74CC747 ' 302 3217 7481 740C750 303 3192 7459 7400753 304 3102 7477 740C756 305 3117 7433 740C759 325 3362 7132 7400819 3 26 3508 7210 740C822 348 3172 7416 74C0888 3 55 3780 67C5 74C0909 358 3179 7433 74CC918 308 33 58 6967 74CC768 309 3376 6954 74C0771 310 3409 69 53 7400774 311 3424 6972 74CC777 312 3450 6912 7400780 313 3398 6888 74CC783 314 33 07 6803 74CC786 315 3311 6782 7400789 316 3283 6 66 7 74CC792 317 3300 66C5 74CC795 318 3282 6590 74CC798 319 3261 6563 740C801 320 3218 6630 740C804 *32l 3162 6 722 740C807 341 3703 6973 74CC867 342 3731 6971 7400870 343 3731 6993 740Ce73 344 3775 7010 740C876 349 3 35 0 6792 740C891 3 50 3410 6759 740C894 351 3573 686 I 7400897 352 3598 6752 74C0900 *3 53 3585 6690 74C0903 356 3743 6871 7400912 357 3797 69 16 74CCS15 8.222 10.015 14.602 14.602 17.398 14.913 28.583 8.421 24.951 13.411 14.606 11.618 18.449 9.057 23. 823 1.361 1. 547 1.495 1.610 1.744 1.590 2. 299 1.033 2.066 1. 4 68 2. 101 1.2C0 1.736 1.106 1.687 14.035 16.218 13.723 16.218 14.659 19.337 15.457 13.313 19.733 19.733 17.760 19.733 22.035 16.444 14.015 16.017 16.017 12.013 21. 132 10.734 13.417 15.765 17.773 17.339 10.442 232. 242. 259. 2 08. 2 33. 226. 341. 156. 351. 164. 344. 2 09. 284. 275 325 402 047 167 774 971 .772 .957 . 522 .437 . 760 .827 .655 .138 .862 .731 68 39. 59. 44. 5 1. 44. 65. 30. 65. 43. 74. 36. 54. 28. 58. 496 1 73 016 590 148 590 574 412 259 083 514 933 957 448 055 0.6 0 0.20 0.42 0.28 0.44 0.22 0.45 0.40 0.6 3 8.2 8.3 8.8 8.2 8.3 8.3 8.5 8.7 8.6 8.5 7. 3 8 1 .349 255.378 38.0 15 8.3 1.4 14 269.107 39.232 8.3 1 .305 263.615 36.648 8. 7 1 .658 324.027 44.35 1 3.3 1 .441 291.075 41. 183 0 . 1 8 8. 6 1.523 296.567 43.033 0. 36 8.3 1. 5 74 339.339 48.156 0. ,26 8.9 2.0 36 333.865 60,52 1 7.6 1 . 737 328.392 5 6.616 3.4 1. 656 311.973 5C.759 0. ,24 8.6 1.683 3 14.709 53.362 8. 4 1.818 361 . 23 2 53. 362 0. .36 8.7 1.818 394.071 61.322 3.9 1.7 10 506.272 6 5.07 6 6.0 1. 473 254.378 35.560 0 .18 3.2 1.727 254.37 3 48.49 1 0 .36 8. 6 2. 032 282.028 6 1.422 0 .2 1 7.5 1.2 95 212.903 36.8 53 0 .27 3. 3 1.681 358.62 1 53.017 0 .5 8 8. 0 1. 1 66 262.069 3 1.034 0 .08 8. 1 1. 508 215. 172 42.672 0 .14 3.4 1.519 284.138 46.552 8. 1 1.953 468.965 85.345 0 .25 8. 0 1.7 09 307.154 5 1.038 1 .50 8.2 1.222 229.336 28.383 0 .29 8.1 AEOLIAN 254 3679 7587 74 C0606 12.926 SAND 2 55 3608 7-54 0 7400609 15.133 2 59 3354 7537 7400621 9.458 264 3627 7460 74G0636 7. 140 265 3549 7273 740C639 4. 544 267 3692 7297 7400645 3.895 269 3728 7366 740C651 8. 763 270 3748 7425 7400654 3.895 271 3729 7 393 74CC657 10.385 1.165 1.451 1.214 1.1 04 0.910 0.8 33 1.414 0.930 1.550 178.971 232.662 218.344 186.443 161.345 132.661 233.053 172.101 276.078 37.127 58.343 35.138 32.859 24. 315 28.258 36.802 21.030 42.059 0.20 0.18 0.20 0.26 8.0 8.0 8. 5 7.3 7.5 7. 2 7.4 7.0 7.8 * Sample rejected for containing anomalously high concentrations of the underlined element (s) + Blank = value not measured. 267 SAMPLE DESCRIPTION SITE NO. U.T.M. (XXDRDINATES E N SAMPLE NO. CU (PPM) FE (%) MN (PPM) ZN (PPM) SE (PPM) PH C HORIZON AEOLIAN 2 72 3183 7249 74CC660 4. Ill 1.191 121.564 30.296 0. 24 7.1 SOIL SAND *274 3200 7248 7400666 4.111 0.711 10011.172 18.441 0. I 0 6.5 275 3210 7343 7400669 4.353 1.115 132.29 I 3 1.614 8.4 276 3175 7350 7400672 2. 902 0.567 221.676 1 C. 999 0. 10 8.3 300 3102 7380 7400744 5.592 0.901 118.785 24.913 0. 13 6.9 327 3564 72 03 7400825 4.315 0.938 220.690 18.143 0. 12 8.4 3 28 3347 7475 740C828 9. 959 1.391 184.828 36.933 7.2 329 3379 7509 7400831 10.622 1 . 500 228.965 40.321 7.2 330 3341 7472 740C834 9.295 1.228 171.034 38.877 8.2 *33l 3324 7440 74C0837 21.909 2.455 353.103 69.978 6. 7 332 3319 7437 7400840 12.282 1 . 664 262.069 5 5.076 0. 18 7.1 333 3623 70E3 7400843 5. 643 0. 835 132.414 24.622 8.7 334 3623 7093 7400846 4.315 0.8 18 132.414 23.974 0. 07 8.5 335 3615 7129 7400849 4.004 0.828 229.493 14.871 0. 07 8.9 336 3763 7204 740C852 6. 0C6 0. 940 132.719 29.741 0. 09 3.1 337 3768 7218 7400855 5.673 0.813 110.599 23.922 7.9 338 369 8 72C8 740G858 7.341 1.2 70 179.723 37.500 8.3 345 3453 7248 740C879 6.373 0. 786 146.207 2 1. 336 0. 0 8 8.5 346 349 2 7327 74CC382 7.044 0.803 137.931 23.276 0. 08 8.1 347 3345 7422 7400885 8.386 1.226 176.552 42.026 8.2 3. RC6ET0WN AREA BEDROCK - BEARPAW FORMATION (TABLE XXVII) MEMBER DRILL SAMPLE SE HOLE NO. (PPM) NO. AOUADELL I C168 740996 0.436 10168 74C998 0.465 10168 7410CC 0.740 10168 741002 1.170 1067 74 1005 1.040 1067 741007 0.610 1067 741C09 0.155 CRU IKSHANK 1067 741010 0.495 1067 741011 0.430 SNAKEBITE 1067 741012 0.460 1067 741014 0. 510 1067 741016 0.600 1067 741018 C.580 1067 741020 0.665 1067 741022 0.810 GSC61- 1 74 1032 0. 655 GSC61--1 741034 0.370 AROKENNITH GSC61-•1 741035 0.370 GSC6 1-• 1 741037 0. 245 GSC61-•1 741039 0.285 BEECHY GSC61--I 74 104 1 0. 62 5 GSC61-•1 741043 0.650 DEKAINE GSC61--1 741044 0.260 GSC61--1 741046 0.260 SHERARO GSC61--1 741047 0.750 GSC61--I 741049 0.575 * Sample rejected for containing anomalously high concentrations of the underlined + Blank = value not measured. 268 SAMPLE DESCRIPTION SITE U.T.M. SAMPLE CU FE MN ZN SE PH NO. COORDINATES NO. (PPM) (%) (PPM) (PPM) (PPM) E N 4. RED DEER AREA SOIL (TABLES XXXI AND XXXIII) A HORIZON GROUND SOIL MORAINE HUMMOCKY MORAINE IAC. 9 3096 7590 730589 12.048 1.346 379.526 5 1.456 7. 3 • 11 3100 7525 73C598 12.851 1.4 77 499.376 52.810 6.4 22 3183 7583 730634 10.442 0.985 366.209 56. 872 5.9 24 3234 7574 73C643 14.458 1 .477 372.867 73.121 5.9 29 3238 7783 730661 16.667 1.723 492.717 83.954 6.4 39 3393 7664 730696 12.048 1.477 319.601 62. 288 6.0 47 3527 7731 73C722 10.442 I. 182 466.084 41.977 5.8 103 2920 7682 73C930 18.349 1. 707 375.556 8C. 053 6.3 115 2667 7662 730962 14.3 60 0.952 336.706 82. 722 7.3 1 18 2722 7813 73C971 17.551 1 .641 505.058 74.716 7.6 * 123 2604 7804 73C990 10.371 1.641 1036.018 80.053 5.6 *130 2527 7793 731013 10.371 1.313 1063.393 60.040 6.5 137 2433 7707 731040 8. 347 1. 501 582.760 82.392 5.6 76 3923 7590 730831 8. 775 1 .280 330.231 49.366 6.9 * 81 406 I 7587 730e50 30.315 2.544 485.63 3 74.716 3. 0 86 4200 7709 73C865 10.371 2.051 679.886 64.043 5. 7 92 4234 7577 73C887 12.764 1 .395 518.009 65.377 5.7 34 3278 7563 730679 14.458 1 . 395 532.667 77.183 6. 5 44 3457 7560 73C713 12.851 1.313 366.209 64.997 6. 1 45 3476 7666 73C716 14.458 1. 641 319.601 54.164 5.9 51 3529 7652 7 3073 8 19.277 1 .305 332.917 67.705 6.6 54 3589 7570 730747 12.851 1. 543 319.601 5 1.456 5.8 58 3657 76 32 73076.3 16.867 2.215 499.376 6 2. 288 5.4 59 3630 7688 730768 12.043 1 . 149 199.750 64.99 7 5.4 56 3730 . 7549 730755 14.458 1. 723 279.651 51.456 6.1 72 3852 7708 730813 11.245 0.985 186.434 58. 226 6. 0 75 3920 7649 730826 12.851 1.444 412.817 66.351 5.5 79 4043 7553 730842 11.967 1.231 518.009 69.380 6.0 89 4163 7548 730876 12.764 1.231 259.004 46.698 7.8 94 4214 7615 730895 8. 775 1 .559 343. 181 54.703 5.5 2 3112 7920 730565 13.655 1. 362 346.234 56.872 8.0 S K 3179 7900 73 0610 16.867 1.674 392.843 63.643 6.8 ICO 3002 7712 730915 15.955 1.6 90 388.507 81.388 7. 1 110 2765 7856 730945 15.955 1.510 485.633 66.711 8.0 111 2783 7800 730948 14.360 1.690 343.181 65. 377 6.3 119 2740 7900 730976 14.360 1. 362 518.009 62.708 7.6 *129 2488 7745 731C08 9. 573 1.559 1133.144 78.719 6.9 133 23 74 7 922 731024 14.360 2.051 271.955 74. 71 6 6.6 136 2393 7772 73103 5 6.382 1.477 349.656 44.029 6. 1 142 4024 7493 73001535 12. 01.5 1 .1 96 367.279 49.793 7.9 147 4081 7712 73001550 10.013 0.926 347.246 51.637 6. 7 * Sample rejected for containing anomalously high concentrations of the underlined element (s) . + Blank = value not measured. 269 SAMPLE DESCRIPTION SITE U.T.M. SAMPLE CU FE MN ZN SE* PH+ NO. COORDINATES NO. (PPM) (%) (PPM) (PPM) (PPM) E N C HORIZON PASK-SOIL APOO GROUND MORAINE * 1 7 8 9 10 11 17 22 23 24 39 49 101 103 105 117 *1 18 122 123 131 3143 3100 3100 3096 3082 3100 3173 3183 32 06 3234 3393 3561 3022 2920 2920 2656 2722 2640 2604 2542 7965 7658 7638 7590 7581 7525 7780 7583 7574 7574 7664 7737 7648 7682 7730 7767 7813 7846 7804 7841 73 0564 73C585 730588 730591 73C597 73C600 730621 730636 73C642 730645 730698 73C732 730920 73C926 73C932 730970 73G973 73C989 730992 731C18 33.929 12.500 12.500 11.607 13.393 9.821 12.621 17.476 20.388 18.447 12.621 23. 301 6.481 24.074 15. 741 12.963 16.667 2C. 370 16.667 20.370 2.926. 1. 183 1 .619 1.146 1.619 0. 996 1 . 922 1.369 1.689 1.529 1. 500 1.893 1. 140 1.698 1.267 1. 337 1.012 1. 742 1.731 1 .846 275.711 229.759 407.002 315.098 328.228 190.372 6 56. 716 171.642 261.194 194.030 247.500 315.000 218.532 276.379 2 44.24 2 282.807 726.299 270.096 321.543 366.560 66.990 31. 664 36.187 37.049 53. 419 31.018 35.015 43. 027 45.994 48. C71 56.119 56.716 27. 378 52.668 41.299 41. 763 51.7^0 46.260 38.515 50.580 8.1 8.7 8.0 7.0 6. 7 8.0 8. 1 7.5 HORSE SHOE ' CANYON GROUND MORAINE 73 76 77 81 85 86 * 88 91 92 39 70 3 92 3 3976 4061 4156 4200 41 42 4270 4234 7734 7590 7563 7587 7 7 53 7 7 09 7616 7553 7577 144 4086 7748 146 3983 7688 73C820 73C833 730338 73C652 730864 73C867 73C875 730886 73C889 73001543 73001549 25.837 17. 225 20.370 18. 519 16.667 12.037 13. 889 19.444 38.889 17.763 12.82 9 1.982 1.3 50 1.638 1.488 1. 292 1. 364 1.315 1.315 2. 100 0. 998 1. 107 397. 309. 2 93. 342. 234. 310. 684 . 790 39 2 C97 495 672 782 989 298 393 233 190 ,097 23 5 422 ,98 1 6C, 50, 49, 50 4C. 51 35 46 69 4 3 34 714 000 .116 ,269 81 5 , 653 ,742 . 580 ,178 , 437 .483 8.3 7.8 5. 1 8.1 PASK APOO HUMMOCKY MORAINE 12 34 35 44 45 46 51 52 55 57 58 59 60 171 3132 32 73 3312 3457 3476 3496 3529 3620 3726 3652 3657 3630 3690 3232 7537 7563 7545 7560 7666 7679 7652 7636 7530 7628 7632 7688 7750 7697 730606 730681 73C684 730715 730718 730721 730740 73C743 730754 730762 730765 730770 73G775 73001627 13.393 13.592 21. 359 12.621 20.388 13.592 22.330 13. 592 7.767 13.397 16.268 7. 656 15.311 4. 025 1.556 1.034 1.646 1. 194 1 .675 1. 150 1.777 1.2 09 1 .063 1.163 1. 2 06 0.977 1.2C6 0.575 347. 208. 270. 187. 285. 217. 292. 165. 180. 213, 228. 110. 250, 107. 921 955 000 500 000 500 500 000 000 ,629 361 497 460 473 45.880 36.202 53.134 34.328 53.134 33.433 53.433 35.224 25. 075 29.762 35.714 28.869 3 5.714 14.45 1 7.9 8.0 8.0 8. 3 8. 1 9. 0 * Sample rejected for containing anomalously high concentrations of the underlined element(s) . + Blank = value not measured. 270 SAMPLE DESCRIPTION SITE U.T.M. SAMPLE CU FE MN ZN NO. COORDINATES t? M NO. (PPM) .(%) (PPM) (PPM) C HORIZON HORSE- 56 3730 754.9 730757 15.311 1.235 206.252 36.310 SOIL SHOE 64 3718 7670 730789 13. 39 7 1 .436 2 94.65 9 36.310 CANYON 65 3736 7548 730792 14.354 1.465 272.560 3 8. 095 HUWDCKY 66 3756 7530 730795 13.397 1 . 178 228.361 36.905 MORAINE 68 3896 757 1 73C801 13.397 1 .178 220.995 3 5.714 69 3868 7633 73C804 22.010 1.695 250.460 55. 952 70 3841 7656 73C807 13.397 1 .235 265.193 35. 119 72 3852 77G8 730815 14.354 1. 250 235.728 36.607 75 3920 7649 730828 17.225 1.408 324. 125 42. 857 * 78 3951 7521 73C841 35. 185 1.973 317. 125 71.483 79 4043 7553 73C844 15.741 I. 419 266.385 41. 045 82 4036 7639 730855 15.741 1.500 215.645 42.429 87 4117 7653 73C872 12.963 1 .592 69.767 39.662 89 4 163 7548 73C878 15.741 0.958 145.677 36.434 90 41 80 7547 730883 16.667 1.338 272.727 47.041 93 4214 7590 73C894 18.519 1.581 266.385 52.575 94 4214 7615 730897 19.444 1 .454 183.932 41. 507 143 403 3 7632 73001540 17.763 1 .197 222.812 44.444 SE (PPM) PH 8. 1 8.0 3.1 8.3 8.7 8. 1 LAC. 3 3111 7897 730573 14.286 1 .345 210.066 4 1.357 DEPOSITS 4 3110 7850 730576 13.393 1. 457 393 .873 48.034 5 3103 7780 730579 10.714 1.494 303.534 31.018 6 3053 7730 73C582 28.571 2.328 479.212 68.067 18 3 198 7732 73C624 1 7. 476 1.427 261. 194 51.92 9 97 3032 7902 730908 3. 333 1.015 234.672 28.132 ICC 3002 77 12 73C917 2C.370 1. 651 276.379 52.204 7.8 104 2361 7742 73C929 22.222 1. 733 295.661 55.684 1 C6 2877 7742 73C935 19.444 1.651 250.670 4 6.4 04 107 2932 7838 730938 26.852 1.977 231 .387 59.397 1 10 2765 7856 730947 16.667 1.535 282.807 45. 940 8. 0 1 11 2783 7 300 73C950 16.667 1 .384 224.960 42.923 8.1 112 2816 77 78 73C955 17.593 1.465 218.532 42.691 119 2 740 7900 730978 11.111 1.212 212.219 37.319 8. 1 128 2489 7727 731007 30.556 2.538 398 .714 74.246 133 2374 7922 731026 2 8. 704 2. 158 334.405 64.501 7.8 134 2370 7863 731031 12.963 1.223 257.235 40.603 135 2420 78C9 731034 22.222 1 .708 308.682 55.220 145 4003 7751 730C1546 20.724 1. 578 265.252 54.023 147 4081 7712 73001552 6. 908 0.862 122.016 19.157 148 4049 7747 73001554 22.697 1.3 62 381.963 57.854 1 49 4003 7767 73001557 17.763 1.723 228.117 54.406 ALLUVIUM-• 27 3309 7890 73C654 11.650 1.267 313.433 35. 015 OUIVJASH * 71 3823 7690 730812 20.096 3.045 1038.674 66.07 1:. DEPOSITS 116 2650 7687 73C967 8. 333 1.128 385.646 27.146 154 2365 7790 7301582 7.895 0.889 185.676 24. 329 164 2830 7756 7301608 10.063 0.997 194. 179 3 1.792 167 3061 7879 7301615 7. 044 0. 843 141.058 24.C85 168 2992 7800 7301619 15.094 1. 802 335.852 43.353 170 3333 76C8 7301624 10.C63 0.958 144.417 24.085 177 3306 7793 7301699 5.006 0.538 90.000 6.773 * Sample rejected for containing anomalously high concentrations of the underlined element (s) . + Blank = value not measured. SWAN RIVER - DAUPHIN AREA STREAM SEDIMENT SAMPLE U.T.M. M0+ NO. COORDINATES (PPM) E N 7200001 3322 7600 7200002 3335 7598 1.5 7200003 3280 7570 0.5 7200004 3158 7507 7200005 2966 7483 720CC06 2953 7617 72C0007 3004 7614 7200008 31C3 75C8 0.5 7200009 3138 '7413 .72000 10 3196 7477 0.5 7200011 3196 7480 720CC12 3192 7531 72000 13 3228 7570 0.5 7200014 3260 7544 0.5 7200015 3243 7468 7200016 3264 74C6 7200017 3285 7410 72000 18 3312 7402 7200019 3337 7486 7 2000 20 334? 747C 7200021 3323 7520 7200022 3336 7600 7200023 3404 7 546 7200024 3413 7548 1 .< 7200025 3428 7547 7200026 3440 7549 7200C 27 3437 75 80 7200028 3430 7595 7200029 3446 7578 . 0.! 7200030 3468 7593 0.' 7200031 3475 7593 7200032 3494 7595 7200 033 3495 7625 7200034 3520 7625 7200035 3540 7630 7200036 358 2 7668 7200037 3608 7675 1 . 7200038 3625 7555 7200039 3645 7510 7200040 3751 7400 7200041 3750 7394 7200042 3 R00 7400 7200043 3802 7402 7200044 3894 7394 7200045 392 1 74C0 7200046 3909 7432 + Blank = value less than detection limit of 0.5 ppm. 272 SAMPLE NO. U.T.M. •COORDINATES MO (PPM) 7200047 3888 7489 7200C48 3860 7540 7200049 3843 7563 7200050 3857 7554 7200051 3850 76C9 7200C52 3846 7 6 28 7200053 3845 764C 72000 54 3815 7730 7200055 3598 7721 7200056 3580 7722 7200057 3529 7723 7200058 3780 7782 720CC59 3738 7782 7200060 3705 7783 7200061 3 657 7783 7200062 3606 7784 7200C63 3597 7786 7200064 3507 7787 7200065 3012 7662 7200066 3020 7715 7200067 3145 7684 7200068 3256 7655 7200C69 3198 7700 720007C 3195 77C3 7200071 3175 7710 7200072 3113 7770 7200073 3114 778C 7200074 3115 7796 7200075 3 196 7773 7200076 3196 7793 7200077 3212 78C1 7200078 3193 7757 7200079 3 192 7722 7200080 3242 7739 7200081 3243 7756 7200082 3253 7801 7200083 3353 7793 7200084 3275 7735 72C0C85 3295 7728 7200086 3291 7666 7200097 3342 7663 7200088 3354 7663 7200089 3441 7654 7200138 39 39 7353 7200137 3931 7377 7200139 3940 7346 7200140 3953 73C8 7200141 3968 7253 7200142 3954 7228 1 .0 0. 5 0.5 0.5 1.0 0.5 l.C 0.5 + Blank = value less than detection limit of 0.5 ppm. SAMPLE U.T.M., NO. (COORDINATES E N 7200143 7200144 7200 145 7200146 7200147 7200148 7200149 7200150 7200151 7200152 7200153 7200154 7200155 7200156 7200157 7200158 720 0159 7200160 7200161 7200162 7200163 7200164 7200165 7200166 7 20 0167 7200168 7200169 720017C 7200171 7200172 7200173 7 200174 720C175 7200176 7200177 7200178 7200179 7200180 7200181 7200182 7200183 7200184 7200185 7200186 7200187 7200188 7200189 7200190 7200191 7200192 3943 3952 3974 3982 3980 4C46 4057 4039 3798 3798 3798 3348 3846 3876 3866 3867 3914 3915 3964 39 63 3963 3965 3915 3963 3962 3960 4026 4 02 7 4029 4029 4028 4028 4 063 4069 3745 3 72 5 3 7 85 3763 3763 3785 3836 3848 3873 3862 3862 3862 3862 4155 4132 4123 7202 7167 7134 7086 7C68 7020 6968 6860 6746 6768 6793 6758 6740 6732 6837 6864 6858 68 86 6884 l.C 6870 6853 6846 2.5 6796 6805 6757 6740 6 733 6752 6814 3.0 6820 1.0 6826 6831 6747 6676 3.5 6704 6630 6680 6624 6584 6580 6581 6582 6580 6 618 6625 6640 6656 6607 4.5 6608 1.5 6580 + Blank = value less than detection limit of 0.5 274 SAMPLE U.T.M. MO+ NO. CXXIRDINATES (PPM) E N 7 200193 4128 6574 0.5 7200194 4020 6543 7200195 4C13 6542 7200196 3992 6563 7200197 3965 6563 720C198 3946 6563 7200199 3921 6580 7200200 3915 6580 7200201 3927 6 6 38 7200202 3969 6627 7200203 3967 6610 7200204 3972 6610 7200205 3981 6610 7200236 4064 6642 7300881 4243 6540 4.0 7300883 4244 6556 3.2 7300884 4250 6590 1.6 7300965 4273 6633 7300966 4288 6635 7300967 4255 6623 7300968 4250 6605 1.6 730C969 4250 6573 1.6 7300977 4090 6590 2.4 7300978 4106 6556 5.6 /30G979 4 123 6564 14.4 73C0S80 4100 6541 7300981 4111 6559 7300983 4142 6592 6.4 7300985 41 88 6603 4.8 7300989 4131 66C8 2.0 7300990 4104 66CC 0.8 7300991 41 57 6624 4.6 7301038 4065 6756 7301039 4045 6759 7301041 4021 6750 1.6 7301C42 399 5 6750 3.2 7301043 3957 6762 7301044 4013 6818 1.6 7301055 3585 7673 2 .4 7301056 3574 7658 0. 8 7301215 3971 6610 7301219 4028 6752 7301469 3610 7656 7400059 4072 6582 7400060 4082 6540 7400061 4071 6.557 + Blank = value less than detection limit of 0.5 ppm. 275 6. SWAN RIVER - DAUPHIN AREA BEDRCCK (TABLES XXXXIII AND LTV) FORMATION UraOLOGbf VERNILLICN RIVER SHALE FAVEL SHALE LIMESTONE BENTON ITE ASHVILLE SHALE SITE U.T.M. SAMPLE MO+ SE++ NO. OOORDINATES NO. (PPM) (PPM) 1 ri 4182 N 6535 730385 20. 0 8 4170 6493 730908 4.0 20. 5 7309 09 10. 0 730910 6. 0 24. 8 15 3245 75 95 731390 15.0 731391 £. 0 10. 3 731392 14.0 731393 15. 0 6. 3 7 31394 12.0 16 3610 7653 731395 15.0 731396 25.0 731397 14.0 731398 30.0 731399 1 C. 0 2 4170 6576 730837 13. 0 1 . 3 730888 8.0 3 4130 6606 730889 3.0 2. 7 730891 3C. 0 4. 4 4 4068 6670 730892 14.0 73C893 14. 0 2. 9 7 30894 14. 0 730896 8.0 . 2 . 5 6 4027 6730 730900 1 5. J 730901 13. 0 9 4243 6528 730921 14.0 730922 14. 0 7 309 2 3 2 5. 0 4. 5 730924 15.0 10 4200 656 5 730970 2 5.0 73C971 12.0 4. 4 12 3584 7673 731048 30.0 731049 4C. 0 4 • 9 731050 15. 0 14 3270 7605 •73 1065 7.0 731067 1 2. 0 15 3245 7595 73 1389 15.0 17 3666 7690 731465 12.0 1. 4182 6535 730886 3. 0 9 4243 6528 730919 5.0 12 3584 76 73 731047 3C.0 15 3245 7595 731333 2.0 17 3666 7690 731464 4.0 3 4130 6606 730890 2. 0 4 4068 6670 730395 4. 0 10 4200 6565 730972 2.0 6 4027 6730 730897 7. 0 7 4128 6690 7309 03 0. 5 730904 C. 5 730905 6. 0 730907 C. 5 10 42 00 6565 730973 13.0 5. . 0 730974 1 3. 0 + Values below the detection limit (1 ppm) given as 0.5 ppm. •H- Blank = value not measured. 276 FORMATION LITHOLOGY SITE NO. U.T.M. CXXJRDINATES E N SAMPLE NO. MO (PPM) SE (PPM) ASHVILLE SHALE SWAN RIVER 11 4160 6605 12 3584 7673 FE CX-GYPSUM 6 402 7 673C SULFUR 7 4128 6690 SAND 13 3540 7673 SILTSTONE SHALF SHALE/SILT 13 3540 7673 13 13 3540 3 540 7673 7673 730975 730976 731217 731051 731052 731053 730899 730906 731057 731058 731062 731063 731059 731060 731061 731064 10.0 5. 0 2.0 15.0 1 3. 0 10. 0 5.0 8. 0 1.0 C.5 0. 5 0. 5 0.5 0. 5 0. 5 0.5 3. 1 6. 1 5.4 7. KELD DETAILED STUDY AREA SOILS AND PLANTS (TABLES XXXXIV, XXXXVI AND LV) SAMPLE DESCRIPTION SITE U.T.M. NO. COORDINATES SOIL E N SHALE- I 18 4142 6544 74CC81 4.0 TILL 1 19 4140 6550 74C085 4.0 128 4126 6558 740118 0 .4 130 4128 6540 74C128 4.0 1 33 4116 6544 740139 7.2 136 41 35 6546 740152 16 .0 139 41C7 6552 740164 1.6 148 4 117 6 5 50 740191 7.2 150 41 33 6550 740199 1 .6 SAMPLE MO1" CU SE PH NO. (PPM) (PPM) (PPM) 7.4 7.8 7.3 7.3 7. 3 7.2 7.7 7.8 8.3 CALC AREOUS TILL 112 4153 6572 740064 1 .6 116 4142 6528 74CC77 0.4 117 4142 6532 74CC79 0 .4 126 4123 6568 740113 2.4 127 4131 6561 74C115 0.4 131 4127 6533 74C133 1 .6 132 4127 6526 740135 0.4 1 34 4111 6528 740147 1.6 135 4111 6 5 33 74C150 0.8 137 4110 6546 740156 0.4 1 38 4107 6558 74C160 2.4 141 4088 6530 74C170 0.8 142 4087 6546 74C172 0.4 143 4095 6562 740176 4.0 144 4100 6558 740180 0.4 145 4112 6566 74C183 2.4 1 46 4093 6578 740186 0.4 147 4111 6576 740183 0.4 + Values below the detection ++ Blank = value not measured limit (1 ppm) given as 0.5 ppm. 8.0 8.1 8. 0 7.7 7.8 7.8 7.8 7.4 7.4 7.8 7.8 7.8 7.9 7.9 8.5 8.3 8.2 277 A HORIZON IAC. SOIL SAND C HORIZON SOIL SHALE-TILL SITE U.T. .M. SAMPLE MO+ CU++ SE""" PH"1"1 NO. OOORDINATES NO. (PPM) (PPM) (PPM) E N 113 4153 6558 740C66 0.4 7.7 114 «1 5 3 6545 74CC69 0.4 7.7 115 4153 6527 74CC73 0.4 7. 9 120 4138 6562 74CG89 0.4 7.9 121 4148 6544 74CC92 0.4 7.9 122 4146 6558 740096 0.4 7.9 123 41 38 6568 740100 0.4 7.8 124 4137 6577 740104 0.4 7.8 125 4123 6572 7401C9 0.4 7.6 118 4142 6544 74C083 8 .0 6.6 119 4140 6550 74CC87 10.4 7.36 3.5 128 4126 6558 740121 6.4 7. 1 130 4128 6540 740131 4.8 2. 18 4.4 133 4116 6544 74C140 4.8 136 4135 6546 740154 3.0 3. 4 139 4107 6552 74C166 5 .6 3.5 148 4117 6550 74C193 20.0 4.88 3.9 150 4133 6550 74C200 2.4 CALC AREOUS TILL 112 4153 6572 74CC65 6.0 7. 2 1 16 4142 6528 740073 2 .4 8.3 117 4142 6532 74CC80 0.4 8.4 126 4123 6568 740114 1.6 8. 3 127 4131 6561 740116 0.4 8. 1 131 4127 6533 74C134 0.4 8.4 132 4127 6526 740136 I .6 7.9 134 4111 6 528 74C148 3 .2 8.3 1 35 4111 6533 74C151 1.6 8. 1 138 4107 6558 740161 I .6 140 4100 6546 740169 0.4 8.3 141 4088 6530 74C171 4.0 8. 2 142 4C87 6546 740173 0 .4 7.8 144 41 CO 6556 74C181 2.4 8. 1 146 4093 6578 74C187 0.4 8.2 147 4111 6576 740189 0.8 7.8 LAC. SAND 113 4153 6558 74CC67 0.4 8.3 1 14 4153 6545 74CC71 0.4 8.4 115 4153 6527 74CC75 0.4 8.4 120 4138 6562 74CC91 8.0 7.7 121 4148 6544 74CC94 0.4 8. 1 122 4146 6558 74C098 0.4 8.3 123 4138 6568 740102 2 .0 8.4 124 4137 6577 74C1C6 0.4 8.8 125 4123 6572 740111 0.4 8.5 + Values below the detection limit (0.8 ppm) given as 0.4 ppm. ++ Blanks = values not measured. 278 GRASS DESCRIPTION SITE U.T.M. SAMPLE MO+ CU++ NO. COORDINATES NO. (PPM) (PPM) E • N SHALE- 118 4142 6544 740084 1.6 6. 926 TILL 119 4140 6550 74CC88 1 .0 6 .518 128 4126 6558 740122 0.6 7.296 130 41 28 6540 740132 1 .2 8 .917 136 4135 6546 740155 1.6 10.133 1 39 4107 6552 74C167 2.4 8.917 148 4117 6550 740194 I .0 9.399 150 4133 6550 740202 1.6 9.399 SE^ (PPM) PH CALC AREOUS TILL 127 4131 6561 740117 0 .4 6.926 132 4127 6526 74C137 0 .8 9.322 134 4111 6528 740149 0 .8 12 .160 *137 4110 6546 74C158 8 .0 11.349 1 28 4107 6558 740162 2 .0 8.917 143 4095 6562 740178 I .8 9 .728 144 4100 6556 74C182 3 .4 8.917 145 4112 6566 740185 0 .6 6 .485 147 4111 6576 740190 0 .8 7.296 LAC. 113 4153 6558 SAND I 14 41 53 6545 115 4153 6527 121 4148 6544 122 4146 6558 123 41 38 6568 124 41 37 6577 125 4123 6572 SHALE- 13? 4116 6544 TILL CALC 122 4127 6526 AREOUS 1 27 4 110 6546 TILL 1 38 4107 6558 142 4095 6562 LAC. 124 41 37 6577 SAND 74 006 8 1.2 9.777 740072 1 .4 8 .962 74CC76 0.4 8.555 74CC95 0.8 6.51 8 74CC99 0.4 7.333 74 0103 2.0 4.0 74 74C107 1 .4 6 .111 740112 1 .4 7 .740 740142 7.0 12.160 740138 7.0 8.917 74C159 10.0 12.970 740163 9 .0 10.5 38 74C179 6.0 10.133 740108 7 .0 10 .592 8. SWAN RIVER VALLEY SOILS AND PLANTS (TABLES XXXXVII, XXXXIX, LV AND LVI) A HORIZON MO-SOIL TOXIC LAC. SILT 2 3240 7630 731C71 1.6 7.4 51 32 6 8 7588 73 1299 2 .4 7.4 144 3222 7624 740445 0.4 6.6 145 3220 7637 740450 0.4 6. 8 146 3243 7649 740454 0.8 7.8 147 3255 7646 740458 0.4 7.5 149 3280 7650 740466 0.4 6.4 + Values belcw the dection limit (0.8 ppm) given as 0.4 ppm. 4+ Blank = value not measured. 279 SAMPLE DESCRIPTION SITE U.T.M. SAMPLE MO+ OjV' SE** PH NO. COORDINATES NO. (PPM) (PPM) (PPM) A HORIZON MO-SOIL TOXIC LAC. SILT 15C 3273 7644 74G470 0.4 6.4 151 3277 7630 74C475 0.4 6.6 152 3245 7622 740479 0.8 6.8 153 3290 76C5 740484 1 .6 7.2 154 3281 7596 74C488 C.8 7.0 155 3276 7577 74G492 0.4 6.6 157 3314 7597 74C500 1 .6 7.1 158 3312 7576 740505 0.8 6.6 159 3328 7576 740508 0.4 7.2 160 332C 7604 740512 0.8 6.8 161 3323 7588 740517 0.8 7. 5 162 3298 7588 740521 0.8 6.4 LAC. SILT AND CLAY CALC AREOUS TILL LAC. SAND 24 3372 7637 731158 0.4 6.8 28 32<;6 7760 731170 0.4 7.9 32 3311 7859 721236 0.4 7. 5 39 3525 7916 731259 0.4 8.0 41 3458 7859 731266 0.4 7.9 49 3293 7686 731293 0.4 7.9 57 3683 7816 731319 0 .4 7.8 59 3676 7917 721225 C.4 7.9 61 3574 7916 731331 0 .4 7.7 63 3555 7857 731337 0.4 8.1 69 3506 764 7 731355 0.4 7.6 75 3459 7663 731373 0 .4 8.2 163 3349 76C4 740525 0.8 6.7 164 3375 7626 74C530 0.4 7. 1 165 3353 7649 740534 0.8 6.2 166 3385 7650 74C538 0.4 6.5 167 3431 7632 74C542 0.4 7.5 10 3621 7658 731 107 2 .4 7.9 14 3458 7542 731123 1 .6 7.6 16 3238 7418 731130 1.6 7.1 25 3389 7727 731162 0.4 7.9 26 3361 7782 731164 0.4 7.9 30 3231 7871 731177 0.4 7.3 35 3370 7941 731246 0.8 7.6 47 3224 7676 731285 1.6 7.6 71 3425 7803 72 1361 0.4 7. 9 5 3385 7665 731C83 0.4 8.0 6 3554 7 996 731089 0.4 6.8 45 3259 7.562 731278 1 .6 6.8 53 3769 7762 731306 0.4 7.9 60 3633 7918 731328 0.4 7.5 64 3580 7853 731340 C.4 7.8 65 3587 7817 73 1342 0.4 8. 0 67 3552 7737 731348 0.4 7.8 73 3466 7598 731367 0.4 7.9 77 3473 7748 731379 2.4 7. 5 + Values below the detection limit (0.8 ppm) given as 0.4 ppm. 4+ Blank = value not mfflsured. 280 SAMPLE DESCRIPTION SITE U.T.M. SAMPLE M0+ CU** SE** PH4 NO. COORDINATES NO. (PPM) (PPM) (PPM) SOIL MO- 1 3230 7633 731C70 0.8 TOXIC 2 3240 763C 731073 2 .4 7.8 LAC. 3 3256 7638 731C79 1.6 SILT 4 3313 7572 731C82 2.4 51 32 68 7588 731301 1 .6 8.2 52 3296 7573 7313C5 C.8 85 3270 7590 731428 0.4 85 327C 7590 74C573 0. 50 99 3282 7634 731478 0.4 144 3222 7624 74C447 0.8 7.9 145 3220 7637 740452 1.6 5.9 146 3243 7649 74C456 0.4 7.4 147 32 55 7646 74 0460 0.4 7.9 148 3261 7620 7 4C464 1.6 7.9 149 3280 7650 74 046 3 0.4 7.8 15C 32 73 7644 740472 0.4 7.7 151 3277 7630 74C477 0.8 6.5 152 3245 7622 740481 0.4 0. 76 7.5 153 3290 76C5 74C486 0.8 0.24 8.0 154 3281 7596 740490 1 .6 7.4 155 3276 7577 74C4 94 0.8 8. 1 157 3314 7597 74C502 1.6 7.8 159 3328 7576 74C510 0.4 8.0 16C 332C 7604 74C514 3.2 0. 63 8.0 161 3323 7588 74C519 0.4 7. 7 162 3298 7588 74C523 0.8 7.6 LAC. SILT AND CLAY 24 3372 7637 731160 1 .6 7.7 27 3287 7767 731169 0 .4 28 3296 7760 731172 1.6 8.2 32 3311 7859 721238 0.4 8.2 34 3350 7890 731245 0.4 39 3525 7916 731261 2.4 8. 1 41 3458 7859 731267 1 .6 7.9 42 3478 7R24 731270 1.6 49 3293 7686 731294 0.4 8.3 50 3290 7722 731298 0.4 56 3667 7776 731318 0.4 57 3683 7816 731321 1.6 7. 9 58 3653 7865 731324 0.8 59 3676 7917 721326 0.4 8.3 61 3574 7916 731332 0.4 8.5 63 3555 7857 731338 0.4 8.0 66 3556 7781 721347 4.0 69 3506 7647 731357 0.4 7.7 72 3436 7 64 3 731366 0.8 74 3502 7638 731372 0.8 75 3459 7663 731375 1.6 . 8.0 76 3457 77C2 731378 C.4 86 3361 7579 731432 0.4 89 3370 7547 731440 0.4 92 3298 7821 731443 0.4 93 328C 7811 731450 0.4 98 3588 7761 721473 0.4 +' Values below the detection limit (0.8 ppm) given as 0.4 ppm. ++ Blank = value not measured. 281 SAMPLE DESCRIPTION SITE U.T.M. SAMPLE MO+ CU** SE44" PH4 NO. COORDINATES NO. (PPM) (PPM) (PPM) C HORIZON SOIL LAC. ICO 3337 7631 731481 0.4 SILT 101 3352 7630 731484 0.4 AND 102 3 391 7632 731487 0.4 CLAY 1 03 34 12 7 63 1 73149C 0.4 104 3451 7.628 731493 0.4 105 3488 7620 731496 0.4 107 3356 7732 731511 0.4 163 3349 7604 740527 0.8 164 3375 7626 740532 1 .6 166 3385 7650 740540 1.6 167 3431 7632 740544 0.4 CALC AREOUS TILL LAC. SAND 9 3768 77C8 731106 1.6 10 3621 7658 731109 1 .6 7.9 11 3 6 02 7633 731115 0.4 13 3496 7562 731122 3.2 14 3458 7542 731125 1.6 7.7 15 3238 7452 7? 1129 0.4 16 3238 7418 731132 2.4 7.8 17 3293 7406 731136 0.8 19 3224 7442 731143 2 .4 26 3361 7782 731165 0.4 8.1 30 3231 7671 73 1179 0.4 7.8 35 3370 794 1 721248 0.4 8. 0 36 3399 7933 731252 0 .8 44 3281 7510 721277 0.4 46 3226 7663 731284 0.4 47 3224 7676 731289 0.4 8.0 48 3226 7684 72 1292 0.4 71 3425 7803 731362 1 .6 8.2 78 3748 7796 731401 C.4 5 3385 7685 731085 0.4 8.2 6 3554 7996 731091 0.4 8.3 23 3342 7586 731157 2.4 25 3389 7727 731163 0 .4 33 3370 7890 731242 0.4 37 3392 7869 731255 4.0 8.0 38 3482 7951 731258 0.8 40 3462 7880 721265 1.6 43 3384 7797 731274 0.4 53 3769 7762 731307 0.4 7.9 6C 3633 7918 721330 0.8 8.2 62 3562 7955 731336 0.4 64 3580 7853 73 1341 0.4 8.0 65 3 5 87 78 17 731343 C.8 8. 5 67 3552 7737 731350 0.8 8.1 70 3502 7722 73136C 0.4 73 3466 759 8 731369 0.4 7.9 77 3473 7748 731381 0.8 8.3 + Values below the detection limit of 0.8 ppm given as 0.4 ppm. ++ Blank = value not measured. 282 GRASS MO-TOXIC AREA SITE U.T.M. SAMPLE MO NO. COORDINATES NO. (PPM) E N ' 1 3230 7633 740569 5 .0 * 85 3270 7590 7301429 20.0 144 3222 762 4 740448 0.8 145 3220 7637 740453 1 .6 146 3243 764 9 740457 0.6 147 3255 7646 740461 3.0 148 3261 7620 74 046 5 5.0 149 3280 7650 740469 2.0 150 3273 7644 740473 3.2 151 32 77 7630 740473 2.6 152 3245 7622 740482 5.0 1 53 3290 7605 740487 8 .0 154 3281 7596 740491 1.8 155 32 76 75 77 740495 1 .6 157 3314 7597 74 05 03 4.0 1 58 3312 7576 740507 2.6 159 3328 7576 740511 5.0 160 3320 7604 74C515 12.0 161 3323 7588 74C520 4.0 162 3298 7583 740524 3.0 CU (PPM) 4 .685 12.910 4.345 5.347 7 . 3 5,2 4.010 10 .695 7.019 5.347 6.684 6.350 4.345 347 003 347 679 687 6.684 7.352 7.013 SE PH (PPM) 4.32 0. 26 0. 68 1.66 OTHER AREAS 5 3385 7685 73C1424 0 .6 11 .8 80 78 3748 7796 7301404 1 .0 9.279 80 3686 7717 7301409 1 . 8 8.2 54 163 3349 76 04 7 4052 8 1 .4 5.013 164 3 37 5 7626 740533 1 .6 6 .350 165 3353 7649 740537 I .4 6.350 166 33 8 5 7650 740541 2 .8 6.016 167 3431 7632 740545 2 .0 4.679 LEGUMES MO-TOXIC AREA OTHER AREAS I 3230 7633 740570 4.0 6 .486 2 3240 7630 7301475 6.0 14.004 144 3222 7624 740449 1.0 6.016 150 32 73 7644 74 04 74 4.0 6.350 152 3245 7622 740483 4.0 6.684 157 3314 7597 740504 6.0 8.689 160 3320 7604 740516 6.0 6 .684 10 3621 7658 7301471 6.0 15.649 16 3238 7418 7301499 5.0 11.038 19 3324 7442 7301500 9.0 11.038 20 3358 7506 7301502 5.0 12.903 21 3378 7548 7301503 2.4 10.256 44 3281 7510 7301501 5.0 10 .737 50 3290 7722 7301508 5.0 11 .038 76 3457 7702 7301436 6.0 14. 187 77 3473 7748 7301474 8.0 14.430 91 3566 7995 7301446 6 .0 11 .0 32 104 3451 7628 7301497 8.0 10.9 10 105 3438 7620 73C1498 4.0 13.755 106 3397 7679 7301507 2.4 5.941 107 3356 7732 7301512 3.0 10.857 163 3349 7604 740529 1.2 5.013 167 3431 7632 740546 4.0 7.111 0. 50 0. 86 0. 66 I. 06 ++ Blank = value not measured. SAMPLE DESCRIPTION SITE U.T.M. ' > NO. COORDINATES E N SAMPLE NO. (PPM) CU^ (PPM) SE"" (PPM) FAVEL DETAILED STUDY AREA SOILS AND PLANTS (TABLES L, LII, LV AND LVI) PH A HORIZON SHALE-SOIL CLAY LAC. SILT AND CLAY 5 5 3665 7705 731312 0.4 no 3633 7698 740287 0.4 ii4 3653 7712 740305 0.4 115 3648 7695 740210 0.4 118 3666 7715 740325 0.4 119 367C 7710 740329 0.4 124 3682 7723 74C358 0.8 128 3705 7728 740375 0.4 129 3698 7725 740379 0.4 e 371C 7716 731098 1 .6 125 3682 7710 740363 0.8 126 3682 7702 740367 1.6 131 3698 7714 74C388 1 .6 123 3702 7709 74C396 0.4 136 3721 7732 74C411 2.4 137 3721 7728 74C414 0.4 138 3717 7720 74C419 0.4 139 3720 7710 740422 0.4 141 3728 7717 740432 1.6 7.1 7.4 6.5 6.8 7.0 8.2 6.9 6.9 7.0 7.9 7.7 7.7 CALC AREOUS TILL LAC. SAND 1G9 3633 7711 740283 0.4 111 3637 7691 740291 0.8 122 3667 7689 740349 0.4 134 3698 7695 74C4C0 0.8 135 3702 7700 740405 0.4 140 3716 77C0 740427 0.4 169 3690 7718 740552 0.4 170 3677 7688 740556 0.4 108 3633 7732 74C280 0.4 112 3650 7729 740295 0 .4 113 3650 7725 74C3C0 0.4 116 3666 7728 740316 0.4 117 3667 7722 740321 0.4 123 3681 7732 74C354 0.4 7.2 7.4 8.0 7.4 7. 4 6.4 6.8 7. 6 7.7 7.3 7.8 7. 8 8.7 7.0 C HORIZON SOIL SHALE-CLAY c c 3665 77C5 . 731314 0.4 80 3673 7712 731410 0.4 1 10 3633 7698 740289 0.4 114 3653 7712 74C3C8 0.4 115 3648 7695 74C212 0.4 1 15 3648 7695 740313 118 3666 7715 74C327 0.8 119 3670 7710 740331 1 .6 124 3682 . 7723 740360 1 .6 128 3705 7728 74C377 0.4 129 3698 7725 740381 0.4 0.92 0. 37 0.37 + Values below the dectionlimit of 0.8 ppm given as 0.4 ppm. ++ Blank = value not measured. 4.7 7.3 7.1 5.3 7. 5 7.7 7. 3 6.8 6.9 6.9 SAMPLE DESCRIPTION SITE U.T.M. NO. COORDINATES E N' SAMPLE NO. C HORIZON SOIL LAC. 8 3710 7716 731101 0.8 SILT 125 3682 7710 740365 2.4 AND 126 36 8 2 7702 740369 3.2 CLAY 131 3698 7714 740390 0.8 133 3702 7709 74C397 0.4 136 3721 7732 74C412 1.6 137 3721 7728 740415 2.4 138 3717 7720 740420 0.4 139 3720 7710 740423 0.8 141 3728 7717 740433 1 .6 142 3732 7 723 740436 0 .4 7.4 7.3 7.8 6. 4 7.8 7.8 8. 2 8.0 8.0 6.7 7.0 CALC 95 3673 7690 731460 0.4 AREOUS 96 3667 7695 731463 0.4 TILL 109 36 33 7711 740285 0.8 111 3637 7691 74C293 0.4 134 3698 7695 740401 0.8 135 3702 7700 740406 0.4 140 371 6 7700 740429 0.4 17C 3677 7688 74C558 0.8 LAC. 54 3682 7732 731311 0.4 SAND 1 12 3650 7 7 29 74C297 0.4 1 13 3650 7725 740302 0 .8 116 3666 7729 74C313 C.4 123 3681 7722 740356 0.4 3RASS CLAY no 3633 7698 74C290 1.0 9.399 114 3653 7712 740309 2.6 11 .108 0. 14 115 3648 7695 74C214 0.6 9.399 118 3666 77 15 740328 2.8 11.535 0. 84 119 3670 7710 740333 0.6 8.117 124 3682 7723 740361 0.6 6.031 0. 12 128 3705 7728 740378 4.0 5. 361 129 3698 7725 74C383 2.0 4.356 IAC. SILT AND CLAY 125 3682 7710 740366 0.6 7 .372 126 3682 7702 74C370 1.2 8.377 127 3701 7734 74C373 1 .4 6.031 131 3698 7714 740391 1 .6 9 .047 136 3721 7732 74C413 1.8 6 .684 137 3721 7728 ' 74C417 1 .2 8.021 142 3732 7723 740437 0.6 8.689 143 3726 7727 74C44I 1.2 7.018 TILL 109 3633 7711 74C286 4 .0 10.681 111 3637 7691 74C294 1 .0 7 .263 122 3667 7689 74G352 I .2 4 .356 134 3698 7695 7404C3 3 .4 4 .356 135 3702 7700 740408 4 .0 6.031 + Soil values below the dection limit of 0.8 ppm given as 0.4 ppm. 4+ Blank = value not measured. SAMPLE DESCRIPTION SITE U.T.M. SAMPLE MO CU SE NO. COORDINATES NO. (PPM) (PPM)- (PPM) E N CALC 140 3716 77C0 AREOUS 170 3677 7688 TILL LAC. 100 3633 7732 SAND 112 3650 7729 113 3650 7725 116 3666 7728 117 3667 7722 123 3681 7732 740430 3.0 5 .681 740559 5.0 5.766 74C282 3.0 8.972 740298 4.0 10.254 740303 3.0 13 .672 740319 0.4 9.399 740324 0.6 8.545 740357 I .6 6.366 LEGUMES SHALE- 55 3665 77C5 731459 20 .0 14 .126 CLAY 115 3648 7695 740315 6.0 10.681 119 3670 7710 740334 16.0 9 .326 124 3682 7723 74036 2 28 .0 5 .696 LAC. SILT 127 3701 7 7 34 740374 10 .0 7.372 AND CLAY CALC 122 3667 7689 740353 3 .4 8 .042 AREOUS 134 3698 7695 74C404 9 .0 5 .361 TILL 140 3716 7700 740431 4 .0 6.016 170 3677 7688 74C560 12 .0 9 . 369 LAC. 112 3650 7729 74C299 12 .0 11 .963 SAND 113 Zt 50 7725 740304 10.0 9 .399 116 3666 7728 740320 4.0 10.681 117 3667 7722 74C323 7 .0 8.117 PARENT 139 3720 7710 74C426 MATERIAL 163 3720 7723 740551 4.00 0.60 UNCERTAIN 10. MANITOBA DEPARTMENT OF AGRICULTURE GRASS ANALYSED FOR SE (TABLE LVI) MO-POOR SAMPLE SECT.-TP.-RANGE SE NO. (PPM) 740004 SE 12-25-25 0.30 740C26 NW 26-2 3-2 6 C.46 740034 S26-2 5-28 0.52 740074 33-27-15 C.42 740093 SE 17-3.7-27 C .46 MO_ 740043 KCCH 74 0C47 740056 74CO83 ++ Blank = value NW27-35-28 C.28 NW29-35-29 0.52 NW 4-37-25 C.36 36-32-23 C.66 measured. PUBLICATIONS Doyle,'P.J. and Fletcher, K., 1977. Molybdenum content of bedrock, soil and vegetation and the incidence of copper deficiency in cattle in west ern Manitoba, in Symposium on molybdenum in the environment. Vol.11. W. Chappell and K. Petersen eds., Marcel Dekker Inc., New York, N.Y. pp. 371-386. Doyle, P. J. and Fletcher, K., 1977. The influence of soil parent material on the selenium content of wheat from west-central Saskatchewan. Can. J. Plant Sci. Doyle, P., Fletcher, K. and Brink, V.C., 1973. Trace element content of soils and plants from the Selwyn Mountains, Yukon and Northwest Territories. Can. J. Botany 51:421-427. Doyle, P., Fletcher, K. and Brink, V.C, 1974. Regional geochemical reconn aissance and the molybdenum content of bedrock, soils and vegetation from the eastern Yukon, in Trace substances in environmental health-VI. A Symposium. D. D. Hemphill ed., University of Missouri, Columbia, Missouri, pp. 369-375. Fletcher, K. and Doyle, P., 1971. Regional geochemistry of the Hess Mountains and eastern Yukon Plateau. CIM Bull. 64:61-67. Fletcher, K. and Doyle, P., 1974. Some factors influencing trace element distribution in the eastern Yukon. CIM Bull. 67:61-65. Fletcher, K., Doyle, P. and Brink, V. C, 1973. Seleniferous vegetation and soils in the eastern Yukon. Can. J. Plant Sci. 53:701-703. 

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