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LIBRARY BINDERS SPBIECPCE r. :3an I ABSTRACT EFFECTS UPON GROWTH AND NUTRIENT COMPOSITION OF CORN (E§§.!5X§) PLANTS GROWN ON TWO DIFFERENT TEXTURED MICHIGAN SOILS CONTAMINATED WITH NICKEL AND CADMIUM BY Mary Frances Traynor Rubicon sand (Muskegon County, Michigan), and Morley clay loam (Washtenaw County, Michigan) were treated with NiCl2 and CdCl2 and cropped with corn under greenhouse con- ditions. Nickel and Cd were applied in equal milliequivalent con- centrations ranging from 0.05 to 1.00 milliequivalent of metal/100 g air—dried soil. Treatments were replicated three times and a control set was included. Rubicon sand was adjusted by liming with CaCO3 to a pH of 6.7; the native pH of Morley clay loam was 6.7-6.8. Plant and soil samples were analyzed for Cd, Cu, Fe, Mn, Ni, and Zn by atomic absorption SpectrOphotometry. Cadmium contamination of both soils resulted in severe growth retardation at all levels of treatment. Increasing concentration of Cd in the soil resulted in an increase in Cd concentration and uptake by the plants. Mary Frances Traynor Nickel contaminated soil did not retard plant growth significantly. Increasing levels of applied Ni created a significant soil x level interaction. At the higher levels of treatment, more Ni was taken up by plants grown on Morley clay loam than those grown on Rubicon sand. Cadmium was more extractable than Ni from both soils. Less Ni was removed by extraction from Rubicon sand than Morley clay loam. Plants grown on both soils took up more Mn with increasing level of Ni treatment. The Cd treated Morley clay loam caused a decrease in plant Mn uptake. Concentrations of Cu, Fe, and Zn were not affected by metal treatment; uptake of these metals was affected. EFFECTS UPON GROWTH AND NUTRIENT COMPOSITION OF CORN (ZEA MAYS) PLANTS GROWN ON TWO DIFFERENT TEXTURED MICHIGAN SOILS CONTAMINATED WITH NICKEL AND CADMIUM BY Mary Frances Traynor A THESIS Submitted to Michigan State University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Department of Crop and Soil Sciences 1974 L .. ”A ‘5'!“ ACKNOWLEDGMENTS The author wishes to gratefully acknowledge her sincere appreciation to Dr. B.D. Knezek for his guidance and patience at all times during this study and in the thesis preparation. His personal concern in planning my program of study has made my educational experience at Michigan State University very rewarding. Gratitude is eXpressed to Drs. B.G. Ellis and C.D. McNabb for their assistance in the planning and preparation of this thesis. Appreciation is extended to Mrs. Betsy Bricker for her assistance with laboratory and statistical analysis of data. The support and help of the Franciscan Sisters of the Eucharist is very gratefully acknowledged. Appreciation is extended to the Tennessee Valley Authority for partial financial support of this project under contract number TV-30410A and agreement number Michigan 1131-74. TABLE OF CONTENTS ACK NOWLEDGME N TS O O O O O O I O O O O O O O O O O O O O O O O O O O ...... O ....... LIST OF TABLES . ................ ..... ................... INTRODUCTION 0 O O O O O O O O I O O O O O C C O I O O ....... O O O O O O O O ..... O 0 CHAPTER 1: LITERATURE REVIEW 0.0.0.000...OOOOOOOOOOOOO. Chemical PrOperties of Cadmium ..... ............... Cadmium in Soil and Plants ........ ...... .......... Sources of Cadmium ........ ......... ............... Cadmium in Water and Air .. ..... ................... cadlniult‘ in Human Health 0000......OOOOOOOCOOOOOOOOO cadl‘limn in FOOdSthfS 0.... ....... OOOOOOOOOOOOOOOOO Chemical Properties of Nickel ..................... Nickel in Soil and Plants ..... ..... ............... Nickel in Enzymatic Systems ....... ..... ........... Nickel as a Carcinogenic Metal ........... ......... Nickel in Foodstuffs .. ..... . ......... ............. CHAPTER 2: EFFECTS OF NICKEL AND CADMIUM CONTAMINATED SOILS ON NUTRIENT COMPOSITION OF CORN PLANTS. In: TRACE ELEMENTS IN ENVIRONMENTAL HEALTH - VII, D.D. Hemphill, Ed., University of Missouri, Columbia, Missouri. 1973. .................................. Abstract .... ..... . ............ ..... ........ ....... Introduction ..................... ...... ........... Methods and Procedures . ............ ............... Results and Discussion .. ...... .................... iii 11 12 13 14 14 16 18 20 page Literature Cited ............OOOOOOOOOOOOOOOO...... 25 CHAPTER 3: INFLUENCE OF NICKEL AND CADMIUM CONTAMINA- TION OF RUBICON SAND AND MORLEY CLAY LOAM UPON CORN GROWTH AND METAL COMPOSITION AND EXTRACTABLE SOIL METALS ..................... ..... ............. 27 Abstract ............ ................ ...... ....... . 27 Introduction ....... ........ .. ..................... 29 Methods and Procedures ...... ........... . ........ .. 30 Results and Discussion ............. ...... ......... 32 Literature Cited ................... ..... .......... 39 CHAPTER 4: SUMMARY AND CONCLUSIONS ... ...... .......... 41 LIST OF REFERENCES ................................ .... 44 APPENDIX ......OOOOOOO...00.0.00.........OOOOOOOOOOOOOO 50 iv LIST OF TABLES Table page CHAPTER 2 1. Characteristic prOperties of Rubicon sand, A horizon. OI......-......OOOOOOOOOOOOOO.....OOOO.... 18 2. Soil treatment, plant growth and metal content of corn grown on nickel-treated Rubicon sand under greenhouse conditions. ............................ 20 3. Soil treatment, plant growth and metal uptake of corn grown on nickel-treated Rubicon sand under greenhouse conditions. ............................ 21 4. Soil treatment, plant growth and metal content of corn grown on cadmium-treated Rubicon sand under greenhouse conditions. ............................ 22 5. Soil treatment, plant growth and metal uptake of corn grown on cadmium—treated Rubicon sand under greenhouse conditions. ............................ 22 6. Soil treatments and soil extractable metal con- centrations of Rubicon sand. ...................... 23 7. Soil treatments and soil extractable metal con- centrations of Rubicon sand. ...... . ..... .......... 24 CHAPTER 3 1. Characteristic properties of Rubicon sand, A horizon and Morley clay loam, Ap horizon. . ....... . 31 2. Comparison of yield and nickel and manganese con- centration and uptake by corn plants grown for 5 weeks on nickel-treated Rubicon sand and Morley clay loam. ........................................ 34 3. Comparison of nickel concentrations extractable from Rubicon sand and Morley clay loam. ........... 35 4. Comparison of yield and cadmium concentration and uptake by corn plants grown for 5 weeks on cadmium- treated Rubicon sand and Morley Clay loam. ........ 37 V Table page 5. Comparison of cadmium concentrations extractable from Rubicon sand and Morley clay loam. ............ 38 APPENDIX la. Comparison of iron and manganese concentrations extractable from nickel-treated Rubicon sand and morley Clay loaf“. ......OOOOOOOOOOOO......OOOOOOOOO 50 2a. Comparison of iron, copper and zinc concentration and uptake on nickel-treated Rubicon sand and Morley Clay loam. 0......0.00.00.........OOOOOOI... 51 3a. Comparison of COpper, iron, manganese and zinc concentrations and uptake by corn plants grown for 5 weeks on cadmium-treated Rubicon sand and Morley clay loam. ................................. 52 4a. Comparison of iron and manganese concentrations extractable from cadmium—treated Rubicon sand and Morley clay loam. ................................. 53 vi INTRODUCTION The distribution of heavy metals from naturally occur- ing ores to various products and wastes is a result of man's activities in altering his environment. Some metals (Zn, Cu, Mn) are essential micronutrients for all living organisms; whereas, others (Ni, Cd, Hg) are not known to have any essen- tial role in life processes. Both types of metals can result in deleterious effects if present in excess of the require- ments of plants and animals (2). Cadmium in all of its Chemical forms is toxic to living species (13). The ubiquitous toxicity of Cd constitutes the basis for enviornmental concern. Nickel, being ten times as toxic as Zn, is also very injurious to plants (46, 69, 71). Due to the potential toxicity of these elements in the environment this study was initiated to determine the effects of the growth of corn (Ze§_may§) plants prOpagated on two different textured soils contaminated with Ni and Cd; the inactivation of these metals by the soil; the release of other nutrients, and the effect upon the nutrient composition of the crOp. These prOperties are of essential importance in the determination of a soil which would be suitable for use as a waste disposal area for materials containing Cd and Ni. CHAPTER 1 LITERATURE REVIEW Chemical Properties of Cadmium The behavior of Cd in its various modes of production, application, dissipation, and toxicity is intimately related to its position in the periodic chart of the elements. Cadmium is chemical element number 48 and has an atomic weight of 112.40. The only stable valence exhibited by Cd is two. Zinc, Cd and Hg follow directly after the so-called transition elements. The behavior of Cd in soils, rivers, lakes and the oceans may be strongly influenced by the fact that cadmium ion (Cd++ atomic radius @ 25 C°is 1.489 A) has the same charge and is nearly the same size as calcium ion (Ca++ atomic radius @ 25°C is 1.971 A). It, therefore, can readily replace this abundant element in minerals and sedi- ments (3). Baes (3) postulates that the toxicity of Cd stems in part from its ability to displace its neighboring element, Zn, and bind itself more strongly to the nitrogen and sulfur groups of enzymes. The most important donor atoms which link metal ions to biological molecules are oxygen (0), nitrogen (N), and sulfur (S). Baes (3) has reported that Cd is held more tightly than, and should 2 replace Mn++ and Fe++ from nitrogen donors. Additionally, Cd is bound to 8 more strongly than all of the essential metals except Cu. Cadmium in Soil and Plants Vinogradov (70) has discussed the geochemistry of Zn, and hence Cd in soils. He has found that parent rock materials of basaltic origin have a higher Cd content than those of granitic rocks. Lagerwerff (32) reports typical low, average, and high concentrations of Cd in soils of 0.11, 0.34, and 0.56 ppm, respectively. Schroeder (59) reports a Cd content of 0.15 ppm for unfertilized field soil, 0.8 ppm for tilled but unfertilized soil and 3.38 ppm for (phOSphate) fertilized soil. In areas of suspected Cd cOntamination in rice (Oryza sativa L.) fields in Japan, concentrations of 1-50 ppm have been reported. Studies of plants grown on contaminated soils indicated that plants can readily absorb Cd from soil (25, 26, 33, 37). John, et al. (24) found that Cd in radish and lettuce plants was significantly related to the ability of the soil to adsorb Cd. Lagerwerff (32), however, found significant increases in radish yields which coincided with increases in the Cd and Zn content of soils. This was perhaps due to alleviation of Zn deficiency. Turner (67) has reported the effect of Cd on Cd and Zn uptake by selected vegetable Species from solution cultures. He found variations in response to Cd treatment between species, particularly sensitive to Cd damage. Most species apparently tolerated Cd levels in nutrient solution up to 0.1 ug/ml. He noted an increase in Zn uptake resulting from Cd treatment. Haghiri (17) showed that although foliar-applied Cd was readily translocated into various parts of soybeans, uptake of Cd via the root system was significantly higher. He showed that Cd in various parts of the soybean plant de- creased in the following order: stem>leaves>pods>beans. Soybean plants appear to be more sensitive to Cd than wheat. In general, there is a depression in yield due to soil-applied Cd. Preliminary studies by Allaway (1) indi- cated that plant growth depression due to Cd toxicity tended to occur after plants had accumulated approximately 3 ppm of this metal. Page (45) states that plants cultured in soils containing soluble Cd will absorb substantial amounts of this element. He also points out that competitive ef- fects of other ions, particularly zinc, may influence the amounts of Cd absorbed by plants. Finding that the uptake of Cd by plants is significantly related to the ability of the soil to adsorb Cd, John (24), has described Langmiur adsorption isotherms for 30 soils from British Columbia. He has determined the adsorption maximum and a coefficient relating to the bonding energy of the soil for Cd. The in- fluence of 13 soil characteristics upon these coefficients was investigated. Sources of Cadmium The natural geochemical partnership of Cd and Zn, reported by Vinogradov (70) accounts for an unusual rate of mobilization into man's environment. The release of Zn and its associated Cd into the environment in the manufacturing and recycling Operations ocCur in two ways: (1) by volati- lization and release of the metals or their compounds to the atmosphere, and (2) by release to streams in aqueous Operations such as electrolysis and wet Chemical processes (15). The apparent U.S. demand for Cd in 1968 was 13,328, 000 pounds which was predominantly used in plating, pigments, plastic stabilizers and metallurgy (15). Approximately 97% of the demand for Cd is in dissipative uses such as paints, plastics or plating (15). Geographically, 58% of the Cd- consuming industry of the U.S., according to a Bureau of Mines Survey (15) is in states bordering the Great Lakes, of these, Michigan accounts for 8%. Cadmium in roadside plants and soils, decreasing with distance from the traffic, was attributed to Cd as an im- purity in Zn-containing additives in motor oils and Zn com- pounds used in vulcanization of rubber tires (33, 34). Cad- mium in the atmosphere, and the subsequent settling of the airborne particles on vegetation and soils, predominantly originates from smelting and electrOplating of metals (27, 31, 39). Particulate fallout from such metallurgical pro- cesses was cited as a source of excessive amounts of the heavy metals in soils near a battery smelter (25). The industrial contribution to Cd enrichment of soil in Grand Rapids, Michigan, was documented by Klein (28). He found that soils of residential and agricultural areas had less Cd and Ni than industrial soils by a factor of about 1.4. Tsuchiya (66) postulated that the Cd, Zn, Pb mining opera- tions and the run-off from waste piles at an upstream site were responsible for contamination of water and rice in Japan. Apart from its association with Zn, Cd compounds used as fungicides (25, 33, 51) and Cd present in super- phosphate fertilizer (56) also resulted in the entry of heavy metals into the soil. Cadmium in Water and Air Bowen (6) has given concentrations of Cd found in water, air, plants and soils. In nonpolluted areas the normal con- centration of Cd in water is 1 ppb. However, values greater than 10 ppb have been reported for natural waters and water for consumption (12). Cadmium enters surface waters from various industrial and agricultural sources and into pro- cessed drinking water supplies from pipes, water heaters, etc. Normal wastewater processing removes only a portion of the metal before returning the water to a surface stream for reuse. Since the water is reused for drinking water, irrigation, livestock watering, and aquatic life, some Cd may reenter the biological processes (19, 30). Cadmium in the air varies with distance from a Cd-emitting source. Hise and Fulkerson (19) reported that the yearly mean concentration of Cd in the air at lower Manhattan was 0.023 ug/m3 while at a nonsuburban site it was 0.003 ug/m3. They report that the average intake by inhalation is very small compared to that from food. Measurements of metal aerosols have been reported for several cities (21, 35, 36, 58). Cadmium in Human Health Cadmium, although not present in as large of quantities as other metals is much more toxic. Poisoning by this ele- ment can occur by intake or injection of Cd salts or by inhalation of CdO. Carroll (7) has made a good correlation between cardiovascular death rates and the concentration of Cd in the air as an industrial pollutant. Cadmium toxicity in mammals is well established (57). EXperiments with mam- mals have shown Cd and its compounds can induce malignant tumors in rats (16). Evidence for the accumulation of Cd in human kidneys and livers, and the possible effects on human health have been reported (48, 49, 54, 55). More in- tensive study of Cd in soils and plants originated when recent reports associated the excessive accumulation of this heavy metal in man with hypertension (54), emphysema, chronic bronchitis (38) and the "ouch-ouch" disease (66). Although magnitudes of this metal in different matrices are small, man accumulates Cd in his kidney and liver (55). Cadmium in Foodstuffs Food is man's largest source of Cd intake. The Cd content of individual foods and of total diet have been analyzed many times with widely varying results (12, 42, 50, 59). Fruits rank the lowest in Cd content, whereas animal liver and kidney and shellfish have the highest contents. Variations may be accounted for by: (a) regional differences in soil and water, (b) agricultural Chemicals used, (c) tendency for plant or animal to retain or concen- trate Cd, (d) processing procedures, and, (e) sampling and analytical procedures (19). Chemical Properties of Nickel Nickel occurs in nature mainly in combination with As, At and S. Only Ni++ occurs in the ordinary chemistry of the element. The chemistry of Ni is not simple because of the existence of complex interconversions of various structures, i.e., octahedral, tetrahedral and square, as well as the formation of polymers by sharing of ligand atoms (8). Stability diagrams for chelates of Cd++ and Ni++ have been presented by Norvell (43) to illustrate one method of estimating the influence of chelating agents on the solubil- ity of potentially hazardous heavy metals in soils. The effectiveness of the chelating agents as chelates for Ni++ in calcareous soils would be in the order: DTPA, HEDTA, EDTA>CDTA>NTA>EDDHA>CIT>OX, EGTA,P3O10 (diethylenetriamine- penaacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, cyclohexanediaminetetra- acetic acid, nitrilotriacetic acid, ethylenediaminedi-Qr hydroxyphenylacetic acid, citric acid, oxalic acid, ethyl- eneglycol-bis(2-aminoethy1ether)tetraacetic acid, and triphosphoric acid, reSpectively). Clearly, DTPA, HEDTA, EDTA, and CDTA could most effectively increase the solu- bility of Ni++ in soils (43). Schnitzer and Skinner (52, J“, Pb, Mn 53) have determined stability constants for Ni+ and fulvic acid. Their log K values for metals of the first transition series fail to follow the Irving-William's sta- bility series (62). Stability constants reported for metal— soil organic-matter complexes are generally lower than those for complexes of the same metal with commercial chelating agents, such as EDTA and HEDTA. Nickel in Soil and Plants Vanselow (68) has noted that there are soils in scattered regions of the United States that have sufficient + to be phytotoxic. Patterson (46) concentrations of Ni+ and Hodgson (20) have reported the range of total Ni in normal soils to be between 5 and 20 ppm but may be as high as 2000 ppm in soils derived from ultrabasic igneous rocks (serpentine), definitely a phytotoxic concentration. Massey (40) has conducted a study on soils contaminated from mining Operations in Kentucky. Of the three metals investigated, Cu, Zn, and Ni, nickel is the most likely to remain in solution in toxic amounts after the pH is raised 10 by liming. He found that approximately 4.3, 2.5 and 1.4 ppm Ni would be found in solution at pH of 4.5, 5.5 and 6.5, re- spectively. This is compared to 2.5 ppm which is toxic to oats (46, 50). Plants affected by Ni toxicity Show two types of symptoms, one specific to the element such as white long- itudinal striping in oats, and the other, chlorosis and necrosis characteristic of induced iron deficiency. This has been investigated by Crooke, et a1. (9, 10, 11). The most likely mechanism for the production of induced iron deficiency is the replacement of iron by the toxic metal in some complex essential to normal metabolism (11). The necrosis produced by Ni might be the result of severe Fe deficiency (22) but Crooke et a1. (10) showed that a high iron SUpply reduced the severity of necrosis no more than could be accounted for by the reduction in Ni content. Hunter and Vergnano (22) described a wide range of crops exhibiting Ni toxicity symptoms. Plant species vary considerably in their susceptibility. Barley is resistant while wheat, ryegrass and beans are little affected. Oats, clover and potatoes are moderately affected, followed by turnips, swedes, cabbage and kale, with beet being the most sensitive crOp. The distribution of absorbed Ni in plants depends on the species (22). Tiffin (65) has found nega- tively charged Ni in xylem exudates of various plants. Although liming has traditionally been used to control tox- icities from developing, the hydrous oxides of Mn and Fe, Ivhich are nearly ubiquitous in clays, soils, and sediments, 11 have been prOposed by Jenne (23) to furnish the principal control on the fixation of Co, Ni, Cu, and Zn. Patterson (46) has reported work conducted upon the pH of the soil and its effects upon Ni toxicity. He found that toxic symptoms developed in wheat plants grown on a soil of pH 5.1 with 80 and 160 ppm Ni applied. At pH 6.5 only slight toxicity symptoms occurred and at pH 7.5 none were visibly affected. Uptake of Ni by the plants was small at pH 6.5 and 7.5 at levels below 80 ppm Ni in soil. He found that Ni tends to concentrate in the grain, the con- tent of which is between two and three times the level in straw. As a general guide it may be taken that if the total Ni in a soil is below 20 ppm at a pH of above 5.5 no damage to crOps may be expected. At a pH level around 7.5 considerably higher levels of Ni can be safe; whereas in more acid soils even 5 to 10 ppm Ni can be toxic. Nickel in Enzymatic Systems Nickel is not known to be essential for plants or animals. Schroeder (58) believes that it behaves like an essential trace element because: (a) it is ubiquitous in the biosphere, (b) shows biological activity in yitgg, affecting certain enzyme systems, (C) is toxic to mammals only in astringent doses, and, (d) has a low molecular weight and two interchangeable valencies. Nickel activates several enzyme systems including arginase (18), carboxylase (61), acetyl coenzyme A synthetase 12 (72), and trypsin (63). It inhibits acid phosphatase under certain conditions (44) and catalyzes the enzymatic decar- boxylation of oxalacetic acid (61). Nickel is found to be consistently present in ribonucleic acid (RNA) from diverse sources in concentrations many times higher than in the native material from which the RNA is isolated (64). Nickel as a Carcinogenic Metal The trace elements most extensively studied in mineral nutrition are Fe, Cu, Mn, and Mo. As the human body ages, a large number of these elements accumulate. When present in excess, they may be responsible for the induction of can- cer. Adequate documentation exists for only a small number of these metals. Unequivocal experiments reveal that Ni, Cd, and some Cr compounds are true metal carcinogens (14). Pure metallic Ni and many of its compounds can be considered as causes of cancer (47). Nickel compounds found to be car- NiO, NiCO cinogenic include Ni3S These are soluble, 2’ 3° insoluble and moderately soluble compounds. The target organ for this element is usually the muscle (14). Human beings are constantly being exposed to carcinogenic hydrocarbons from the atmosphere. The lungs and liver inac- tivate these hydrocarbons by an induced enzyme system, benzyrene hydroxylase. Nickel inhibits this enzyme (64); thus, it may permit the hydrocarbon to exist for longer periods allowing a longer time for the carcinogen to inter~ act with the tissues. 13 Nickel in Foodstuffs Nickel occurs regularly in soils and plants in concen— trations substantially higher than those normally present in animal tissues and fluids. Common pasture plants contain 0.5-3.5 ppm Ni on a dry weight basis (41, 60). Kent and McCance (27) give an estimate of 0.3 to 0.5 mg Ni/day, and Schroeder et a1. (58) give a similar calculated range of 0.3-0.6 mg Ni/day for human adults. The amounts and pro- portions of the different classes of foodstuffs consumed result in intakes of Ni which vary greatly. Schroeder et a1. (58) indicate that vegetarian diets supply more Ni than nonvegetarian diets. He estimates that 0.7-0.9 mg Ni/day is consumed in a vegetarian diet in comparison to 0.003-0.01 mg Ni/day of a diet high in refined foods and low in vegetables. Data on the Ni content of foods are meager. Approxi- mately 50 years ago Bertrand and Macheboeuff (4, 5) reported levels of 1.5 to 3.0 ppm Ni on a dry weight basis for green leafy vegetables and 0.15 to 0.35 ppm for fruits, tubers, and grains. Schroeder et a1. (58) have recently confirmed these data. CHAPTER 2 EFFECTS OF NICKEL AND CADMIUM CONTAMINATED SOILS ON NUTRIENT COMPOSITION OF CORN PLANTsl Abstract Rubicon sand from Muskegon County, Michigan was treated with NiCl2 and CdCl2 and crOpped with corn. The nutrient status of the soil was determined before and after cropping by chemical extractions, and the plant tissue was analyzed for several metals. Nickel and Cd were applied in equal amounts of milli- equivalents per 100 9 soil. Treatments ranging from 0.05 to 1.00 milliequivalent of metal/100 9 soil were replicated three times. A control set was included. The soil was limed to a pH of 6.8. The corn was harvested 5 weeks after planting. The dried, ground corn plant tissue was subjected to a nitric- perchloric acid digestion and analyzed for Cd, Cu, Fe, Mn, Ni and Zn by atomic absorption spectrophotometry. The soil metal levels after crOpping were determined by extractions with 0.1 N HCl, 1 N NH OAC or 0.005 M DTPA. 4 1Michigan Agricultural Experiment Station Journal Article No. 6416.‘ 14 15 The Cd-treated soils retard grown more than Ni-treated soils indicating a greater toxicity due to Cd than to Ni for corn. Likewise, Cd was taken up by corn to a greater extent than was Ni. 16 Introduction The natural geochemical partnership of Cd and Zn reported by Vinogradov (l9) accounts for entry of Cd into the environment. Atmospheric Cd, and the subsequent settling of the airborne particles on vegetation and soils, originates predominatly from smelting and electrOplating of metals (7). Apart from its association with Zn, Cd compounds used as fungicides (3, 9, 12) and Cd present in superphosphate fer- tilizer (14) also resulted in the entry of heavy metals into the soil. Intensive study of Cd in soils and plants originated when recent reports associated the excessive Cd accumu- lation in man with hypertension (15), emphysema, chronic bronchitis (10) and the "ouch-ouch" disease (17). In considering the soil-plant-animal-human system into which heavy metals may enter at any point and affect the entire system, one must direct attention to the most probable points of entry. Drinking water and diet are chief sources of Cd intake (16). Dustfall Cd enters water and food supplies in substantial amounts whereas Cd in inspired air contributes only 1-3% of the daily human intake. Cadmium level studies of plants grown on contaminated soils indicate that plants can readily absorb Cd from a soil (3, 4, 8). John, et al. (4) found that the Cd in radish and lettuce plants was significantly related to the soils' ability to adsorb Cd. l7 Nickel occurs commonly in soils and plants in concen— trations substantially higher than those normally present in animal tissue and fluid. Kent and McCance (5) and Schroeder, et a1. (13) estimate a 0.3 to 0.5 mg Ni intake per day for human adults. Vanselow (18) reported that soil contains 10 to 1000 ppm Ni and that soils in scattered regions of the United States have sufficient concentrations of Ni to be phytotoxic. EXperimentation has shown that Ni, Cd and some Cr compounds are true metal carcinogens (1). Increasing public concern with the problems of waste diSposal have brought pressures to solve not only municipal but also industrial pollution problems. The metal-plating industry in particular is somewhat unique because the wastes are not principally organic in nature. But rather, they are toxic because they contain heavy metal ions (Cd, Cr, Cu, Ni, and Zn) which interfere with the metabolism of living sys- tems. The need for treatment of these wastes and the fact that soil has a cation exchange capacity with Specific bonding sites offers interesting possibilities for inacti- vation and renovation of these metal ions by wastewater application to soil. If agricultural lands were (irrigated) over a period of time with effluent containing considerable quantities of heavy metals three phenomena could occur: (a) the metals being precipitated or strongly bound to the soil complex, unavailable for plant Uptake, (b) the metals passing through the soil profile and entering underground water supplies, or, 18 (c) the reSponse and nutrient composition of crOps grown on this soil. In an attempt to verify these points, research was initiated using a soil originating from a 10,000 acre dis- posal site near Muskegon, Michigan. A greenhouse study of the reSponse of corn grown on Ni and Cd contaminated soil and the nutrient composition of the crOp was done. Methods and Procedures Surface (0-4 in.) soil samples were collected from the site of the waste disposal area at Muskegon, Michigan. The soil was passed through a 20 mm stainless steel screen, air dried and stored in plastic containers. Samples for labora- tory work were passed through a 20 mm plastic screen. Soil physical analysis, pH, and organic matter content were determined by the MSU Soil Testing Laboratory. Cation exchange capacity was determined by the sodium saturation method (2) (Table 1). Table 1. Characteristic properties of Rubicon sand, A horizon. % Sand 89.38 % Silt ' 1.18 % Clay 9.44 % O.M. 2.16 C.E.C. (me/100g soil) 5.7 PH 5.0 19 A greenhouse project was designed to test the response of corn (Egg gays) to a soil contaminated with Cd and Ni; the inactivation of these metals by the soil; the release of other nutrients, and the effect upon the nutrient compo- sition of the crOp. Six treatments, each in triplicate, of NiCl and CdCl2 (0.05, 0.10, 0.20, 0.50, 0.75 and 1.00 me/ 2 1009 soil) as well as triplicate controls were utilized in this experiment. Two and a half kilograms of soil/pot received lime (to adjust pH to 6.8) fertilizer (NPK) and metal treatments, mixed in by hand. The pots, containing drainage holes, had distilled water added to 15% by weight and were allowed to equilibrate for 1 week, then 12 kernals were planted per pot. After emergence the seedlings were thinned to 8 plants/pot. Plants were harvested after five weeks of growth, dried in a forced air oven at 60°C and ground in a Wiley stainless steel mill with a 20 mesh screen. Soil core samples were removed from each pot and air-dried. Plant samples were digested with a nitric-perchloric acid mixture then analyzed for Cd, Cu, Fe, Mn, Ni, and Zn on a Perkin-Elmer 303 atomic absorption Spectrophotometer. The soil samples were equilibrated with three extractants: 0.005 M DTPA (diethylenetriaminepentaacetic acid) (11), l N NH4OAC, and 0.1 N HCl, and analyzed for Cd, Cu, Fe, Mn, Ni and Zn. 20 Results and Discussion Increasing levels of Ni when added to the soil, did not significantly increase plant Ni concentration and uptake, except at the highest level of treatment, 294 ppm (Tables 2 and 3). These data indicate that corn plants have an effective mechanismfor excluding Ni from uptake and/or translocation under the conditions studied. Data (Table 2) indicate that very high levels of added Ni tended to reduce plant growth slightly, but the degree of toxicity was low. These results indicate that Ni was being removed from soil solution very quickly and effectively. Table 2. Soil treatment, plant growth and metal content of corn grown on nickel-treated Rubicon sand under greenhouse conditions.a Soil Treatment Dry Plant Metal Concentration Nickel Weight Cd Cu Fe Mn Ni Zn me/100 9 ppm g/plant ---------- ppm ------------ 0.00 0 0.70 0 15 102 50 15 37 0.05 15 0.66 0 18 156 63 15 38 0.10 29 0.67 0 20 158 74 16 44 0.20 59 0.65 0 16 132 82 19 47 0.50 147 0.66 0 18 148 94 16 34 0.75 220 0.67 0 20 148 98 19 40 1.00 294 0.55 0 17 144 116 25 31 LSD (0.05) NS ns ns 13.0 6.4 ns aEach value is the average of 3 replications. 21 Table 3. Soil treatment, plant growth and metal uptake of corn grown On nickel-treated Rubicon sand under greenhouse conditions.a Soil Treatment Dry Plant Metal Uptake Nickel Weight Cd Cu Fe Mn Ni Zn me/IOO 9 ppm g/plant - ------- ug/plant --------- 0.00 0 0.70 0 10 71 35 10 26 0.05 15 0.66 0 12 104 42 10 25 0.10 29 0.67 0 13 104 50 11 29 0.20 59 0.65 0 10 86 53 12 32 0.50 147 0.66 0 12 97 62 10 22 0.75 220 0.67 0 13 99 66 13 27 1.00 294 0.55 0 10 81 64 l4 l7 LSD (0.05) NS ns ns 14 ns 8.1 aEach value is the average of three replications. Cadmium was much more toxic to the corn plants than was Ni. Addition of Cd to the soil resulted in severe plant growth retardation and elevated Cd concentration and uptake by plants (Tables 4 and 5). The plant growth decreased from 0.70 g/plant in the control to 0.29 g/plant at 281 ppm Cd added to the soil. Levels of plant Cd concentration rose from less than 0.5 ppm Cd to 131 ppm Cd with the same treat— ments. Cadmium was readily taken up and translocated in the plant and as a result was relatively toxic to the plants. As with Ni, Fe and Mn desorption by soils and concentration in plants was increased by increasing soil Cd levels. 22 Table 4. Soil treatment, plant growth and metal content of corn grown on cadmium—treated Rubicon sand under greenhouse conditions.a Soil Treatment Dry Plant Metal Concentration Cadmium Weight Cd Cu Fe Mn Ni Zn me/100 9 ppm g/plant ----------- ppm ------------- 0.00 0 0.70 - <1 15 107 50 15 37 0.05 28 0.53 26 13 185 71 10 56 0.10 56 0.40 47 14 171 73 15 43 0.20 112 0.44 55 13 206 67 16 37 0.50 281 0.29 131 19 146 84 15 33 0.75 422 0.32 131 10 149 95 12 36 1.00 562 0.25 133 12 128 86 15 30 LSD (0.05) 0.123 25.6 ns 54.8 21.0 ns ns aEach value is the average of 3 replications. Table 5. Soil treatment, plant growth and metal uptake of corn grown on cadmium-treated Rubicon sand under greenhouse conditions.a Soil Treatment Dry Plant Metal Uptake Cadmium Weight Cd Cu Fe Mn Ni Zn me/100 9 ppm g/plant --------- ug/plant --------- 0.00 0 0.70 <1 10 71 35 10 26 0.05 28 0.53 14 7 99 38 6 31 0.10 56 0.40 19 6 66 29 6 17 0.20 112 0.44 24 6 91 30 7 16 0.50 281 0.29 37 3 42 24 4 10 0.75 422 0.32 42 3 48 30 4 12 1.00 562 0.25 34 3 33 22 4 8 LSD (0.05) 0.123 10.0 2.1 27.4 ns ns 13.4 aEach value is the average of 3 replications. Soil extractants after cropping (Table 6) indicated that little Ni was extractable compared to the amount added to the soil. Most of the Ni was inactivated in a form that could resist removal by rather strong chemical treatments. 23 Therefore, most of the added Ni was probably not available to the corn plants. Langmiur adsorption isotherm data in- dicated much of the Ni was inactivated through an adsorption mechanism. Manganese was desorbed by the soil as Ni levels added were increased, and the increased Mn in soil solution resulted in increased Mn uptake by corn plants (Tables 2, 3, 6). Although the chemical extractants removed only a small part of the Ni added to the soil, the amount extracted cor- related well with the amount of Ni added in the original treatment. There was a poor correlation between plant growth or Ni uptake and the amount of Ni added or soil extractable Ni. Except for the increased Mn concentration and a possible increase in plant Fe concentration due to soil Ni addition, the treatments had no effect on metal composition of the plants or on the relative amounts of metals extractable from the Rubicon sand. Table 6. Soil treatments and soil extractable metal concen- trations of Rubicon sand.a Soil Metal Concentration Soil Treatments 0.1 N 0.005 M 1 N 0.1 N 0.005 M 1 N Nickel HCl DTPA NH4OAc HCl DTPA NH4OAc me/lOO 9 ppm ------ ppm Ni ------------- ppm Mn -------- 0.00 0 <1 <1 <1 18 5 2 0.05 15 8 4 <1 23 5 3 0.10 29 17 8 <1 15 5 7 0.20 59 31 15 2 l9 8 4 0.50 147 73 40 7 21 8 7 0.75 220 96 57 19 28 9 5 1.00 294 155 81 24 10 8 6 LSD (0.05) 21.0 5.7 5.6 8.8 ns 1.5 aEach value is the average of 3 replications. 24 The soil extraction of most metals was not influenced by Cd additions, but the Cd remained more soluble and ex- tractable than did the Ni (Table 7). Relative amounts of Cd extracted from the soil after crOpping correlated well with the Cd added to the soil and the amount taken up by plants. Table 7. Soil treatments and soil extractable metal con- centrations of Rubicon sand.a Soil Metal Concentration Soil Treatments 0.1 N 0.005 M l N 0.1 N 0.005 M 1 N Cadmium HCl DTPA NH 4OAC HC 1 DTPA NHAOAC me/100 9 ppm ----- ppm Cd ------------- ppm Mn -------- 0.00 0 <1 <1 <1 18 5 2 0.05 28 22 23 10 7 5 2 0.10 56 46 41 16 15 4 2 0.20 112 92 79 40 13 7 3 0.50 281 239 206 116 10 9 6 0.75 422 319 309 181 14 ll 11 1.00 562 378 364 224 10 ll 10 LSD (0.05) 38.9 38.8 31.9 ns 2.9 2.2 aEach value is the average of 3 replications. 10. 11. 12. 25 Literature Cited Furst, A. 1971. Trace elements related to Specific Chronic disease: Cancer. In: Environmental Geo- chemistry in Health and Disease, H.L. Connor and H.C. Hopps, Ed. The Geological Society of America, Inc., Boulder, Colorado, pp. 109-123. Jackson, M.L. 1958. Soil Chemical Analysis. Prentice Hall. John, M.K., H.H. Chuah and C. Van Laerhoven. 1972. Cadmium contamination of soil and its uptake by oats. Environ. Sci. Technol. 6:555-557. John, M.K., C. Van Laerhoven and H.H. Chuah. 1972. Factors affecting plant uptake and phytotoxicity of cadmium added to soils. Environ. Sci. Technol. 6: 1005-1009. Kent, N.L. and R.A. McCance. 1941. Adsorption and ex- cretion of minor elements by man (I) Ag, Au, Li, B and V (II) Co, Ni, Sn, and Mn. Biochem. J. 35:837-877. Kirby, A.R. 1971. Polluted rain revealed in Great Lakes area. Canada Center for Inland Waters, Burlington, Ontario, Press Release, Ottawa, Canada. Lagerwerff, J.V. 1967. Heavy metal contamination of soils. Soil and water conservation Research Division, A.R.S. Beltsville, Maryland. Lagerwerff, J.V. and A.W. Specht. 1970. Contamination of roadside soils and vegetation with Cd, Ni, Pb and Zn. Environ. Sci. Technol. 4:583-586. Lagerwerff, J.V. and A.W. Specht. 1970. Occurrence of environmental cadmium and zinc and their Uptake by plants. In: Trace Substances in Environmental Health - IV D.D. Hemphill, Ed. University of Missouri, Columbia, Missouri, pp. 85-93. Lewis, G.P., H. Lyle and S. Miller. 1969. Association between elevated heptic water soluble protein-bound Cd levels and chronic bronchitis and/or emphysema. Lancet II:1330-1333. Lindsay, W.L. and W.A. Norvell. 1969. DevelOpment of a DTPA micronutrient soil test, Agronomy Abstracts. p. 84. Ross, R.G. and D.K.P. Stewart. 1969. Cadmium residues in apple fruit and foliage following a cover spray of CdClz. Can. J. Plant Sci. 49:49-52. 13. 14. 15. 16. 17. 18. 19. 26 Schroeder, H.A., J.J. Balassa and I.H. Tipton. 1961. J. Chronic Dis. 15:51. Schroeder, H.A. and J.J. Balassa. 1963. Cadmium: Up- take by vegetation from superphosphate. Soil Science 140:819. Schroeder, H.A. 1965. Cadmium as a factor in hyper- tension. J. Chronic Dis. 18:647-656. Schroeder, H.A., A.P. Nason, I.H. Tipton and J.J. Balassa. 1967. Essential trace metals in man: Zinc, relation to environmental cadmium. J. Chronic Dis. 20:179-210. Tsuchiya, K. 1969a. Causation of "ouch-ouch" disease. Part I. Nature of the disease. Keio J. Med. 18:181- 194. Part II. Epidemiology and elevation. Keio J. Med. 18:195-211. Vanselow, A.P. 1966. Diagnostic Criteria for Plants and Soils, H.D. Chapman, Ed. Div. Agr. Sci. U. Calif. Berkeley, pp. 302-309. Vinogradov, A.P. 1959. The Geo-Chemistry_of Rare and Dispersed Chemical Elements in Soils, 2nd ed., N.Y. Consultants Bureau. CHAPTER 3 INFLUENCE OF NICKEL AND CADMIUM CONTAMINATION OF RUBICON SAND AND MORLEY CLAY LOAM UPON CORN GROWTH AND METAL COMPOSITION AND EXTRACTABLE SOIL METALS Abstract For a greenhouse investigation, Rubicon sand and Morley clay loam were contaminated with NiCl2 and CdCl2 by metal additions ranging from 0.05 to 1.00 me/100 g of soil. Rubi- con sand was adjusted to a pH of 6.7-6.8 with CaCO3 while the Morley clay loam was at a native pH of 6.7-6.8. The soils were planted to corn after being equilibrated with the metal additions for one week. The plants were harvested after five weeks of growth and analyzed for Cd, Cu, Fe, Mn, Ni and Zn after being dried in a forced-air oven at 60°C. Separate air-dry soil samples which were obtained after plant harvest, were extracted with 0.1 N HCl, and 0.005 N DTPA. Each extract was analyzed for Cd, Cu, Fe, Mn, Ni and Zn. Results indicate that Rubicon sand is more capable of bonding Ni than is Morley clay loam. Nickel levels affected yield only at the highest level of treatment on both soils. Manganese was released by each soil with increasing level of 27 28 Ni. Cadmium caused severe toxicity symptoms on plants grown on either soil with growth retardation even at the lowest level of Cd addition. Extractable Cd was similar for both soils at each level of treatment. Concentration of Cu, Fe, and Zn were not affected by metal treatment; Uptake of these metals was affected. 29 Introduction The increasing needs for alternative methods of waste- water diSposal for industrial, agricultural and domestic uses have resulted in efforts to utilize the natural filtering system of the soil. Industrial wastewaters, in particular, may contain heavy metals (Cd, Cr, CU, Ni, and Zn) which are toxic and interfere with the metabolism of living systems. Intensive studies of Cd in soils, plants, animals and humans originated after several cases of Cd poisoning were reported in Japan as a result of run-off from wastepiles at mining Operations (12). Considerable investigation has also been conducted to determine the sources of Cd pollutants in the environment (6, 9, 10, 14). In order to ascertain the influence of Cd Upon plants and various food crOps, a number of investigators (3, 4, 5, 7, ll, 13) have initiated programs of study. Most of the metals which are potentially hazardous in the environment belong to the transition elements of the periodic table. The electrode potentials of these elements indicate a tendency to yield aqueous solutions of their ions. However, the concentrations of metal ions are found to be lower than predicted by solubility due to their adSOprtion and/or COprecipitation with other compounds. Due to their electronic structure, the transition metals form a large number of complex compounds; therefore, chelating agents which may be present in wastewater may therefore cause an 30 apparent increase in the solubility of the metal (1). It would be very useful to know how different tex- tured soils respond to heavy metal contamination. Therefore, before using soils to treat wastewaters, certain prOperties of the soil and metals must be known: (a) the capacity of a soil for fixation of metals of this type; (b) the leaching potential of metal cations and anions in a specific soil; and (c) the response and nutrient composition of crops grown on this soil and the differences between soil types. Methods and Procedures Rubicon sand from Muskegon County and Morley clay loam from Washtenaw County, Michigan were obtained from the tOp four inches of the profile. The soils were passed through a 20 mm stainless steel screen, air-dried and stored in plastic containers. Samples for laboratory work were passed through a 2 mm plastic screen and were used on an air-dry basis. Soil physical analysis, pH and organic matter content were determined by the MSU Soil Testing Laboratory. Cation exchange capacity was determined by the sodium saturation method (2) (Table l). Morley clay loam contains twice the amount of organic matter as Rubicon sand. It also has a much higher cation exchange capacity and more surface area due to the higher Clay content. 31 Table 1. Characteristic prOpertieS of Rubicon sand, A horizon and Morley clay loam, Ap horizon. Soil % Sand % Silt % Clay; % O.M. CEC pH_ Rubicon sand 89.38 1.18 9.44 2.16 5.7 5.0 Morley clay loam 40.40 28.72 30.88 4.17 14.9 6.7 Six treatments each in triplicate, of NiCl2 and CdCl2 (0.05, 0.10, 0.20, 0.50, 0.75, and 1.00 me/100 9 soil) [15, 29, 59, 147, 220 and 294 ppm Ni; 28, 56, 112, 281, 422 and 562 ppm Cd], as well as triplicate controls were used in the greenhouse experiment. Two and a half kilograms of soil per pot received lime (to adjust to pH 6.8 on the Rubicon sand). The Morley clay loam had a native soil pH of 6.7. Fertilizer (NPK) and metal treatments were mixed in by hand. The pots, containing drainage holes with filter paper on the bottom, had distilled water added to 20% and 15% by weight for Morley clay loam and Rubicon sand, respectively. They were allowed to equilibrate for one week and were then arranged in a randomized complete block design. Twelve kernels of corn were planted per pot. After emergence the plants were thinned to 8 plants per pot and were harvested after five weeks of growth. All plants were dried in a forced air oven at 60°C and ground in a Wiley stainless steel mill with a 20 mesh screen. Soil core samples were removed from each pot after plant harvest and were air-dried. Plant samples were digested with a nitric-perchloric acid mixture. Separate subsamples were equilibrated with 2 32 extractants; 0.005 N DTPA (diethylenetriaminepentaacetic acid) (8), and 0.1 N HCl (hydrochloric acid). Both plant and soil samples were then analyzed for Cd, CU, Fe, Mn, and Zn on a Perkin-Elmer 303 atomic absorption spectrOphotometer. Results and Discussion Results indicate that nickel treatments did not result in toxicity to the plants grown on either soil type; how- ever, there was a slight decrease in yield with increasing level of treatment. There is a significant soil-level inter- action of Ni concentration and Uptake by the plants. At the higher levels of treatment the plants grown on the Morley clay loam concentrated more Ni than those grown on the Rubi- con sand (Table 2). A significantly greater amount of Ni was extractable from the Morley clay loam than from the Rubi- con sand. There was a good correlation between level of treatment and 0.1 N HCl extractable Ni on both soils (Table 3). With increasing level of metal treatment on both soils, plants took Up significantly more Mn; 50-60 percent more than the control plants. Plants grown on Morley clay loam took up more Mn at each level of treatment than did those grown on Rubicon sand (Table 2). Soil extractions (Table 1a) indicated that the Morley clay loam contained considerably more Mn (5-7 times more) than the Rubicon sand and more Mn was extractable with each level of treatment. Soil extrac- tions (Table 1a) indicate the Rubicon sand contained 3.3 times more extractable Fe than Morley clay loam. However, Fe 33 uptake by the plants was not affected by soil type or treat- ment (Table 2a). COpper and Zn concentration and uptake were not affected (Table 2a); soil extractions likewise were not affected. 34 .coauOMUODCA Ho>wq x Hwom uUMOHmwcmfim m on map owumasono uoz+ + + + + Hmo.o Aam>mqv Amo.ov omq + + + + mc Aaflomv Amo.ov 0mg m.ma N.mm 0.5 m.ma ms Aam>mq x Hwomv Amo.ov omq Hm nma ow om om.o mo: we baa vH mm mm.o mom van oo.H moa mma ma mm no.0 mo: mm mm ma ma no.0 mam omm mn.o em HvH 5H mm no.0 mo: mm «m OH ma wo.o mom hva om.o he mos NH SH as.o mos mm mm NH ma mm.o mam mm om.o mm Sn OH «H on.o mos om vs HH ma no.0 mom mm oa.o me mm m Ha mm.o mo: me mm 0H ma mm.o mom ma mo.o mm mm b m mh.o mo: mm om 0H ma on.o mom 0 oo.o u:ma@\ms 8mm ucmam\mo Ema unwam\m Ema m ooa\wE mxmumm‘ aoflumuucmocoo mxmums cofiumuucmocoo mama» HHOm meowz mmmcmmcmz HOMOAZ .EUOH moan awake: can pawn coowndm cmummuulawxow: :0 mxmm3 m How czoummbcm~m CHOU Sn mxmums 6cm GOwumuucmocoo mmmcmmcme can HOMOAG can Gama» mo acmwummsoo .N OHQMB 35 Table 3. Comparison of nickel concentrations ex from Rubicon sand and Morley Clay loam tractable Nickel Soil 0.1 N HCl 0.005 MNDTPA me/100 9 ppm --------- ppm Ni --------- 0.00 0 RUB <1 <1 MOR <1 <1 0.05 15 RUB 8 4 MOR 10 8 0.10 29 RUB 17 8 MOR 18 16 0.20 59 RUB 31 15 MOR 40 35 0.50 147 RUB 73 40 MOR 108 82 0.75 220 RUB 96 57 MOR 163 123 1.00 294 RUB 155 81 MOR 219 155 LSD (0.05) (Soil X Level) 14.7 5.8 LSD (0.05) (Soil) + LSD (0.05) (Level) + +Not calculated due to a significant Soil X Leve interaction. It would be expected that more Ni would be from the Rubicon sand than from the Morley clay has a high cation exchange capacity and organic tent. The high Fe concentration of the Rubicon responsible for complexing the Ni in a form not with 0.1 N HCl. The fact that the Rubicon sand may also be responsible for this phenomenon; th of insoluble NiCO3 may have taken place. 1 extractable loam which matter con- sand may be extractable was limed e formation 36 It appears that Ni is replacing Mn from its' bonding site on both soils and making it more available for plant uptake. However, the Morley clay loam contains 5-7 times as much Mn as the Rubicon sand but the plants grown on the Morley Clay loam take up only one and one half times as much Mn as those grown on Rubicon sand. The Ni on the Rubi- con sand may be replacing more Mn hence making it available for uptake and the Ni then being fixed to the Mn sites. Both soils contaminated with Cd caused severe plant growth retardation and toxicity. Soil type and treatment level significantly affected yield (Table 4). Cadmium Uptake by the plants was significantly affected by increasing level of treatment. There was no significant soil x treatment interaction in plant Cd Uptake. Soil extractions (Table 5) indicate a significance due only to level of treatment. Extractable Cd from both soils is similar at each treatment level. Plant Mn uptake was not affected by soil type. There was, however, a significant soil x treatment interaction (Table 3a). With increasing level of treatment, less Mn was taken up by the plants. Uptake by plants grown on Morley clay loam decreased much more than those grown on Rubicon sand. Soil extractions (Table 4a) indicate a higher Mn con- tent in the Morley clay loam than the Rubicon sand. Iron uptake was significantly affected by both soil type and level of treatment (Table 3a). Increasing level of treatment caused less Fe to be taken up by the plants. Soil 37 extractions, (Table 4a), however, showed no significant affect due to treatment. There was a significant difference due to soil type. The Cu and Zn uptake by the plants de- creased significantly with level of treatment. This may correspond to the plants gradually dying at the higher levels of treatment. Table 4. Comparison of yield and cadmium concentration and Uptake by corn plants grown for 5 weeks on cadmium- treated Rubicon sand and Morley clay loam. Cadmium Cadmium Soil Yield concentration uptake me/lOO 9 ppm g/plant ppm ug/plant 0.00 0 RUB 0.70 <1 <1 MOR 0.72 <1 <1 0.05 28 RUB 0.53 26 14 MOR 0.48 28 13 0.10 56 RUB 0.40 47 19 MOR 0.46 40 18 0.20 112 RUB 0.44 55 24 MOR 0.33 55 18 0.50 281 RUB 0.29 131 37 MOR 0.23 117 27 0.75 422 RUB 0.32 131 42 0.16 198 31 1.00 503 RUB 0.25 133 34 MOR 0.20 422 43 LSD (0.05) (Soil X Level) 0.101 71.6 ns LSD (0.05) (Soil) + + ns LSD (0.05) (Level) + + 7.9 + . . . . . Not calculated due to a Significant 5011 X Level inter- action. 38 Table 5. Comparison of cadmium concentrations extractable from Rubicon sand and Morley Clay loam. Cadmium Soil 0.1 N HCl 0.005 M DTPA me/100 9 ppm --------- ppm Cd --------- 0.00 0 RUB <1 <1 MOR <1 <1 0.05 28 RUB 22 23 MOR 22 14 0.10 56 RUB 46 41 MOR 44 28 0.20 112 RUB 92 79 MOR 96 85 0.50 281 RUB 239 207 MOR 211 223 0.75 422 RUB 319 309 MOR 297 325 1.00 562 RUB 378 364 MOR 378 367 LSD (0.05) (Soil X Level) ns ns LSD (0.05) (Soil) ns ns LSD (0.05) (Level) 19.5 27.6 10. 11. 12. 39 Literature Cited Argaman, Yerachmiel and Clark L. Weddle. The fate of heavy metals in physical-chemical treatment processes. Environmental Water Projects Dept., Betchel Inc., San Francisco, California. Jackson, M.L. 1958. Soil Chemical Analysis. Prentice Hall. John, M.K., H.H. Chuah and C. VanLaerhoven. 1972a. Cadmium contamination of soil and its Uptake by oats. Environ. Sci. Tech. 6:555-557. John, M.K., C. VanLaerhoven and H.H. Chuah. 1972b. Factors affecting plant Uptake and phytotoxicity of cadmium added to soils. Environ. Sci. Tech. 6:1005- 1009. Lagerwerff, J.V. 1971. Uptake of Cd, Pb and Zn by radish from soil and air. Soil Science. 111:129-133. Lagerwerff, J.V. and A.W. Specht. 1970. Contamination of roadside soils and vegetation with Cd, Ni, Pb and Zn. Environ. Sci. Tech. 4:583-586. Leep, R.H. and B.D. Knezek. 1973. Effect of soil heavy metal contamination upon plant growth and nutrient com- position. Am. Soc. of Agronomy Abstracts. Lindsay, W.L. and W.A. Norvell. 1969. DevelOpment of a DTPA micronutrient soil test. Agronomy Abstracts. p. 84. Ross, R.G. and D.K.P. Stewart. 1969. Cadmium residues in apple fruit and foliage following a cover spray of CdClz. Can J. Plant Sci. 49:49-52. Schroeder, H.A. and J.J. Balassa. 1963. Cadmium uptake by vegetation from superphosphate. Soil Science. 140: 819. Traynor, M.F. and B.D. Knezek. 1973. Effects of nickel and cadmium contaminated soils on nutrient composition of corn plants. In: Trace Substances in Environmental Health. D.D. Hemphill, Ed. Univ. of Missouri, Colubmia, Missouri. (In Press). Tsuchiya, K. 1969a. Causation of ouch-ouch disease. Part I. Nature of the disease. Keio J. Med. 18:181-194. Part II. Epidemiology and eleviation. Keio J. Med. 18: 195-211. 40 13. Turner, M.A. 1973. Effects of Cd treatment on Cd and Zn Uptake by selected vegetable Species. J. Environ. Quality. 2:118-119. 14. Vinogradov, A.P. 1959. The geochemistry of rare and dispersed chemical elements in soils, 2nd ed. N.Y. Consultants Bureau. Chapman and Hall, Ltd., London, pp. 149-154. CHAPTER 4 SUMMARY AND CONCLUSIONS A greenhouse study was conducted to evaluate the response of corn to two different textured soils contaminated with Cd and Ni; the release of other nutrients, and the effect upon the nutrient composition of the crop. The results from these experiments are summarized below. 1. Dry weight production was affected only at the highest level of treatment on Ni-contaminated Rubicon sand and Morley clay loam. 2. There was no significant increase in Ni concentration or uptake on Ni-Contaminated Rubicon sand. However, a signif- icant increase in Ni concentration and uptake occurred with increasing treatment on Morley clay loam. There was a signif- icant soil x level interaction of plant Ni concentration and Uptake. 3. A very significant increase in plant Mn concentra- tion and uptake was found on both soils with increasing metal treatment. 4. A decrease in plant Fe concentration and uptake occurred on Ni-contaminated Morley clay loam. Rubicon sand showed no changes in plant Fe concentration or Uptake. Rubi- con sand naturally contains three times as much extractable 41 42 Fe as Morley clay loam. 5. Extractable Ni levels from Morley clay loam were much higher than extractable levels from Rubicon sand. These differences may have resulted from the addition of CaCO3 to Rubicon sand when raising the pH to 6.7. The Morley clay was at a higher pH naturally and no CaCO3 was added. The CaCO3 could then bind the Ni in a precipitated form and result in less Ni being extractable from the Rubicon sand. 6. Extractable soil Mn concentrations increased significantly with increasing Ni treatment on Morley clay loam, but there was no significant change in extractable soil Mn concentration on Rubicon sand. 7. Other elements (CU, Fe, Zn) extractable from the soil were not significantly affected by Ni treatment. 8. At. all levels of treatment, Cd drastically de- creased plant dry-weight production on both soils. 9. Plant Cd concentration and Uptake increased with increasing Cd treatment. 10. Plant Mn concentration and Uptake increased with increasing Cd treatment on Rubicon sand. Cadmium treatment increased plant Mn concentration but decreased Mn Uptake on Morley clay loam. 11. Generally there was a decrease in plant Fe uptake with increasing levels of applied Cd on both soils. Other than a decrease in Zn uptake with Cd treatment on Morley clay loam-the Uptake of other elements were not influenced. 43 12. Comparable levels of extractable Cd were obtained from both soils and a high percentage of the applied Cd was easily extractable after crOpping. 13. No significant change in extractable soil Mn con- centration occurred with treatment of Cd on either soil. 14. Other elements extractable from the soil were not significantly affected by Cd treatment. 15. At all levels of treatment, Cd appeared to be much more toxic than did Ni. LI ST OF REFERENCES 10. 11. LIST OF REFERENCES Allaway, W.H. 1968. ‘Agronomic controls over the envi- ronmental cycling of trace elements. Advances in Agronomy 20:235-274. Argaman, Yerachmiel and C.L. Weddle. The fate of heavy metals in physical-chemical treatment processes. Environmental Water Projects Dept., Bechtel Inc., San Francisco, California. Baes, C.F. Jr. 1973. The properties of cadmium. In: Cadmium The Dissipated Element. W. Fulkerson and R.E. Goeller, Eds. Oak Ridge National Laboratory, pp. 29-59. Bertrand, G.M., C.R. Macheboeuff. 1925. Acad. Sci. 180:1380, 1993. Bertrand, G.M., C.R. Macheboeuff. 1926. Acad Sci. 183:5. Bowen, H.J.M. 1966. The biogeochemistry of the elements. In: Trace Elements in Biochemistry. Academic Press. London, pp. 179, 194. Carroll, R.E. 1966. The relationship of Cd in the air to cardiovascular disease death rates. J. Amer. Med. Assoc. 198:267-269. Cotton, F.A. and C. Wilkinson. 1966. The elements of the first transition series. In: Advanced Inorganic Chemistgy. Interscience Publishers, John Wiley and Sons, New York, pp. 878-879. Crooke, W.M. 1955. Further aspects of the relationship between Ni toxicity and Fe supply. Ann. Appl Biol. 43:465. Crooke, W.M., J.G. Hunter, and O. Vergnano. 1954. The relationship between Ni toxicity and Fe supply. Ann. Appl. Biol. 41:311. Crooke, W.M. and A.H. Knight. 1955. The relationship between Ni-toxicity symptoms and the absorption of Fe and Ni. 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Comparison of iron and manganese concentrations extractable from nickel-treated Rubicon sand and Morley clay loam. 0.1 N 0.005 M 0.1 N 0.005 M Nickel Soil HC1_ DTPA_ HC 1" DTPA— me/100 9 ppm --- ppm Fe ---- --- ppm Mn ----- 0.00 0 RUB 70 47 18 5 MOR 21 45 128 37 0.05 15 RUB 71 48 23 5 MOR 21 44 107 32 0.10 29 RUB 75 51 15 5 MOR 22 46 108 36 0.20 59 RUB 70 45 19 8 MOR 20 43 100 38 0.50 147 RUB 61 41 21 8 MOR 25 42 145 35 0.75 220 RUB 59 45 28 9 MOR 24 41 160 41 1.00 294 RUB 62 39 10 8 MOR 26 40 167 36 LSD (0.05) (Soil X Level) 10.5 ns 14.9 ns LSD (0.05)(Soil) + 1.5 + 2.7 LSD (0.05) (level) ns 2.9 + ns +Not calculated due to a significant Soil X Level inter- action. 51 .coHuomumucfl Hm>mq x aflom HCMOAMSGmwm m on map Uwuwasoamo uoz+ m: w: m: + m.m m: Aam>oqv Amo.ov omq m.m m.m m: + me n: AHflomv Amo.ov qu m: m: ma m.m¢ ma ma AHm>mA x HflOmv Amo.ov omq mm mm mv ooa m ma mos ha Hm om vva 0H NH mom vmm oo.H om mm mm mm NH ma mo: hm ov mm mva ma om mom omm m>.o mm vm hm oma ha mm mo: mm vm hm mva NH ma mom nva om.o om mv on boa ma ma mo: mm 5v mm NmH 0H ma mom mm om.o mm mv mm mma ma Hm mo: mm vv voa mma ma om mom mm 0H.o om ow mm wNH NH ma mos mm mm voa me NH ma mam ma mo.o mm om moa Hma ma ma mo: mm mm an NOH 0H ma mom 0 oo.o unmam\ms Ema ucmHm\ms Ema ucmHm\ms Ema Sam 0 ooa\oE mxmums .ocoo mxmumd .ocoo mxmums .ocoo Aflom meoflz ocfiu COHH Hmmmou .EMOH xmao amauoz new team coownam cmummuuuawx0fi: co oxmums cam coflumuucoocoo OCHM can Hmmmoo .coufi mo cowaummfioo .MN OHQMB 52 .COHHOOHODCH HO>OH x HHOO DCOOHMHSOHM O OH mac OOHMHDOHOO uoz+ 0.0 m: + + + P + O.N AHO>OHO AO0.00 OOH m: 0.0 ms + + m: m: O.H HHHomO HO0.00 omH m: ma 0.0 O.HN O.HN 0.00 O.N m: AHO>OH x HHomO Amo.oc own O OO OH OOH ON OON H HH mo: O OO NN OO OO ONH O NH mom NOO OO.H O OH OH OOH OH OO N HH mo: NH OO OO OO Ow OOH O OH mom NNO O0.0 HH Ow ON OHH ON HHH N OH mos OH OO ON OO NO OOH O NH mam HON O0.0 NH OO ON OO HO OOH O OH mo: OH NO OO OO HO OON O OH mam NHH ON.O ON OO ON «O OO OOH O OH mos OH Ov ON On NO HOH O OH mom OO OH.O ON «O OO OO OO vHH O OH mos HO OO OO HO OO OOH O OH mam ON O0.0 OO OO OO OO OOH HOH OH OH mo: ON OO OO OO HO NOH OH OH mom O O0.0 ucmHmNOs Ema HGMHQ\OD Ema ucmHONOS Ema ncmHmNm: Ema Ema m OOH\OE mxmums .Ocoo Oxmum: .ocoo mxmumn .osOo Oxmums .OCOO HHom EOHEOOO OGHN mmmcmmcmz couH memwo .EOOH OOHU OOHHOS can Ocmm COOHQDM OOHOOHHLESHEUOO :0 me03 O Mom USOHO mucmHm Shoo On mxmumn can mcoHumuucmocoo OCHN UGO Ommammcma .GOHH .memoo mo COMHMOQEOU .MM mHnma 53 Table 4a. Comparison of iron and manganese concentrations extractable from cadmium-treated Rubicon sand and Morley clay loam. 0.1 N 0.005 N 0.1 N 0.005 N Cadmium Soil HCl DTPA HCl DTPA me/lOO g ppm --- ppm Fe --- --- ppm Mn --- 0.00 0 RUB 70 47 18 5 MOR 21 45 128 39 0.05 28 RUB 52 54 7 5 MOR 25 48 170 30 0.10 56 RUB 65 56 15 4 MOR 23 32 133 15 0.20 112 RUB 73 49 13 7 MOR 23 34 151 22 0.50 281 RUB 66 48 10 9 MOR 23 32 154 34 0.75 422 RUB 78 53 14 ll MOR 22 . 30 127 26 1.00 562 RUB 83 39 10 11 MOR 22 24 137 23 LSD (0.05) (Soil X Level) 13.3 6.0 17.5 5.9 LSD (0.05) (Soil) + + + + LSD (0.05) (Level) ns + + + +Not caluclated due to a significant Soil X Level inter- action. MIC iHIGAN STATE UNIVERSITY LIBRAR