565..."..8 . r7 .«a-nug—c l~w~‘u;u-' «n PLANT RESPONSE TO AND (SOIL 7. ’ ' 73.7.: ' IMMOBIIJ you 0F mngASINGLEVELs-i OFZ ‘ ANDCR+ APPLIEDTDT -7 :-‘ : f 5);; ACATEAIA‘OF SANDY SOILS. * " PET} ? ; Dissertatmn Io: the: Degree of Ph D MICHIGAN STATE UNIVERSITY ' .; ‘ A mommsepn SCHUENEMAN ;: . * é ,. L z 1374 "flux-JV an I. Am 'r~ 4:“ n" ADD :3A R K 3-. LIE'R I": 1? rug‘CI‘O’l'l 5mm ' 213;, bug-yr) L ,~----a-\-V.I¢‘: ~“M A This is to certify that the thesis entitled PIANT RESPONSE TO AND SOIL MOBILIZATION OF INCREASING LEVELS. OF ZN-l-2 AND CR+3 APPLIED TO A CATENA OF SANDY SOIIS presented by . Thomas Joseph Schueneman has been accepted towards fulfillment of the requirements for Ph.D. degreein Department of Crop and Soil Sciences fiV/Jffle Major professor Date September 6, 1974 0-7639 :61 MN ‘3' many "DAB & SOIS' BO 0 K BINDERY LIBRARY BINDERS xrnmeroarmcmm t”. g l ‘1‘? I Aw I" :3' r9“??? 1'. WI? 2 ‘3 [7,77 ILA/kac 2 MAR 3971931 3: O U.” I ’1' 3mmfiew1 ABSTRACT PLANT RESPONSE TO AND SOIL IMMOBILIZATION OF INCREASING LEVELS OF zN+2 AND CR+3 APPLIED TO A CATENA OF SANDY SOILS BY Thomas Joseph Schueneman The response and metal composition of corn, field beans and tomatoes grown on four Zn and four Cr treated soils were examined in a greenhouse study. The leaching potential of the added metals as well as the capacity of the individual soils to fix increasing amounts of metals were also studied. Four sandy soils originating from the same parent material but differing in natural drainage conditions and vegetative cover were treated with increasing levels of ZnCl2 or CrCl3. Levels of Zn were 0, 50, 100, 150, 200, and 400 ppm and levels of Cr were 0, 50, 100, 200, and 400 ppm. Separate soil sam- ples were extracted with H o, 15 NH OAc, 0.005ngTPA and 0.1N 2 4 HCl. After harvest, plant digests and soil extractions were analyzed for Cr, Zn, Mn, Fe, and Cu on an atomic absorption spectrophotometer. A pH determination was made on all soil samples. Plant-Zn concentration and uptake increased with in- creasing ambient soil+Zn concentration, the highest amounts Thomas Joseph Schueneman being, with one exception, in plants growing in soil with the lowest organic matter content and C.E.C. The exception was the Rubicon sand which had the lowest C.E.C., 3.9 meg/100 g of soil, but displayed a capacity to neutralize high Zn levels similar to a soil with 8.9% organic matter and a C.E.C. of 19.5 meg/100 g of soil. This is partially explained by the Rubicon sand's high Mn content and well aerated condition. In- creasing soil-Zn levels increased plant-Mn concentrations. No Cr was detectable in the crops grown until an ambient soil-Cr concentration was reached which caused severe growth reduction to the plants, usually at the 100 or 200 ppm Cr level. In 70% of the plants significant growth reduction occurred at the 50 ppm Cr treatment level and in 100% of the plants at the 100 ppm Cr level. Plant-Mn concentration was increased at low Cr levels and decreased at high Cr levels. 0, NH With increasing soil-Zn treatment levels, H OAc, 2 4 DTPA and HCl extractable Zn increased, H 0, NH OAc and DTPA 2 4 extractable Mn increased, and H 0 and NH OAc extractable Fe 2 4 decreased. With increasing soil-Cr treatment levels, NH4OAc, DTPA and HCl extractable Cr increased, and H20, NH4OAc and DTPA ex- tractable Mn increased and Fe decreased. At the 400 ppm Cr treatment level less than 25% of the Cr was extractable with 0.1N'HC1 and less than 2% was extractable with 1E.NH OAc. 4 PLANT RESPONSE TO AND SOIL IMMOBILIZAT 0N 0F INCREASING LEVELS OF 2N+2 AND CR+ APPLIED TO A CATENA 0F SANDY SOILS BY Thomas Joseph Schueneman A DISSERTATION Submitted to Michigan State University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Crop and Soil Sciences 1974 To my wife, Marilyn, and the children, Paul, Philip, Gregory and Carrie for persevering in Spartan Village and help- ing to bring this program to a successful conclusion. ii ACKNOWLEDGMENTS I sincerely acknowledge the guidance and encouragement of Dr. B. G. Ellis during my entire Ph.D. program at Michigan State University. His willingness to personally participate in the many projects continually going on is an example I will try to follow. The continual availability of Dr. B. D. Knezek to the author for discussions and suggestions is gratefully appre- ciated. The support and suggestions of the other members of my guidance committee is gratefully acknowledged: Drs. A. E. Erickson, Dr. D. Penner and Dr. H. C. Price. The support and assistance of Mrs. Elizabeth Shields and other members of the soil chemistry staff is appreciated. I wish to also express my appreciation to other faculty members and fellow graduate students in the CrOp and Soil Sciences Department who helped further my understanding of soil science during my course of study. iii TABLE OF CONTENTS Page LIST OF TABLES................... .......... ............ vi LIST OF FIGURES.... ...... .......... ............ . ....... xvi INTRODUCTION.......... ......... ............... ........ . 1 LITERATURE REVIEW............................... ....... 3 Effluent Sources of zinc and Chromium............ 3 Zinc in Soils............ ......... . ....... ....... 6 Chromium in Soils................................ 16 Plant-Zinc Relations............................. 19 Plant-Chromium Relations................... ...... 23 Soil Analysis for Zinc and Chromium.............. 25 MATERIALS AND METHODS.................................. 28 RESULTS AND DISCUSSION................................. 34 Plant Response to Soil-Zinc Additions............ 34 Effects of Added Zinc on Soil pH and Extract- ability of Zinc, Manganese, Iron and Copper...... 45 Plant Response to Soil-Chromium Additions........ 49 Effects of Added Chromium on Soil pH and Extract- ability of Chromium, Zinc, Manganese, Iron and copperOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO 59 Probable Soil-Plant Relations after Irrigation with Effluents Containing Zinc and Chromium...... 63 Suggested Research Areas......................... 65 SUMMARY AND CONCLUSIONS............. ...... . ..... . ...... 67 iv Page APPENDIXOCCOOOOOOOO0.0..0..0...OOOOCOOOOOOOOOOOOOOOOOOO 71 LIST OF REFERENCES.... ..... ............................ 123 Table 1. 10. 11. 12. 13. 14. 15. 16. LIST OF TABLES Page Characterization of the soils collected for study from Muskegon, Michigan...... ...... ......... Total content of Cr, Zn, Mn, Fe and Cu in the ex- perimental soils as determined on perchloric acid- hydrofluoric acid digested non-treated samples.... Summary of Zn concentrations in plants due to soil- zn additionSOOOOOO.I...OOOOOOOOOOOOOOIOOOOOOOCO... Summary of Mn concentration in plants due to soil- zn additions...00.00.0000...OOOOOOOOOOOOOOOOCOOOOO Summary of Mn uptake by plants in response to seil-zn additions...I000......OOOOOOOOOOOOOOOO0..O Summary of pH data on Zn-treated soils............ Summary of extractable Zn from Zn-treated soils... Summary of extractable Mn on Zn-treated soils..... Summary of plant dry weight data for plants on Cr- treated 805.18.00.00...0..OOOOOOOOOOOOO0.0.0.000... Summary of plant-Cr concentrations resulting from increasing additions of Cr to soils............... Summary of plant-Cr uptake in response to Cr addi- tions to the SOilOOOOOOOOOOOOOOO0.00...0.0.0.0.... Summary of plant-Mn concentration in response to cr additions to the 8011....OOOOOOOOOOOOOOOOOOOOOO Summary of pH data on Cr-treated soils............ Summary of extractable Cr from Cr-treated soils... Summary of extractable Mn from Cr-treated soils... Summary of extractable Fe from Cr-treated soils... vi 29 29 41 43 44 46 47 48 50 57 58 58 S9 61 63 63 Appendix Table l. 10. Effects of soil type and treatment level on plant dry weight, zinc concentration and uptake by corn I grown on zinc-treated soils under greenhouse conditions....................................... Effects of soil type and treatment level on plant dry weight, zinc concentration and uptake by field beans grown on zinc-treated soils under greenhouse conditions...00.....OOOOOOOOOOOIOOOOOOOOOOOOOOOOO Effects of soil type and treatment level on plant dry weight, zinc concentration and uptake by to- matoes grown on zinc-treated soils under green- house conditions................................. Effects of soil type and treatment level on plant dry weight, zinc concentration and uptake by corn II grown on zinc-treated soils under greenhouse conditions....................................... Effects of soil type and treatment level on plant dry weight, manganese concentration and uptake by corn I grown on zinc-treated soils under green- house conditions................................. Effects of soil type and treatment level on plant dry weight, manganese concentration and uptake by field beans grown on zinc-treated soils under greenhouse conditions............................ Effects of soil type and treatment level on plant dry weight, manganese concentration and uptake by tomatoes grown on zinc-treated soils under greenhouse conditions............................ Effects of soil type and treatment level on plant dry weight, manganese concentration and uptake by corn II grown on zinc-treated soils under greenhouse conditions............................ Effects of soil type and treatment level on plant dry weight, iron concentration and uptake by corn I grown on zinc-treated soils under greenhouse conditions....................................... Effects of soil type and treatment level on plant dry weight, iron concentration and uptake by field beans grown on zinc-treated soils under greenhouse conditions............................ vii Page 71 71 72 72 73 73 74 74 75 75 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. Effects of soil type and treatment level on plant dry weight, iron concentration and uptake by to- matoes grown on zinc-treated soils under green- house conditions................................. Effects of soil type and treatment level on plant dry weight, iron concentration and uptake by corn II grown on zinc-treated soils under greenhouse conditions....................................... Effects of soil type and treatment level on plant dry weight, copper concentration and uptake by corn I grown on zinc-treated soils under green- house conditions................................. Effects of soil type and treatment level on plant dry weight, copper concentration and uptake by field beans grown on zinc-treated soils under greenhouse conditions............................ Effects of soil type and treatment level on plant dry weight, copper concentration and uptake by tomatoes grown on zinc-treated soils under green- house conditions................................. Effects of soil type and treatment level on plant dry weight, c0pper concentration and uptake by corn II grown on zinc-treated soils under green- house conditions................................. Influence of zinc treatments on soil pH - first sampling prior to planting corn I and field beanSOOOOOOOOOI.OOOOOOOOOICIOOOOOOOOOO0.0.0.0.... Influence of zinc treatments on soil pH - second sampling prior to planting corn II and tomatoes.. Soil treatments and soil extractable metal con- centrations for zinc-treated AuGres sand prior to cr0pping with corn I under greenhouse condi- tionSoooooococo-ooooooooooooooooo...00.000.00.000 Soil treatments and soil extractable metal con- centrations for zinc-treated Roscommon sand prior to cropping with corn I under greenhouse condi- tlons........0.00.0000...COO-OOOOOOOOCOOOOOOOO... Soil treatments and soil extractable metal con- centrations for zinc-treated Rubicon sand prior to cropping with corn I under greenhouse condi- tions...OOOOOOOIOOOOOOOOOOCC0.0.0.0000...0......O viii Page 76 76 77 77 78 78 79 79 80 80 81 22. 23. 24. 25. 26. 27. 28. 29.~ 30. 31. Page Soil treatments and soil extractable metal concen- trations for zinc-treated Granby loamy sand prior to cropping with corn I under greenhouse condi- tlonSOOOIOOOOOOOUOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO 81 Soil treatments and soil extractable metal concen- trations for zinc-treated AuGres sand prior to cropping with field beans under greenhouse condi— tlons.‘.OOOOOOOOOOOOOOOOOOOOOC00....OOOOOOOOOOOOO 82 Soil treatments and soil extractable metal concen- trations for zinc-treated Roscommon sand prior to cropping with field beans under greenhouse con- ditions.......................................... 82 Soil treatments and soil extractable metal concen- trations for zinc-treated Rubicon sand prior to cropping with field beans under greenhouse con- ditions.......................................... 83 Soil treatments and soil extractable metal concen- trations for zinc-treated Granby loamy sand prior to cropping with field beans under greenhouse con- ditions.......................................... 83 Soil treatments and soil extractable metal concen- trations for zinc-treated AuGres sand prior to cropping with tomatoes under greenhouse condi- tionBOOOOOOOOOOOOOOOOOOOOOOOOOCOOOOOOOOOCOOCOOOOO 84 Soil treatments and soil extractable metal concen- trations for zinc-treated Roscommon sand prior to cropping with tomatoes under greenhouse condi- tlons...OOOOOOOOOOOOOOOOOOOOOOOOIOOOOOCCOOOOOCOOO 84 Soil treatments and soil extractable metal concen- trations for zinc-treated Rubicon sand prior to cropping with tomatoes under greenhouse condi- tionSOOIOO00......OOOOOOOOOIOOOOOOOIOOOOO00...... 85 Soil treatments and soil extractable metal concen- trations for zinc-treated Granby loamy sand prior to cropping with tomatoes under greenhouse condi- tiOl‘Sooo-oooooooooooooooooooooooooooooooooooooooo 85 Soil treatments and soil extractable metal concen- trations for zinc-treated AuGres sand prior to cr0pping with corn II under greenhouse condi- tlonSOOOCO0.0.0....OOOOOOOOOOOOOOOOOOOOOOOO...0.. 86 ix 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. Page_ Soil treatments and soil extractable metal concen- trations for zinc-treated Roscommon sand prior to cropping with corn II under greenhouse condi- tlons....00....0.00.00.0000...0.0.0.0....000000.. Soil treatments and soil extractable metal concen- trations for zinc-treated Rubicon sand prior to cropping with corn II under greenhouse condi- tlonSCOOOOOOOOCOOOOOCOOO0......OOOOOOOCIOOOOOOOOO Soil treatments and soil extractable metal concen- trations for zinc-treated Granby loamy sand prior to cropping with corn II under greenhouse condi- tlonSIOOOOO0.....00...0..OOOOUIOOOOOCOOCOOOOOOOOO Effects of soil type and treatment level on H20 extractable zinc concentrations from zinc-treated soils under greenhouse conditions................ Effects of soil type and treatment level on lg NH4OAc extractable zinc concentrations from zinc- treated soils under greenhouse conditions........ Effects of soil type and treatment level on 0. 005M DTPA extractable zinc concentrations from zinc- treated soils under greenhouse conditions........ Effects of soil type and treatment level on 0.1N HCl extractable zinc concentrations from zinc- treated soils under greenhouse conditions........ Effects of soil type and treatment level on 820 extractable manganese concentrations from zinc- treated soils under greenhouse conditions........ Effects of soil type and treatment level on 1N NH4OAc extractable manganese concentrations from zinc-treated soils under greenhouse conditions... Effects of soil type and treatment level on 0.005M DTPA extractable manganese concentrations from zinc-treated soils under greenhouse conditions... Effects of soil type and treatment level on 0.1N HCl extractable manganese concentrations from zinc-treated soils under greenhouse conditions... Effects of soil type and treatment level on H20 extractable iron concentrations from zinc-treated soils under greenhouse conditions................ 86 87 87 88 88 88 89 89 89 9O 9O 9O 44. 45. 46. 47. 48. 49. so. 51. 52. 53. 54. Effects of soil type and treatment level on 1N NH4OAc extractable iron concentrations from thc- treated soils under greenhouse conditions........ Page 91 Effects of soil type and treatment level on 0.005M DTPA extractable iron concentrations from zinc- treated soils under greenhouse conditions........ Effects of soil type and treatment level on 0.13 HCl extractable iron concentrations from zinc- treated soils under greenhouse conditions........ Effects of soil type and treatment level on plant dry weight, chromium concentration and uptake by corn I grown on chromium-treated soils under greenhouse conditions............................ Effects of soil type and treatment level on plant dry weight, chromium concentration and uptake by field beans grown on chromium-treated soils under greenhouse conditions............................ Effects of soil type and treatment level on plant dry weight, chromium concentration and uptake by tomatoes grown on chromium-treated soils under greenhouse conditions............................ Effects of soil type and treatment level on plant dry weight, chromium concentration and uptake by corn II grown on chromium-treated soils under greenhouse conditions............................ Effects of soil type and treatment level on plant dry weight, manganese concentration and uptake by corn I grown on chromium-treated soils under greenhouse conditions............................ Effects of soil type and treatment level on plant dry weight, manganese concentration and uptake by field beans grown on chromium-treated soils under greenhouse conditions............................ Effects of soil type and treatment level on plant dry weight, manganese concentration and uptake by tomatoes grown on chromium-treated soils under greenhouse conditions............................ Effects of soil type and treatment level on plant dry weight, manganese concentration and uptake by corn II grown on chromium-treated soils under greenhouse conditions............................ xi 91 91 92 92 93 93 94 94 95 9S 55. S6. 57. 58. 59. 60. 61. 62. 63. 64. Effects of soil type and treatment level on plant dry weight, zinc concentration and uptake by corn I grown on chromium-treated soils under greenhouse conditions............................ Effects of soil type and treatment level on plant dry weight, zinc concentration and uptake by field beans grown on chromium-treated soils under greenhouse conditions............................ Effects of soil type and treatment level on plant dry weight, zinc concentration and uptake by to- matoes grown on chromium-treated soils under greenhouse conditions............................ Effects of soil type and treatment level on plant dry weight, zinc concentration and uptake by corn II grown on chromium-treated soils under green- house conditions................................. Effects of soil type and treatment level on plant dry weight, iron concentration and uptake by corn I grown on chromium-treated soils under greenhouse conditionSOOOOOOOOOOOOOO00......OOOOOOOOOOOOOOOOO Effects of soil type and treatment level on plant dry weight, iron concentration and uptake by field beans grown on chromium-treated soils under greenhouse conditions............................ Effects of soil type and treatment level on plant dry weight, iron concentration and uptake by to- matoes grown on chromiwm-treated soils under greenhouse conditions............................ Effects of soil type and treatment level on plant dry weight, iron concentration and uptake by corn II grown on chromium-treated soils under green- house conditions................................. Effects of soil type and treatment level on plant dry weight, copper concentration and uptake by corn I grown on chromium-treated soils under greenhouse conditions............................ Effects of soil type and treatment level on plant dry weight, copper concentration and uptake by field beans grown on chromium-treated soils under greenhouse conditions............................ xii Page 96 96 97 97 98 98 99 99 100 100 65. 66. 67. 68. 69. 70. 71. 72. 73. 74. 75. Effects of soil type and treatment level on plant dry weight, c0pper concentration and uptake by tomatoes grown on chromium-treated soils under greenhouse conditions............................ Effects of soil type and treatment level on plant dry weight, copper concentration and uptake by corn II grown on chromium-treated soils under greenhouse conditions............................ Influence of chromium treatments on soil pH - firs sampling prior to planting corn I and field beans Influence of chromium treatments on soil pH - second sampling prior to planting corn II and to- matoeSOOOOCOCCOOOOOOOOOOOOOOOIOOOOOO0.0.0.0000... Soil treatments and soil extractable metal concen- trations for chromium-treated AuGres sand prior to cropping with corn I under greenhouse condi- tions...OOOOOOOOOOOOOOOOOO0.0000000000000000COOOO Soil treatments and soil extractable metal concen- trations for chromium-treated Roscommon sand prior to cropping with corn I under greenhouse condi- tionSCOOOOOOOCOOOOOOOICOOOOCCCOOCCOOOOOIOOOOCOOCO Soil treatments and soil extractable metal concen- trations for chromium-treated Rubicon sand prior to cropping with corn I under greenhouse condi- tionSoo0.00.00.00.00.0.0.0.0000...-000.000.000.00 Soil treatments and soil extractable metal concen- trations for chromium-treated Granby loamy sand prior to cropping with corn I under greenhouse conditions....................................... Soil treatments and soil extractable metal concen- trations for chromium-treated AuGres sand prior to cropping with field beans under greenhouse conditions....................................... Soil treatments and soil extractable metal concen- trations for chromium-treated Roscommon sand prior to cropping with field beans under greenhouse con- ditiODSococo-00.00.000.00oooooooooooooooooooooooo Soil treatments and soil extractable metal concen- trations for chromium-treated Rubicon sand prior to cropping with field beans under greenhouse conditions....................................... xiii Page 101 101 t 102 102 103 104 105 106 107 108 109 76. 77. 78. 79. 80. 81. 82. 83. 84. 85. 86. Soil treatments and soil extractable metal concen- trations for chromium-treated Granby loamy sand prior to cropping with field beans under green- house conditions................................. Soil treatments and soil extractable metal concen- trations for chromium-treated AuGres sand prior to cropping with tomatoes under greenhouse condi- tions..... ........ ............................... Soil treatments and soil extractable metal concen- trations for chromium-treated Roscommon sand prior to cropping with tomatoes under greenhouse condi- tionSoooooooo ..... ............................... Soil treatments and soil extractable metal concen- trations for chromium-treated Rubicon sand prior to cropping with tomatoes under greenhouse con- ditions.......................................... Soil treatments and soil extractable metal concen- trations for chromium-treated Granby loamy sand prior to cropping with tomatoes under greenhouse conditions....................................... Soil treatments and soil extractable metal concen- trations for chromium-treated AuGres sand prior to crOpping with corn II under greenhouse conditions Soil treatments and soil extractable metal concen- trations for chromium-treated Roscommon sand prior to cropping with corn II under greenhouse condi- tionSoo0.0000000000000000oooooooooooooooooooooooo Soil treatments and soil extractable metal concen- trations for chromium-treated Rubicon sand prior to cropping with corn II under greenhouse condi- tions...... ..... ................................. Soil treatments and soil extractable metal concen- trations for chromium-treated Granby loamy sand prior to cropping with corn II under greenhouse conditions....................................... Effects of soil type and treatment level on H20 extractable chromium concentrations from chromiumr treated soils under greenhouse conditions........ Effects of soil type and treatment level on 1N NH4OAc extractable chromium concentrations fram chromiwm-treated soils under greenhouse conditions xiv Page 110 111 112 113 114 115 116 117 118 119 119 87. 88. 89. 90. 91. 92. 93. 94. 95. 96. Page Effects of soil type and treatment level on 0.005M DTPA extractable chromium concentrations from chromium-treated soils under greenhouse condi- tions..................................... ...... . 119 Effects of soil type and treatment level on 0.1g HCl extractable chromium concentrations from chromium-treated soils under greenhouse condi- tions............................................ 120 Effects of soil type and treatment level on H20 extractable manganese concentrations from chromium- treated soils under greenhouse conditions........ 120 Effects of soil type and treatment level on 1N NH4OAc extractable manganese concentrations from chromium-treated soils under greenhouse conditions 120 Effects of soil type and treatment level on 0.005M DTPA extractable manganese concentrations from chromium-treated soils under greenhouse condi- tions............ ..... ........................... 121 Effects of soil type and treatment level on 0.1§ HCl extractable manganese concentrations from chromium-treated soils under greenhouse condi- tions............................................ 121 Effects of soil type and treatment level on H20 extractable iron concentrations from chromium- treated soils under greenhouse conditions........ 121 Effects of soil type and treatment level on 1N NH4OAc extractable iron concentrations from chromium-treated soils under greenhouse condi- tions............................................ 122 Effects of soil type and treatment level on 0.005! DTPA extractable iron concentrations from chromium- treated soils under greenhouse conditions........ 122 Effects of soil type and treatment level on 0.1§ HCl extractable iron concentrations from chromium- treated soils under greenhouse conditions........ 122 XV Figure 1. LIST OF FIGURES The effect of zinc treatment on dry matter yield of corn I as influenced by soil type ...... The effect of zinc treatment on dry matter yield of field beans as influenced by soil type....... The effect of zinc treatment on dry matter yield of tomatoes as influenced by soil type.. ........ The effect of zinc treatment on dry matter yield of corn II as influenced by soil type........... The effect of chromium treatment on dry matter yield of corn I as influenced by soil type...... The effect of chromium treatment on dry matter yield of field beans as influenced by soil type. The effect of chromium treatment on dry matter yield of tomatoes as influenced by soil type.... The effect of chromium treatment on dry matter yield of corn II as influenced by soil type..... xvi Page 35 36 37 38 51 52 S3 54 INTRODUCT ION Many soils in the state of Michigan are of marginal ag- ricultural value because of a low organic matter content coupled with a low water holding capacity. The necessity of costly irrigation equipment and water procurement often makes the farming of these marginal lands economically unsound. In many of these same areas disposal of municipal waste materials, par- ticularly from sewage sources, is a large and serious problem. Federal laws prohibit the discharge of untreated wastes into streams and rivers. The quantity of water involved is usually large and often contains undesirable substances such as soluble and chelated heavy metals which have passed through treatment facilities. A highly organic material referred to as sludge remains in the treatment facility as filter cake or lagoon sediment and also must be disposed of. The idea of solving both the agricultural and the waste disposal problems at the same time through the application of municipal waste effluents to these marginal lands (and good agricultural soils in some instances) is only recently gaining in popularity in this country even though it has been practiced in some European countries for many years. The particulate matter would help buildup the soil organic matter level while supplying some nutrients and the effluent would supply the water needed for adequate plant growth as well as supply solu- ble nutrients. But what about the undesirable substances such as heavy metals present in both the sludge and the effluent? This study was initiated to elucidate the separate effects of two of these heavy metals, Zn and Cr, on plant growth and concentration and uptake of selected metals by corn, field beans and tomatoes as influenced by soils of varying texture, chemical composition and organic matter content. The inactiva- tion of Zn and Cr by these soils as measured by plant growth response and ease of soil-metal extraction with selected ex- tracting agents was studied. Also the leaching potential of high application rates was examined. LITERATURE REVIEW Effluent Sources of Zinc and Chromium Hodgson (1963) presents the following chart describing the normal fate of micronutrients in soils: PRIMARY MINERAL WEATH RING PLANT UPTAKE COMPLEX WITH IN- thi £{///’2780LUBLE ORGANIC \/ _, MATTER M++¢aMCh (EFFLUENT)- - - -> FREE ION -- -- -— -)(LEACHING) IN SOLUTION COMPLEX ,\ * OCCLUSION IN \ DEVELOPING PRECI- PITATES ,}7 INCORPORATION SURFACE INTO MICROBIAL ADSORPTION TISSUE \/ OXIDATION REDUCTION SOLID STATE DIFFUSION INTO SOIL MINERALS PRECIPITATES OF OXIDES OR PHOSPHATES OF Fe or Mn This balanced system may be drastically changed by the addition of two more components; an input of sewage effluent and a leaching component. The effluent input component will vary greatly with the amount of effluent applied and the load of micronutrients it carries. Ellis, Erickson, Knezek and Wolcott (1972) state that the average effluent concentrations for Detroit, Michigan for Cr and Zn were estimated to be 0.14 and 0.44 ppm, respec- tively. For a 35 week spray year at two inches per week this amounts to 2.22 pounds of Cr and 6.96 pounds of Zn added per acre per year and would result in an increase when compared to the naturally occurring Cr and Zn of 1.1 percent and 7.0 percent, respectively. The actual amount of these added metals which would be removed by plants would be 0.06 percent for Cr and 1.46 percent for Zn which essentially means that for these metals the soil is becoming a sink and eventually the leaching component added to Hodgson's balance chart may become important. In a California study Young, Young and Hlavka (1973) found that the concentrations for Cr and Zn in six urban effluents was 0.06 to 0.86 and 0.18 to 2.4 ppm, respectively. Eighty- five percent of the Cr and 90 percent of the Zn was associated with the organic particulate matter in these effluents. In another California study, Pound and Crites (1973) were only able to find 0-7 ppb and 0-200 ppb Cr and Zn concentrations in several effluents they studied. Blakeslee (1973) sampled 58 Michigan wastewater treatment effluents and found ranges for Cr and Zn to be <.01 to 1.46 ppm and 0.03 to 4.7 ppm, respectively, with medians of 0.025 ppm and 0.19 ppm, re- spectively. The U.S. Army Corps of Engineers (1972) reports effluent averages for both Cr and Zn to be 0.2 ppm. Bruland, Bertine, Koide and Goldberg (1974) measured the amounts of various metals being deposited in waters along the Southern California coastal zone and separated them into natural (erosion) and anthropogenic (municipal and industrial waste disposal) sources. They found 5.2 ug/cmZ/yr from natural and about half this amount from anthropogenic sources for both Cr and Zn. On a yearly basis this amounted to 350 metric tons of Cr and 250 metric tons of Zn being deposited over a 12,000 km2 area. Henry, Moldenhauer, Engelbert and Truog (1954) found sewage effluent to be useful and beneficial when used for irri- gating crops. However, effluents vary greatly in their suit- ability to de disposed of on land. Ellis et al. (1972) de- scribed the Detroit effluent mentioned earlier with regards to Cr and Zn as being suitable for irrigation. The U.S. Public Health Service (1965) on the other hand described the Grand Rapids, Michigan effluent as having an average of 2.5 ppm Cr and 0.8 ppm Zn. These figures along with the fact that the amount of Cu and Ni in the Grand Rapids effluent is ten times higher than that of Detroit makes the Grand Rapids effluent unsuitable for land disposal. The equilibrium pH of land receiving large amounts of effluent would be expected to approach but remain slightly below the pH of the effluent. The U.S. Army Corps of Engineers (1972) found the average effluent pH to be 7.0. Kardos and Sopper (1973) found the average pH of the effluent they stud- ied to be 7.6 over eight years and actually found (unpublished) the soil pH over this period to approach neutrality. Bouwer (1973) found in an Arizona study that, although the effluent pH was 7.7 to 8.1, the groundwater pH was 6.9 to 7.2 due to production of CO2 and organic acids. Several large effluent disposal projects are being planned or are already in operation. The Detroit wastewater disposal system studied by Ellis et al. (1972) is still in the planning stages. Several large systems are already in operation, two of them being the Muskegon County, Michigan system (Ag. Econ. Dept., MSU, 1970; Bauer and Matsche, 1973) consisting of 10,000 total acres with 6,000 being irrigated, and the Chicago Metropolitan region (Bauer and Matsche, 1973) involving over 700 square miles of actual irrigation area. The undertaking of these projects as well as the numerous small spray effluent disposal systems underscores the need for research in soil-waste metal relationships. Zinc in Soils Randhawa and Broadbent (1965A) found that retention of Zn by pure compounds was determined primarily by the pH of the solution. The critical pH was determined by the acidity, type of exchange site, and the nature of the cation. The I problem of working with pure systems and then extrapolating to soils was demonstrated by Lagerwerff and Brower (1973) who found a 100 to ZOO-fold difference in the solubility of lead at pH 7 when they went from a solution system to a soil system. Still, pH is one of the most useful indices relating to the availability of Zn in soils (Peech, 1947; Ellis and Knezek, 1972; DeMumbrum and Jackson, 1957; and Lindsay, 1972). Truog (1946) pointed out that Zn deficiencies sometimes occur under calcareous conditions and Lindsay (1972) has shown that the solubility of Zn increases a hundred—fold for each unit decrease in pH. Using equilibrium data he calculates that 2 in solution is approximately 10 at pH 5 the concentration of Zn+ 4 10- M (6.5 ppm) and at pH 8 it is 10- M (.007 ppb). The actual compounds controlling Zn solubility in soil systems are still unknown. Lindsay and Norvell (1969B) pos— tulated the presence of ZnSiO3 as the controlling factor but upon recalculating thermodynamic equilibrium data decided ZnSiO3 was too soluble (Norvell and Lindsay, 1970). Fried and Broeshart (1967) state that Zn precipitates at higher pH's as the carbonate and hydroxide. Krauskoph (1972) states that in basic solutions, if the concentration of Zn+2 is 4 greater than 10- M, Zn(OH)2 will precipitate. Minimum solu- bility of Zn(OH)2 occurs at pH 9.5, forming the zincate 2 anion, Zn(OH); , above this pH. Zn+2 can also precipitate as ZnCO3 (Smithsonite) and Zn(OH)ZSiZO7H20 (Hemimorphite). However, all the Zn compounds normally found in soils are sufficiently soluble so as not to be regarded as the con- trolling factor in Zn solubility. Udo, Bohn and Tucker (1970) found the solubility product for the Zn-soil complexes and 16 to 10-19. carbonates to range from 10- In clay systems Elgabaly (1950) found that in minerals with Al in the octahedral arrangement, Zn was thought to be fixed in the holes not occupied by Al ions, thus causing a decrease in the cation exchange capacity and an increase in the anion exchange capacity of these minerals. With Mg in the octahedral position there was no reduction in cation ex- change capacity because Zn substituted for the Mg instead of adding to it. In a clay system fixation of Zn was di- rectly related to pH and amount of Zn added (Reddy and Perkins, 1974). Kaolinite fixed relatively little compared to bentonite or illite and this fixation was accentuated by repeatedly wetting and drying. This fixed Zn was found by Elgabaly, Jenny and Overstreet (1943) to be available for uptake by barley roots. Reddy and Perkins (1974) concluded after an examination of X-ray and DTA data that the Zn was fixed as a result of precipitation, physical entrapment, and/or strongly adsorbed at the exchange sites rather than penetrating the crystal lattice structure. Cation exchange capacity values were in- versely related to the amount of Zn fixation. However, using infrared spectrosc0py, DeMumbrum and Jackson (1956B) showed that with Cu and Zn saturation the 2.8 micron hydroxyl ad- sorption intensity showed a decrease indicating these metals reacted with the octahedral OH in the layer silicates. McBride and Mortland (1974) have found that Cu fixation in the hexagonal cavities of montmorillonite did occur when the system was dehydrated and that 50 percent or more of this fixation was irreversible when the dehydration took place at temperatures over 150°C. Fixation in this manner lowered the layer charge. Nelson and Melsted (1955) found that in a Ca-soil system added Zn became increasingly fixed over time but that this fixation did not reduce the cation exchange capacity. They also studied a H-soil system and concluded that nothing but a normal cation exchange took place. The acid soluble Zn did not occupy exchange positions of the soils and clays used in their study. Misra and Tiwari (1966) and Udo et al. (1970) did obtain adsorption maxima for Zn which exceeded the C.E.C.'s of the calcareous soils they were working with and attributed this partly to the formation of the basic carbonate in the presence of soluble and insoluble carbonates. Misra and Tiwari (1966) also proposed the possibility of the hy- drolysis of divalent Zn ions into monovalent hydroxylated Zn ions (Zn0H+). Bingham, Page and Sims (1964) examined the effect of various anions on the solubility of Zn in clay systems and found that when the pH was below 5.5-6.5, the retention of Zn was the same for C1-, N0; and so: salts and equal to the cation exchange capacity. Excess retention at higher pH was explained as precipitation of Zn(OH)2. Keefer, Singh, Horvath and Henderlong (1972) found that 58 percent of the Zn applied as ZnEDTA to the soil was bound to the clay frac- tion after two croppings of corn while only 38 percent of the Zn applied as ZnSO4 was located on the clay fraction. The mechanisms by which soil organic matter forms com- plexes with metals was placed in three categories by Mortensen (1963); ion-exchange, surface adsorption, and chelation-reaction 10 mechanisms. Carboxyl, hydroxyl, and amide groups are probably involved as well as complex coagulation and peptization re- actions which take place between organic matter and insoluble minerals. Wallace (1963) lists two important reactions between organic chelating agents and nutrients. One removes nutrients from solution while the other maintains the nutrients in an available form. From titration data Beckwith (1959) and Khanna and Stevenson (1962) concluded that metals of the first transition series of the periodic table formed complexes with organic matter, the stability of which followed the Irving- Williams series. Irving and Williams (1948) stated that, regardless of the method or nature of the complexing agent, stability of organo-divalent metal complexes follows the order; Pb>Cu>Ni>Co>Zn>Cd>Fe>Mn>Mg. Himes and Barber (1957) found that soil organic matter reacted with divalent metal ions in a manner similar to chelation reactions. Upon removal of the organic matter by oxidation the ability of the soil to chelate was destroyed. When they removed the hydrous silicates with hydrofluoric acid and left the organic fraction intact they did not influence the reaction of Zn by the soil. Car- boxyl groups did not appear to be important. Hodgson, Lindsay and Trierweiler (1966) found that 60 percent of the Zn in some Colorado calcareous soils was in a complexed form and this complexation correlated with the soluble organic matter. Geering and Hodgson (1969) separated this soluble organic fraction into two parts; a non-dialyzable fraction of soil solution ligands, and a dialyzable fraction made-up primarily 11 of aliphatic and amino acids. The ratio of non-dialyzable to dialyzable as 1/40, but the non-dialyzable fraction was more effective in complexing Zn. Randhawa and Broadbent (19658) found that species of Zn complexed by the humic acid fraction vary with pH. At pH 7.0, 70 percent of the Zn retained was in the divalent species; whereas, at pH 3.6, 75 percent of the Zn was monovalent. Total Zn retained in- creased with increasing pH up to pH 8.5, then declined at higher values. Randhawa and Broadbent (1965A) found that on the humic acid complexes Zn was more stable than Ca but less than Cu and Fe+2 and this stability is different than the Irving-Williams series. These complexes were of three dis- tinct types. Zn desorbed from the humic acids by 0.01N_acetic acid could be attributed to phenolic sites of low to medium acidity and to carboxyls of pKa 2.8-4.4. Zn desorbed by 0.01M HNO is that retained by strong acid carboxyl groups of pKa 3 less than 2.0. The third type of site, usually less than one percent of the total cation exchange capacity, is that from which Zn was desorbed by 0.lN_and lllHNo3 and may be important as a reserve source of Zn for the plant. Schnitzer and Skinner (1966) looked at the fulvic acid fraction and separated the reaction into two distinct areas; a major one where both acidic carboxyls and phenolic hydroxyls participated simultaneously, and a minor one which involved only acidic carboxyls. Cu was more stable than Fe which was more stable than Zn, and again these do not follow the Irving- Williams series. Zn was found to form more but weaker bonds. 12 Warncke and Barber (1973) found that there was a greater buffering effect of the solid phase on the Zn in solution as the cation exchange capacity and the organic matter increased. Similar results were found by Martens, Chesters and Peterson (1966) where an increase in organic matter content at con- stant clay levels increased the amount of Zn bound by the organo-clay complex thereby increasing the 0.1g HCl extractable Zn. DeMumbrum and Jackson (1956A, 1956B) foundani increment of exchange capacity in both peat and montmorillonite that is specific for cations such as Zn and Cu in acid or neutral solutions. Infrared studies with peat indicated numerous shifts in the double bond regions of the spectrum which are indicative of chelation with C=0 and N=0 groups or alcoholic hydroxyls. However, McBride and Mortland (1974) were unable to show any specific adsorption sites for Cu that would not also be available for any other similar sized cations under dehydrated conditions. Time is an important factor when considering availability of Zn in the soil because metals slowly revert to chemical forms of lower solubility (Chaney, 1973). Most researchers have used low levels of Zn when studying fixation, usually be- low one symmetry. Sharpless, wallihan and Peterson (1969) using 1/4 and 1/8 symmetries found that 75 percent of the Zn applied as ZnSO4 was found on the exchange sites after one minute. Subsequently there was a gradual shift from ex- changeable Zn to acid extractable Zn. Boawn, Viets, Crawford 13 and Nelson (1960) applied 4.5 kg per ha of Zn at the be- ginning of a six year study. There was a rapid decline in 0.15 HCl extractable Zn during the first year and by the end of four years the added Zn was barely detectable over the background. Follet and Lindsay (1971) found that only 44 percent of the added Zn in an experiment was extractable with DTPA after 14 weeks. Jamison (1943) and Himes and Barber (1957) found that the prOportion of Zn adsorbed by or displaced from the soil decreases as the concentration of Zn added is increased. Also Jamison (1943) and Allen and Terman (1966) found that mixture with the soil and fineness of grind are more important than solubility when assessing availability of Zn in different carriers to plant uptake. Many interactions in the soil between Zn and other elements have been reported. Early reports of a Ca-Zn antag- onism were examined by wear (1956). He was able to show that the effects attributed to Ca were pH effects and that when the Ca carrier was changed from carbonate to sulphate no re- duction in Zn availability was recorded. Chaudhry and Loneragen (1972) examined Cu-Zn interactions and found that excess Cu strongly inhibited Zn absorption in wheat seedlings whereas Mn and Fe had no effect. Gilbey, Greathead and Cartrell (1970) found that in areas of Cu and Zn deficiencies, especially on coarse textured soils, appli- cation of Zn needs careful control. If Zn was applied in too large amounts, the Zn induced a Cu deficiency in both wheat and barley. 14 The Zn-P relationship has been extensively studied. Jackson, Hay and Moore (1967) reported that sweet corn grown on low-Zn medium contained high levels of P. Ambler and Brown (1969) obtained similar results with pea beans. Also, fertilizing with P reduced the Zn content of the plants. Ellis (1965) reported that heavy P applications often in- duced Zn deficiencies on pea beans, especially on fine tex- tured calcareous soils. Sharpless et al. (1969) studied 23 arid zone soils and found no significant relation between Zn retention by the soils and P content. The mechanism of the Zn-Fe antagonism was partly un- raveled by Chaney, Brown and Tiffin (1972) when they were 3 able to demonstrate an obligatory reduction of Fe+ chelates 2 to the Fe+ ion in order for root uptake by soybeans to occur. Zn prevented this reduction. Ambler et al. (1970) had earlier 3 to Fe+2. shown that Zn interferes with the reduction of Fe+ Lingle, Tiffin and Brown (1963) found that Zn was the strongest interfering ion that depressed Fe uptake. Rosell and Ulrich (1964) found that increasing the Zn concentration in solution from 0 to 200 ppb reduced the plant Fe concentration in sugar beets from 917.0 ppm to 48.0 ppm. A similar reduction was seen in the Mn concentration. Ambler and Brown (1969) and Watanabe, Lindsay and Olsen (1965) showed that under Zn de- ficiency regimes Fe uptake is increased, but that under low Fe regimes, Zn fertilization accentuated an Fe deficiency. In recent years the role of hydrous oxides in the ad- sorption of heavy metals has been receiving more attention. 15 Jenne (1968) proposed that hydrous oxides of Mn and Fe, in general, furnish the principal control on the fixation of Co, Ni, Cu, and Zn in soils and fresh water sediments, and since these oxides are nearly ubiquitous in clays, soils, and sediments as particle coatings they exert chemical ac- tivity far out of proportion to their total concentration. Stanton and Burger (1967) found that Zn adsorbed by hydrous Fe oxides through the medium of polyvalent phosphate aniOns is unavailable to plants. In the absence of phosphate ions only the more strongly—crystalline Fe oxides, such as goethite, fix Zn against plant uptake. Wilkinson (1972) found that in acid soils less replenishment of nutrient ions can be attri- buted directly to insoluble compounds than to ions adsorbed on Fe, Al or Mn oxides or hydroxides, or clay surfaces. Krauskopf (1972) states that while hydrated Fe+3 oxides carry a positive charge below pH values of 5 or 6, Mn-oxide sols carry a nega- tive charge. This is usually the explanation given for the large concentration of cations commonly found in psilomelane, a Mn oxide mineral, the cations having been adsorbed and later incorporated. Lagerwerff and Brower (1973) used the role of Al-polyhydroxides from alkaline corrosion of the soil matrix as a possible explanation for the lower solubility of Pb in neutral soils than in solution. When considering effluent disposal on land the rate of application and drainage conditions will determine the oxygen status of the soil. Bouwer and Chaney (1974) stress the im- portance of maintaining aerobic soil conditions to help 16 immobilize metals. Swaine and Mitchell (1960) found that under anaerobic conditions Zn was more easily extracted whereas Cr was not affected. Chromium in Soils Sauchelli (1969) states that the element Cr appears to be the next candidate for the elevation to an essential ele- ment, that is, having an essential function in the complex process of living organisms. Cr belongs to the first series of the transition elements and its position is surrounded by three elements with a known biological function; V, Mn and Mo (Mertz, 1969). Cr can occur in every one of the oxidation states from -2 to +6, but only the 0, +2, +3, and +6 oxidation states are very common (Cotton and Wilkinson, 1972). The divalent chromic ion is a strong reducing agent and its compounds are unlikely to occur in biological systems: Cr+3 + e = Cr+2 E0 = -o.41v The Cr+6 species is always linked to 02, either as chromate (Crozz) or dichromate (Cr20;2). Under acid conditions the dichromate solutions are strong oxidants: 2 3 - + _ + _ Cr207 + 14 H + 6e - 2 Cr + 7 H20 Eo - 1.33V The chromate ion in basic solution is much less oxidizing: -2 _ - _ - Cr207 + 4 H20 + 3e - Cr(OH)3 + 5 OH Eo - 0.13V However, under anaerobic conditions, such as an anaerobic digester in sewage treatment, the chromate acts as a source of electrons and is quickly reduced to the +3 species (U.S. 17 Public Health Service, 1965). Mertz (1969) has pointed out that under agricultural conditions the main Cr species will normally be Cr+3. Research work on soil Cr reactions is very limited (Allaway, 1968 and Mertz, 1969). Pratt (1966) and Berrow and webber (1972) reported that Cr occurs naturally in most soils ranging from 5 to 1,000 ppm and averages about 100 ppm. On some soils, however, notably those derived from serpentine rock, levels of Cr as high as 4 percent have been recorded by Soane and Saunder (1959). Cr in the +6 oxidation state added to soils would be gradually reduced to the +3 state (Mertz, 1969). Only under alkaline oxidizing conditions could the +6 oxidation state exist in nature for any length of time (Allaway, 1968). Argaman and Weddle (1973) reported the solubility product of Cr(OH)3 to be 1 X 10"30 7 X 10-31. Also, Mallory (1968) lumped Cr with elements whose and Murrmann and Koutz (1972) give it as sulfides or hydroxides are precipitated from neutral or slightly ammoniacal solution. Maximum recovery was at pH 8. Soane and Saunder (1959) were able to grow oats, corn and grass on soils containing up to 4 percent Cr by adding 12 tons of CaCO3 per acre. This raised the pH from 6.1 to 8.2. Lindsay (1973) describes the normal effluent Cr as being oxidized or reduced to the Cr+3 state and then precipitating as the hydroxide. In a charged clay system soluble Cr would be expected to participate in base exchange reactions. Gieseking and Jenny (1936) attribute positions in the adsorption and release 18 series to electric charge and size of the ion and that higher charge means less mobility. Therefore, Cr+3 would be expected to be very immobile in the soil. Cotton and Wilkinson (1972) and Mertz (1969) list Cr second only to Co in the slow rate of ligand exchange and surpassed only by Zr+4 in the tendency of its aquo complexes to hydrolyze, olate, and precipitate. This indicates that the Cr bound or chelated by organic matter would be very stable and probably not available for plant up- take. Beckwith (1959) and Khanna and Stevenson (1962) con- cluded from titration data that metals of the first transition series in the periodic table formed complexes with organic matter. Pavel (1959) found this to be true for Cr. He re- ported fulvic acids to form four types of chelates with Cr. However, Cropper (1969) found that of the two soils he was working with, the one with the more organic matter showed the greater Cr toxicity to plants at all levels of Cr applied. Leep (1974) found that organic matter binds Cr very strongly. With a 350 ppm Cr treatment to a Houghton muck only 2.3 ppm was extractable with O.lN_ HCl. The Cr treatment increased the extractable Mn and decreased the extractable Fe, indi- cating a displacement of Mn from the organic matter and the possible formation of a Cr-Fe complex. Murrmann and Koutz (1972) list both Zn and Cr as elements which form coprecipi- tates with Fe and Al hydroxides. The possibility of Cr adsorption on the surface of hydrous oxides of Mn, Fe, and A1 as suggested by Stanton and 19 Burger (1967) and Jenne (1968) for divalent heavy metals should also be considered. Plant-Zinc Relations Moore (1972) reviewed the mechanisms for micronutrient uptake by plants and pointed out that both cation and anion absorption are affected by pH. Hydrogen ion sharply reduces cation absorption at pH values below 5 while maximum absorption occurs between pH 5-7. If the nutrient remains available ab- sorption remains at this rate up to pH lO-ll. Absorption of cations may occur as an exchange for metabolically generated H+. According to Jacobson, Hannapel and Moore (1958) there are two types of nutrient uptake, metabolic or energy re- quiring and non-metabolic. Metabolic uptake is characterized by constant uptake at variable ambient concentrations, usually against a gradient, while non-metabolic uptake increases as ambient concentration increases. Jenny (1966) found root surfaces covered with a mucigel which appears negatively charged, perhaps as a consequence of dissociated carboxyl groups. This mucigel has cation ex- change properties as evidenced in the light microscope by staining with methylene blue cations and destaining with CaClz. Depending on the ions in high concentration the properties of the mucigel change. For instance, when the mucigel was swollen by Na saturation anions were excluded. This exclusion is caused by a swelling shut of macrointerstices in the mucigel which corresponds to free space. 20 Bowen (1969), after studying absorption of Zn by sugar- cane, concluded that Zn uptake was coupled with oxidative phosphorylation since uptake was nearly stopped by using dinitrophenol (DNP). Findenegg and Broda (1965) using ex- cised barley roots and 65Zn, came to the opposite conclusion. They found that accumulation of Zn from a nutrient solution was not metabolically active since there was a quick equili- brium, DNP had no effect, killing the roots or grinding the tissue increased rather than decreased uptake, and the pre- sence of competitive metal ions reduced uptake. Findenegg and Broda (1965), Broda (1965), and Schmid, Haag and Epstein (1965), studying Zn uptake by both barley roots and chlorella, came to the same conclusion. Several authors have pointed out that both mechanisms are at work for many elements, a metabolic component at low ambient concentrations and a passive system at high ambient concentrations (Bange and Overstreet, 1960; Maas, 1969; and Laties, 1969). Polson and Adams (1970) found Zn concentrations in roots and leaves of two navy bean varieties to be relatively constant at 0.005 and 0.05 ppm ambient Zn concentrations in nutrient solutions but increased seven-fold in leaf tissue and over ten-fold in roots at an ambient Zn concentration of 5.0 ppm. The 5.0 ppm ambient Zn concentration was toxic to the Sanilac variety but did not affect the Saginaw variety. Rosell and Ulrich (1964) found that sugar beets took up increasing amounts of Zn from solution as the ambient concentration increased, in- dicating passive uptake. Leep and Knezek (1973) found a 21 similar result with corn. Brouwer (1965) pointed out that at relatively high salt concentrations ion movement to the shoot is related to H20 movement, but this fact alone is in- sufficient to prove that passive transport is involved. The role of chelating agents in mobilizing soil nutrients and making them more available for plant uptake was demonstrated by Elgawhary, Lindsay and Kemper (1970). Using simulated roots they found that by passing various complexing substances through the roots Zn transport to the roots was increased. The effectiveness of these agents was as follows; EDTA>HCl>citric acid>amino acid mixture>glucose. 3 The use of 10- M; EDTA increased l7-fold over H 0 the influx 2 of Zn into the root. This study demonstrated how complexing agents or acids from root exudates or from decomposing organic matter residue in soils may increase transport and availability of insoluble nutrients. Muir, Logan and Brown (1964) working with mobilization of Fe with pine needle extracts, and Hiatt and Lowe (1967), working with exudates of barley roots, have shown this to be true. The need for Zn and the response to excessive applica- tions of Zn vary from plant to plant. The normal plant Zn concentration ranges from 1 ppm for grass and 2.5 to 100 ppm for corn to 112 ppm for alfalfa (Sauchelli, 1969 and Chapman, 1967). Normal field bean concentration is 15 to 20 ppm Zn (Lessman, 1967) and the range of Zn found in tomato plants varies from 15 to 198 ppm, probably depending on what plant parts were sampled (Gauch, 1972 and Geraldson, Klacan and 22 Lorenz, 1973). Toxic levels of Zn in various plants are 150 to 200 ppm for corn (Sauchelli, 1969 and Chapman, 1967), 526 to 1,489 ppm for tomato (Gauch, 1972), and 50 ppm for field bean (Judy, 1967). The effect of pH on Zn uptake is related to the effect pH has on Zn solubility (Wear, 1956). Lee and Page (1967) were able to overcome toxic levels of Zn in old peach orchard soils by liming to a pH of 7. Lee and Craddock (1969) found that by adding coarsely ground snap corn meal along with a lime application a more complete control of Zn toxicity was accomplished. Of the numerous interactions between Zn and other ele- ments, probably the most important are between Zn and Fe, and Zn and P. Chaney et a1. (1972) demonstrated that the Zn-Fe antagonism is located at the root surface where Zn prevents the obligatory reduction of the ferric ion to the ferrous ion which is the form absorbed by the plant. Under low Zn regimes plant Fe increases and under high Zn regimes plant Fe is reduced (Ambler and Brown, 1969; Watanabe et al., 1965; Leep, 1974; and Warnock, 1970). Rosell and Ulrich (1964) ob- tained a dramatic decrease in Fe and Mn concentration in sugar beets with increased Zn levels. The nature of the Zn-P interaction has not been so clearly spelled out, but Ellis (1965), Jackson et al. (1967) and Ambler and Brown (1969) all demonstrated that low Zn plants contained high levels of P and that heavy P fertiliza- tion sometimes caused Zn deficiency symptoms to appear. 23 Stanton and Burger (1967) have shown that with the presence of phosphate anions in the soil Zn is adsorbed by hydrous Fe oxides through the medium of polyvalent phosphate ions and this Zn is not available for plant uptake. Labanauskas et al. (1972) have demonstrated that under a low root oxygen regime Zn decreased in the tops and in- creased in the roots of citrus seedlings. Plant-Chromium Relations More work has been done with plant responses to low and high levels of both indigenous and applied Cr than has been done with soil reactions. Bertrand and deWolf (1968) obtained a 42 percent increase in potato yields when Cr was applied at the rate of 40.6 grams/ha. Arnon (1937) caused a growth increase in barley that had NH: as the N source by adding 0.05 ppm Cr to the solution culture. This increase did not occur when N0; was the N source. Pratt (1966), Allaway (1968) and Mertz (1969), in their reviews of Cr, have listed several published reports on enhanced growth, yield, sugar content, or enzyme activity increases on widely varying crops as the result of low applications of chromium, both as soil fertilizers and foliar sprays. Mertz (1969) sites the extensive work of Dobrolyubskii in Russia where both soil and vine applications of chromic sulfate increased the weight of grapes by 21 percent, the size and sugar con- tent by 18 percent and 23 percent, respectively, and total yield from 205 to 245 kg/ha. The mechanism of increase in 24 sugar content as the result of Cr additions may be to that found in animal systems by Schroeder (1967). He found that a deficiency of Cr influences glucose and lipid metabolism and affects atherosclerosis. Leep (1974) found a significant increase over controls in corn dry-weight yields with Cr applications up to and including 350 ppm on an organic soil. The Cr additions increased the availability of Mn to the plant which was listed as the probable cause for increased growth. No Cr uptake into the plants was detected. While studying Mo nutrition of lettuce Warrington (1946) found that Cr produced a similar response and concluded that Cr substituted for Mo. Schroeder, Balassa and Tipton (1962) found that fresh tomatoes generally contain 0.01 ppm Cr, navy beans had 0.08 ppm Cr, and sweet corn had 0.02 ppm Cr. The highest Cr levels were found in spices, with thyme containing 10.0 ppm and black pepper averaging 3.7 ppm. Cr toxicity is widespread, especially on ultra basic and serpentine soils (Pratt, 1966 and Allaway, 1968). Soane and Saunder (1959) using KZCrO4 in sand culture, found that corn did not readily take up Cr even though levels in the ambient solution were toxic to the plant. Allaway (1968) found plants suffering from induced Cr toxicity frequently are found to contain about the same concentrations of Cr in the tOps as are found in unaffected plants. Leep (1974), growing corn on an organic soil, found no uptake of Cr at levels studied, the highest being 2 meq per 100 g of soil. 25 On the other hand, Cropper (1969) found that a silt loam produced more severe Cr toxicities than a loamy sand even though the loamy sand had a lower organic matter content. Haas and Brusca (1961), vergnano (1959), Spence and Millar (1963), Hewitt (1953), Walker and Grover (1957), DeKock (1956), Cannon (1960) and Hunter and Vergnano (1953) have all shown toxicity to plants associated with high levels of Cr. Causes of Cr toxicity have been examined by numerous authors. Turner and Rust (1971) found that rates of 0.5 ppm 6 in solution culture decreased concentration and of Cr+ total uptake of Ca, P, K, Fe, and Mn in soybean tops and K, Mg, P, Fe and Mn in soybean roots. Similar effects were observed on a loam soil at the 5 ppm Cr+6 level. Spence and Millar (1963), Vergnano (1959), Soane and Saunder (1959) and Cropper (1969) associated Cr levels with reduced P uptake and a possible P—Cr interaction. Visual symptoms of Cr toxicity included purpling of the basal tissues. Cannon (1960), Hewitt (1953), DeKock (1956) and CrOpper (1969) associated a Cr toxicity with reduced uptake of Fe, indicating a Fe-Cr interaction, possibly similar to that of Zn-Fe. In attempting to isolate a carrier for Cr in tomato xylem, Tiffin (1972) was unable to make a carrier analysis due to low amounts of Cr recovered in the exudate. Lyon, Peterson and BrOoks (1969) using 51Cr+6 from NaZCrO4 isolated trioxalochromate III ion along with two other anions in leaf tissue of the Manuka tea plant (a Cr accumulator), but could 26 51 only find Cr0: in the xylem sap. They likened Cr transport to that of S and P which are transported as inorganic ions. Soil Analysis for Zinc and Chromium Viets and Boawn (1965) describe ammonium acetate (NH OAc) 4 extractable and water soluble Zn as the two types of Zn re- garded as readily available to plants. However, since both of these methods extract extremely low quantities of Zn they recommend a complexing agent such as EDTA or dithizone and CCl to increase extractability of the Zn with NH OAc. Brown 4 4 (1950) used 0.02N H2804 and 5N acetic acid to reduce the pH and extract much of the precipitated Zn not extractable with neutral salts. Brown, Quick and Eddings (1971) made a study of 1N_NH4OAc and 0.1N'HC1 extractable Zn and concluded that plants saw both types. More and more work is being done with chelates, especially DTPA, as an indices of what is available to the plant (Dolar et al., 1971; Lopez and Graham, 1970; Lindsay and Norvell, 1969A; Norvell, 1972; Viets and Lindsay, 1973; and Brown et al., 1971). The DTPA method calls for using 0.01NCaC12 to insure constant ionic strength and 0.1N. triethanolamine as a buffer at pH 7.30. Perkins (1970) has proposed a 0.075N acid mixture of 0.05N_HC1 and 0.025NHZSO4 as a means of evaluating Zn status of coastal plain soils. Pratt (1965) described the traditional way of doing total Zn analysis by the HNO3, HC104, and HF acids method. Bertrand and deWolf (1968) used a pH 7 acetate extrac- tion for available Cr. Leep (1974) used lN’NH4OAc, 0.005 DTPA 27 and 0.1N7HC1 extractable Cr to try and characterize pools of Cr available for plant uptake. He was unable to extract any Cr with the NH4OAc or DTPA extractants. Very little work has been done on correlating Cr extraction techniques with Cr uptake by plants. MATERIALS AND METHODS In order to examine the effects of high levels of Zn and Cr on plants and how these effects are modified by soil properties, a greenhouse study was conducted using increasing Zn and Cr treatment levels on three plant types grown on four different surface soils. The soils selected were from Muskegon County, Michigan and are all being currently used for effluent waste disposal. These four soils have developed from the same parent material but under different drainage con- ditions and consequently different vegetative cover. Charac- terizations of these soils are presented in Tables 1 and 2. The Rubicon sand is very well drained, the AuGres sand is somewhat poorly drained, the Roscommon sand is poorly drained, and the Granby loamy sand is very poorly drained. The experimental soils were selected from areas as homogeneous as possible and prior to any applications of wastewater. The soils were air dried, passed through an approximately 2mm plastic colander to remove roots and other foreign objects, and stored in thirty gallon plastic con- tainers until needed. Soil texture and particle size distri- bution were determined by the hydrometer method described by Day (1965). Cation-exchange capacities (C.E.C.'s) were de- termined by the "displacement and distillation for adsorbed 28 29 Table 1. Characterization of the soils collected for study from Muskegon, Michigan. Soil Series AuGres Roscommon Rubicon Granby Texture Sand Sand Sand Loamy Sand 7th Approx. Entic Mollic Entic Typic Name Haplaquod Psammaquent Haplorthod Haplaquoll pH 7 5.2 5.2 4.9 6.2 Lime Index 6.1 6.1 6.2 6.2 C.E.C. 4.4 7.9 3.9 19.5 % Sand 92.3 87.4 90.0 81.5 % Silt 5.1 9.7 6.3 12.6 % Clay 2.6 2.9 3.7 5.9 % O.M. 1.9 4.4 4.4 8.9 Depth Sampled Inches 0-6 0-6 0—3 0-12 Table 2. Total content of Cr, Zn, Mn, Fe and Cu in the ex- perimental soils as determined on perchloric acid- hydrofluoric acid digested non-treated samplesa. Metals -------------------- Soils ---------------------- AuGres Roscommon Rubicon Granby loamy Sand Sand Sand Sand --------------------- ppm-—---——-------———--———— Chromium 5.4 10.7 6.5 13.0 Zinc 19.6 24.2 31.0 37.8 Manganese 40.9 80.2 132.1 87.5 Iron 1146.0 7389.6 3284.7 6405.7 Copper 48.8 45.6 23.3 34.9 aEach value is the average of 30 determinations. 30 ammonium” method described by Chapman (1965). The percentage of organic matter was determined by dry-ashing according to the method described by Mitchell (1932). This method uti- lizes temperatures of 350°C to 400°C for six to eight hours and is acceptable in this instance since these are acid soils and have few, if any, carbonates present to induce error. The pH and lime index as well as fertilizer needs were de- termined by the Michigan State University soil testing labora- tory. Four kilograms (kg) of soil per plastic lined pot were used for AuGres and Roscommon sands while only 3.6 kg were used.for Granby loamy sand and 3.2 kg for Rubicon sand. The organic matter present in the Rubicon sand was predominantly forest floor litter and as such had a low bulk density. In contrast the organic matter of the other three soils was very fine and humified. The treatment levels for Zn were 0, 50, 100, 150, 200 2 and 400 parts per million (Ppm) Zn+ applied as ZnCl2 and 3 for Cr were 0, 50, 100, 200 and 400 ppm Cr+ applied as the CrC13. These treatments were applied as liquids mixed with a liquid N-P-K fertilizer solution at the rate recommended by the M.S.U. soil testing laboratory and enough water necessary to bring the soil to field capacity, usually 400 m1. This solution and the soil were thoroughly mixed in a large plastic container and then returned to the pots to equilibrate three weeks before planting. 31 A lime treatment equivalent to five tons per acre was mixed with each pot prior to adding the treatments. The weight of each pot was recorded after the application of the treatments in order to facilitate watering to field capacity by weight in the future. Each treatment was replicated three times. Two crops were grown during the same period in separate pots. A second cropping followed. The first crops were corn (Zea mays var. 380) and field beans (Phaseolus vulgaris var. Sanilac). The pots were thinned to three plants in the corn pots and four plants in the bean pots. Watering was done with distilled water. Harvesting was done after six weeks and both fresh and dry weights recorded. The pots were allowed to dry out, as many roots as possible removed, and then refertilized with N, P and K. In addition, 10 ppm Mn were added to the Granby loamy sand to correct a slight nu- tritional deficiency which had appeared on the field beans. The Zn and Cr treatments were not repeated. The same variety of corn followed the previous corn crop while transplant tomatoes (Lycopersicon esculentum Mill. var. Glamor) followed the field beans. The tomatoes were harvested after six weeks in the pots and the corn after seven weeks. There was one plant in the tomato pots and four plants in the corn pots. After harvest both fresh and dry weights were recorded. Soil samples were taken from each pot prior to the first cropping and again prior to the second cropping. Plant samples were ground in a Wiley stainless steel mill. 32 Two-tenths gram subsamples were digested in high pressure, low temperature nitric-perchloric acid mixture by a procedure described by Adrian (1973). Analysis was made on these sam- ples for Zn, Cr, Mn, Fe and Cu on a Perkin-Elmer model 303 atomic absorption spectrophotometer (Issac and Kerber, 1971) . Four separate extractions were made on the soil samples to determine relative immobilization or release of the same elements analyzed for in the plant tissue. Water, 1N neutral ammonium acetate (NH4OAc), 0.005N diethylenetriaminepentaacetic acid (DTPA) and 0.1N hydrochloric acid (HCl) were the extracting agents used. The amount of each element removed by these ex- tracting agents should reflect the leaching component, easily exchangeable component, the organically bound component and the more tightly bound and precipitated components, respec— tively. For all extractions a uniform shaking time of two hours in a reciprocal Shaker at 200 rpm was used. Five grams of soil to 50 ml of solution was used for H 0, NH OAc and 2 4 HCl extractions. Ten grams of soil to 20 ml solution was used for the DTPA extractions. The soil solutions were cen- trifuged and the supernatant analyzed as above. The pH's were measured on all soil samples using a 1:1 soil to distilled water ratio. An analysis for total metal content for the soils studied with respect to Zn, Cr, Mn, Fe and Cu was made using the HC104-HNO3-HF procedure for total soil analysis as out- lined by Pratt (1965) (Table 2). 33 Statistical analysis procedures consisted of an analysis of variance appropriate for a completely randomized block de- sign. The analysis was conducted by the Michigan State Uni- versity computer center. Three separate LSD's were computed for the bulk of the data. First, a treatment within soil LSD was computed to examine differences on individual soils. Second, a soil within treatment LSD was computed to examine how different soils react to the same treatment. Third, a treatment among soils LSD was calculated to look at the soil X treatment interaction. RESULTS AND DISCUSSION Plant Response to Soil-Zinc Additions The effects of added Zn on plant growth are determined primarily by treatment level, soil type, and to a lesser ex- tent by the species of plant under investigation (Figures 1- 4). The highest levels of Zn applied were 200 and 400 ppm and these rates resulted in significant decreases in dry weight of all crops grown on the AuGres sand. This soil has only 1.9% organic matter, 2.6% clay and a C.E.C. of 4.4 meq per 100 g of soil (Table 1). The toxic effects of Zn should be reduced on soils with more organic matter, clay and C.E.C. Indeed this was the case for Roscommon sand and Granby loamy sand which had 4.4% and 8.9% organic matter, 2.9% and 5.9% clay, and 7.9 meq/100 9 soil and 19.5 meq/100 9 soil C.E.C., respectively. It appears from the growth and Zn uptake data (Appendix Tables 1-4) that the untreated Granby loamy sand had insufficient Zn available for maximum plant growth. In contrast, the Rubicon sand has 4.4% organic matter, 3.7% clay, but only 3.9 meq per 100 9 soil C.E.C. This low C.E.C. confirms visual observation that, although the organic matter content is high, the organic matter is coarse, 34 Yield of Corn I (g dry wt) 35 5- s- 4- “'Granby 34 Rubicon 2+ Roscommon 1- AuGres 0 5’0 160 15% 7 260 460 Zn Treatment (ppm) Figure 1. The effect of zinc treatment on dry matter yield of corn I as influenced by soil type. Yield of Field Beans (g dry wt) N w l J Granby Rubicon Roscommon AuGres Figure 2. l l r T l 50 100 150 200 400 Zn Treatment (PPm) The effect of zinc treatment on dry matter yield of field beans as influenced by soil type. 37 7 6~ Granby Rubicon 54 3’ 3 x H o 3 4-I U) O 0 JJ m e :9 3n “-4 o o Roscommon H O 'H >4 2- AuGres 1.— 1 0 5'0 :50 1'50 300 400 Zn Treatment (ppm) Figure 3. The effect of zinc treatment on dry matter yield of tomatoes as influenced by soil type. 38 15- 14- 12- Rubicon 11- 10- (g dry wt) I ——-Granby Roscommon Yield of Corn II ipw uGres 1- I I I l I 0 50 100 150 200 400 Zn Treatment (ppm) Figure 4. The effect of zinc treatment on dry matter yield of corn II as influenced by soil type. 39 undecomposed litter and consequently of low exchange capacity. It was expected that this soil would exhibit similar Zn fix- ing properties as the AuGres sand, that is, relatively high toxicity to plants at the 200 ppm and 400 ppm Zn levels. However, with the exception of field beans, plant growth on Rubicon sand at these levels approached the Granby loamy sand, and in the case of corn II, exceeded it. These two soils exhibit rather similar properties with respect to Zn inactivation but have organic matter contents, clay contents and C.E.C.'s very different from each other. A possible explanation is the higher content of Mn in the Rubicon sand and will be discussed in more detail later. Corn appears to be more tolerant to high levels of Zn than tomatoes which were in turn more tolerant than field beans. At the 400 ppm Zn level on AuGres sand lack of shoot emergence of field beans was a problem. The seed germinated satisfactorily but geotropism seemed to have been affected since in some instances roots emerged through the surface and shoots went other directions. Also hypocotyl elongation was reduced and germinated seeds had to be carefully un- covered to allow growth to occur. Tomato transplants were used and only one plant was used per pot. This factor caused a somewhat large variation between replications which reduced the level of significance in some of the statistical analysis. Immediate wilting of the transplanted tomatoes occurred on AuGres sand at the 200 ppm and 400 ppm Zn levels and on Roscommon sand at the 40 400 ppm Zn level. Recovery did occur but the plants grew poorly. A very significant decrease in the dry weight of both corn crOps occurred at the 50 ppm and 100 ppm treatment levels on AuGres sand whereas corn on the Roscommon sand usually exhibited an increase in dry weight when compared to the con- trol at all treatment levels except the 400 ppm level. On the Rubicon sand and Granby loamy sand all crops ex- cept field beans on Granby have a downward slope on the dry weight curves between the 200 ppm and 400 ppm treatment levels. This trend indicates that the Optimum level of Zn application on these soils for the crops grown has probably been exceeded. Zn, Mn, Fe and Cu concentrations in plant tissue and total uptake of these elements by the different plants re- ceiving Zn treatments are presented in Appendix Tables 1-16. Summary tables are presented here to facilitate discussion. Plant Zn concentrations depend on soil type, plant type, and treatment level, but always increased with increasing treatment levels indicating a non-metabolic or passive type uptake (Table 3). Field beans generally contained the least Zn in the plant tissue followed by tomato and then corn. Re- call that the 400 ppm Zn level on the AuGres sand caused serious growth reduction on all plants. This soil has the lowest buffering capacity of the four studied and would be expected to have the highest level of Zn available for plant uptake at each treatment level, which is actually the case as will be shown later. Plants grown on this soil would be 41 Table 3. Summary of Zn concentrations in plants due to soil- Zn additions. (See Appendix Tables 1-4). Zn ppm pIEntjfn concentratIOn in: Soil tmt Corn I Field Bean Tomato Corn II AuGres sand 0 43 26 92 64 400 737 493 406 957 Roscommon sand 0 47 35 94 115 400 934 390 653 730 Rubicon sand 0 76 40 105 59 400 891 458 630 444 Granby loamy sand 0 64 46 96 55 400 750 190 413 498 expected to have the highest concentration of Zn in the tissue. The figures in Table 3 do not always Show this but if we ex- amine the 200 ppm Zn treatment in Appendix Tables 1-4 it is generally the case. It appears that the ability of the root to take up Zn has been reduced at the 400 ppm level. The plants on Granby loamy sand generally had the lowest level of Zn which was expected. Rubicon sand was next, followed by Roscommon sand. It should be pointed out that it is not necessarily the Zn level in the plant which is toxic. Com- paring field beans on AuGres sand and Granby loamy sand one sees that the Zn contents were 406 and 413 ppm, respectively, but the dry weights were 0.9 g and 4.2 g, respectively. Over- all plant nutrition and nutrient balance, especially between Zn,Iu.Fe, and Mn, is probably a large but unknown factor. Normal plant-Zn levels in corn were found by Jones (1967) to be 39-41 ppm and excessive levels to be over 100 ppm. Lessman (1967) found normal plant-Zn levels in field beans to be 15-20 ppm and Judy (1967) found 50 ppm to be the toxic level for field beans. For tomatoes, Gauch (1972) found 15-198 42 ppm Zn to be normal and 526-1,489 ppm Zn to be toxic. In this study the plant-Zn concentrations for the control plants were generally within the suggested ranges for "normal con- centrations". However, except for tomatoes, the cited toxic levels have already been exceeded in plants growing on the 50 ppm Zn treated soils with no noticeable ill effects, rein- forcing the fact that nutrient balance is as important as tissue-Zn concentration (Appendix Tables 1-4). Increase in total Zn uptake per pot was statistically significant in all but two instances and these were on AuGres sand. This was due to the great variability between replica- tions at the 400 ppm Zn level (Appendix Tables 1-4). These uptake data indicate that if high Zn content of crops used for livestock feed is the objective then maximum growth may not be desirable since maximum uptake always occurred at less than maximum growth. Morrison (1951) estimates for silage corn a yield per acre of 8 tons with a dry matter con- tent of 4,384 pounds. Using this dry matter figure and the data from Appendix Table l for Roscommon sand to calculate total uptake, the 100 ppm Zn treatment had a dry weight of 3.7 g (4,384 pounds on an acre basis) and a Zn concentration of 1,012 ppm for a total Zn removal of 4.4 pounds, or 4.4% of that applied. While the 200 ppm Zn treatment reduced growth by 30% and increased Zn content to 1,629 ppm, the percentage of that added which was removed by the crop dropped from 4.4% to 2.5%. Under the conditions of continuous waste applications the soil would become a sink for this metal. 43 Increasing Zn levels Significantly influenced the Mn concentration in the plant tissue (Table 4). Table 4. Summary of Mn concentration in plants due to soil— Zn additions. (See Appendix Table 5-8). Zn ppm plant-Mn concentration in: Soil tmt Corn I Field Bean Tomato Corn II AuGres sand 0 89 67 101 79 400 101 225 362 339 Roscommon sand 0 124 107 156 89 400 215 251 255 227 Rubicon sand 0 134 89 321 145 400 337 542 776 293 Granby loamy sand 0 25 34 109 36 400 88 23 72 39 The soil type is very important and it is interesting to note the similarity of the numbers for each soil across crop types. From Table 2 the total soil Mn contents in the various soils are found to be 41, 80, 132 and 88 ppm for AuGres, Roscommon, Rubicon and Granby soils, respectively. This high level of Mn in the Rubicon sand coupled with its relatively high avail- ability for plant uptake (Tables 5-8) may be one of the rea- sons why crops grown on Rubicon sand show less growth reduc- tion due to high levels of Zn than other soils. The avail- ability of the Mn for plant uptake is more readily influenced where there is excess Mn, such as the Rubicon sand, than where the Mn is tightly bound as in the Granby loamy sand. Traynor and Knezek (1973) found a similar result on Rubicon sand with additions of both Ni and Cd. Field beans grown on Granby loamy sand actually exhibited 44 a Mn deficiency when Zn was added. This was the result of a large growth increase due to added Zn and an inability of the plant roots to absorb sufficient Mn to meet the plant's re- quirements. The NH4OAc extractable Mn in the Granby loamy sand is 1.0 ppm or less whereas Rubicon sand has 10 to 20 times that quantity (Appendix Table 40). Plant-Mn concentrations, as listed by Jones (1972), are 20-500 ppm as sufficient and over 500 ppm as toxic. The ranges found in this study were generally within these limits. Mn uptake generally increased with increasing Zn addi- tions up to 200 ppm (Table 5). Table 5. Summary of Mn uptake by plants in response to soil- Zn additions. (See Appendix Tables 4-8). Zn ug/pot plant-Mn uptake by: Soil tmt Corn I Field Bean Tomato Corn II AuGres sand 0 302 113 268 631 150 332 172 1126 838 400 140 287 686 7 500 Roscommon sand 0 294 294 880 983 150 537 378 1756 1429 400 406 357 566 1830 Rubicon sand 0 438 291 1925 1982 150 705 999 2400 2392 400 1014 870 4016 3752 Granby loamy sand 0 141 95 599 355 150 167 171 487 567 400 346 95 426 359 With the exception of plants grown on Rubicon sand, Mn uptake generally decreased sharply at the 400 ppm Zn treatment. This was primarily the result of lower plant weights and in some cases lower plant Mn concentrations. 45 Zn treatments generally had little effect on Fe or Cu concentrations in the plant tissues. In order to substantiate reports that Zn reduces iron uptake, measurements of plant- Fe content were made. No significant trend could be noted. Since Fe and Cu concentrations did not vary greatly with treatment, uptake of these elements generally followed plant weight changes (Appendix Tables 9-16). Effects of Added Zinc on Soil pH and Extractability of Zinc, Manganese, Iron and Copper With the addition of Zn ions to a soil system one would expect several reactions to occur. A hydrolysis reaction be- tween water and Zn ions forming ZnOH+, or Zn(OH)2 and H+ ions Should occur. Precipitation of Zn(OH)2 should remove some Zn from the system along with a lowering of the soil pH. Ex- change reactions and chelation reactions should also occur as well as a small fraction remaining in solution. All of these in fact occur. The pH shows a significant decrease in all soils, the actual decrease depending on the buffering capacity of the soil (Table 6). If the buffering capacity is based solely on the C.E.C. then the characteristics of the Roscommon and Rubicon soils are reversed. According to Jenne (1968), a more important factor in controlling the availability of transition elements is the hydrous oxides of Mn and Fe present. And since Rubicon sand has a larger amount of Mn than the other soils this could be the controlling factor. However, 46 Table 6. Summary of pH data on Zn-treated soils. (See Appen— dix Tables 17 and 18). pH change in soil under: Zn Corn I & Corn II & Soil tmt Field Bean Tomato AuGres sand 0 7.49 7.51 400 6.84 6.79 change 0.63 0.72 Roscommon sand 0 7.28 7.27 400 6.91 6.70 change 0.37 0.57 Rubicon sand 0 7.23 7.01 400 6.94 6.65 change 0.29 0.36 Granby loamy sand 0 7.43 7.40 400 7.16 7.14 change 0.27 0.26 when looking at the change in extractabilities of different metals with increasing Zn additions, the fact that the pH does drop 0.26 to 0.72 pH units must be kept in mind. Four extracting agents were used (Table 7) and the efficiency of each depended on soil type and treatment level. It appears that with each increasing amount of Zn added a relatively larger proportion of the added amount is extract- able with a given extractant in a given soil (Appendix Tables 35-38). Water extractable Zn represents the leaching potential with additions of pure water. From 0 to 200 ppm added Zn al- ways increased the H 0 extractable Zn but only slightly. A 2 much larger increment, amounting to 1.4% of that added on AuGres sand and 0.25% of that added on Granby loamy sand was removed at the 400 ppm treatment level. 47 Table 7. Summary of extractable Zn from Zn-treated soils. (See Appendix Tables 35-38). Zn ppm Zn extracted by: Soil tmt H20 111 NH4OAC .005! DTPA .1131 HCl AuGres sand 0 0.3 0.5 0.9 2.6 400 5.9 126 144 373 Roscommon sand 0 0.4 0.4 1.6 3.0 400 2.5 79 164 343 Rubicon sand 0 0.4 0.6 1.9 6.4 400 3.5 87 125 317 Granby loamy sand 0 0.5 0.5 2.4 5.5 400 1.6 67 239 384 Easily exchangeable Zn ions are those removed by 1N NH4OAC and represent the leaching potential caused by efflu- ents carrying exchangeable cations. Here as with H20 ex- tractable a higher percentage of that added was removable on the AuGres sand than the Granby loamy sand, 31% and 17%, respectively, with the other soils intermediate. This frac- tion is sometimes considered that which is available to the plants. Organic matter plays an important role in binding Zn as is shown by the 0.005N DTPA extractable fraction. The Granby, containing 8.9% organic matter, retained 59% of the 400 ppm treatment in a DTPA extractable form. The Rubicon sand had the lowest level of DTPA extractable Zn at the 400 ppm treatment, 31%, indicating further the nondependence of this soil on organic matter for its metal inactivation pro- perties. The 0.1N HCl extractable Zn includes the tightly bound and precipitated forms of Zn. The Granby loamy sand released 48 90-95% of the added Zn with the HCl treatment. The AuGres and Roscommon sands were somewhat lower, ranging from 50 to 92%. An interesting feature is that the Rubicon sand has a much larger fraction than the other soils which is not ex- tractable with HCl, approximately 25% at the 400 ppm Zn treat- ment level. This indicates that the mechanism of binding Zn is quite different between Rubicon sand and the other soils. The effects of added Zn on the extractability of Mn is summarized in Table 8. Added Zn had no effect on the extract- ability of Mn with any of the extractants on Granby loamy sand. Table 8. Summary of extractable Mn on Zn-treated soils. (See Appendix Tables 39-42). Zn ppm Mn extracted by: Soil tmt H20 lNLNH4OAc .OOSM DTPA .lN HCl AuGres sand 0 0 1.5 1.4 6.5 400 1.4 4.6 3.2 8.0 Roscommon sand 0 0 2.3 3.5 13.7 400 0.7 5.4 6.3 16.4 Rubicon sand 0 O 9.5 6.6 58.1 400 3.2 23.5 18.4 82.4 Granby loamy sand 0 0 0.9 1.2 18.8 400 0.1 1.1 1.8 18.2 0 = not detectable In this case the Mn appears too strongly bound. With the other soils increasing Zn treatment levels caused an increase in the Mn extracted with H20, 1N NH4 smaller but fairly consistent increase in 0.1N7HC1 extractable OAc and 0.00593 DTPA. A Mn may be due to the treatment effect of lowering the soil pH with increasing Zn levels. pH was found by Maas et al. (1968) 49 to greatly influence availability and plant absorption of Mn. The large amount of 1N NH OAc extractable Mn obtained 4 from all soils and especially Rubicon sand is an indication that the Zn and Mn are participating in an exchange reaction. Also a similar amount of Mn is extracted by DTPA and indicates organic matter is an important site for Zn fixation. The effect of Zn treatments on Fe extractability was not as dramatic as for Mn. H 0 and 1N NH OAc extractable Fe 2 4 appeared to decrease as the treatment level increased. In most cases the trend was significant. In some instances the 0.005N DTPA and 0.1N HCl extractable Fe levels were significant but the interpretation is difficult since the change was erratic (Appendix Tables 43-46). The total soil content of Cu (Table 2) was low and no consistent influences of soil Zn treatments on extractable Cu were noted (Appendix Tables 19-34). Plant Response to Soil-Chromium Additions The effects of added Cr on plant growth are determined by soil type, treatment level, and to a lesser extent by the crop grown. Cr is much more toxic to plant growth than similar additions of Zn. A summary of plant dry weight data is pre- sented in Table 9. Noticeable growth reduction was Observed at the lowest rate of Cr application, 50 ppm, in every case but four. Corn I on Roscommon sand, field beans on Granby loamy sand, and tomatoes on Rubicon sand and Granby loamy 50 Table 9. Summary of plant dry weight data for plants on Cr- treated soils. (See Appendix Tables 47-50). Cr g/pot plant dry weight of: Soil tmt Corn I Field Bean Tomato Corn II AuGres sand 0 3.4 1.6 2.4 7.9 400 0.1 NP 1.0 0.2 Roscommon sand 0 2.3 2.8 5.5 11.0 400 0.1 NP 1.2 0.4 Rubicon sand 0 3.3 3.5 6.3 13.8 400 1.9 1.5 2.5 3.1 Granby loamy sand 0 5.7 3.6 5.8 10.4 400 1.6 1.2 3.0 4.7 NP = no plant sand all had increased dry weight at the 50 ppm Cr level. However, the dry weight in all cases at the 100 ppm Cr treat- ment level was below that of the control plants (Figures 5-8). An examination of the growth curves reveals two distinct portions of the decreasing phase. The first is a rapid drop in dry weight and the second is a continued decrease but at a much slower rate. This indicates that the mechanism of toxicity operates at relatively low Cr concentration to re- duce plant growth and that once this has happened it takes proportionally greater concentrations to further reduce growth. AuGres and Roscommon sands generally produced similar results, at the various treatment levels. The main difference between these soils is that Roscommon sand appears to have a higher initial level of fertility. With the one exception mentioned earlier, plant dry weight on these two soils fell off dramatically at the 50 ppm Cr level. (g dry wt) Yield of Corn I 51 2- Rubicon Granby 1.. Roscommon AuGres L l l r r 0 50 100 200 400 Cr Treatment (ppm) Figure 5. The effect of chromium treatment on dry matter yield of corn I as influenced by soil type. 52 Figure 6. 54 33 5.. 3 >. u 'o 3‘ m 4- c O O m 'o H .3 m 3- *H o 'o H O -H w 2.. Rubicon Granby 1.. Roscommon i : -s T I l 0 50 100 200 400 Cr Treatment (PPm) The effect of chromium treatment on dry matter yield of field beans as influenced by soil type. . Yield of Tomatoes (9 dry wt) 53 ‘7.- I I I I I 6 \ A 5+ \ ‘\ \ \ \ \ \\ 44 \ \ \\‘ \“ \“ \\‘ 3-J ‘Granby 'ubicon 2- Roscommon 14 AuGres i I I I l 0 50 100 200 400 Cr Treatment (ppm) Figure 7. The effect of chromium treatment on dry matter yield of tomatoes as influenced by soil type. 147 13‘ 12‘ 11 94 74 Yield of Corn II ( g dry wt) 44 3-I 2d 10‘\\ 54 Granby Rubicon Roscommon AuGres Figure 8. I T l I 50 100 200 400 Cr Treatment (ppm) The effect of chromium treatment on dry matter yield of corn II as influenced by soil type. 55 The Rubicon sand and the Granby loamy sand-produced somewhat similar growth curves for tomatoes and corn II and produce similar curves for corn I and field beans at the 200 and 400 ppm Cr treatment levels. The sharp increase in dry weight of field beans on Granby loamy sand at the 50 ppm Cr level can be attributed to a release of bound Mn by the Cr ions and a consequent alleviation of the Mn deficiency exhibited by the control plants. The fact that Rubicon sand acts more like Granby loamy sand than AuGres sand with respect to buffering the system against increasing levels of Cr is difficult to explain. It is possible that the observations of Jenne (1968) that transition metals are bound to the sur- face of Mn and Fe hydrous oxides holds true for Cr as well as Zn. At the 400 ppm Cr level on both AuGres and Roscommon sands field beans would not grow. Germination occurred but the hypocotyl would not elongate and early roots appeared brownish. Tomato plants severely wilted immediately upon transplanting at both the 200 and 400 ppm Cr level on these two soils. Recovery occurred in about half the cases and replants were used where plants died. Eventually there was a tomato in every pot, but the tomatoes in the 400 ppm Cr treated pots never grew and eventually withered. Barber and Koontz (1963) attribute these symptoms to a possible disruption of the plasmalemma allowing a great influx of various ions which are in solution. Another possibility is the formation of a Cr olate, a series of Cr ions bridged 56 together by water molecules, on the root surface thus re- ducing water flow into the root. Some wilting of the transplants occurred at the 400 ppm Cr rate on Rubicon sand and Granby loamy sand, but all plants recovered. Corn germinated well and emerged in a uniform manner at all treatment levels but the plants on the AuGres and Roscommon sands at the 400 ppm Cr rate soon stopped growing, turned brown and died. At 100 ppm Cr levels the plants continued growing for awhile but were stunted and eventually died. It appeared to be a cumulative problem that became more severe as the plants became older. On the Rubicon sand the plants grew well on the 400 ppm Cr treated soil for three weeks, then withered and died within about a week. All corn I grown on Cr treated soils exhibited purpling of the stalk and lower leaves. Only the higher levels of Cr caused this on corn II and was not present on tomatoes or field beans. Spence and Millar (1963), Soane and Saunder (1959), and others have described this as a Cr-P interaction. A summary of the plant Cr concentration data is pre- sented in Table 10. Even though the levels of Cr in the plant tissue are usually very low at the 200 ppm treatment and not detectable at the 50 ppm level, dramatic growth reduction has usually already occurred at these levels. The problem is therefore not in the plant t0ps since visual toxicity symptoms occur long before detectable levels are found in the tops. The site of Cr influence is not known but is possibly at the 57 Table 10. Summary of plant-Cr concentrations resulting from increasing additions of Cr to soils. (See Appen- dix Tables 47-50). Cr ppm plant-Cr concentration in: Soil tmt Corn I Field Bean Tomato Corn II AuGres sand 0 0 0 0 0 200 4.2 32.9 3.4 11.1 400 1.9 NP 35.8 22.7 Roscommon sand 0 0 0 0 0 200 0 4.6 10.0 1.5 400 0 NP 10.0 7.6 Rubicon sand 0 0 0 0 0 200 0 1.5 2.8 0 400 0.8 67.9 4.0 3.8 Granby loamy sand 0 0 0 0 0 200 0 2.3 3.1 0 400 0 6.9 2.2 2.3 NP = no plant; 0 = not detectable root surface. Granby loamy sand does the best job in keeping Cr concentrations in the plant low, followed closely by Rubi- con sand. Cr uptake by the various plants is generally very low due to the fact that as the plant Cr concentration is in- creasing the dry weight is decreasing (Table ll). In this study there does not seem to be a great difference between the plant type grown and the amount of Cr uptake. Field beans seem to be more sensitive than corn or tomatoes to high treatment levels of Cr. The controlling factor would appear to be the soil type. There is a statistically significant change in the Mn content of all crops studied (Appendix Tables 51-54). This change is generally an increase but when the plant is ob- viously distressed by the Cr treatment applied then the plant 58 Table 11. Summary of plant-Cr uptake in response to Cr addi- tions to the soil. (See Appendix Tables 47-50). Cr ug/pot plant-Cr uptake by: Soil tmt Corn I Field Bean Tomato Corn II AuGres sand 0 0 0 0 0 200 1.7 31.8 5.5 11.1 400 0.4 NP 37.1 1.5 Roscommon sand 0 O 0 0 0 200 0 6.5 10.4 1.5 400 0 NP 16.2 3.3 Rubicon sand 0 0 0 O 0 200 0 3.4 8.7 0 400 1.5 101.9 9.8 13.4 Granby loamy sand 0 0 0 0 0 200 0 5.0 6.8 0 400 O 8.6 7.3 9.7 NP = no plant; 0 = not detectable Mn concentration decreases and sometimes rather sharply (Table 12). Where there is Mn available such as in the Rubicon sand there is a larger increase in plant-Mn concentration. Table 12. Summary of plant-Mn concentration in response to Cr additions to the soil. (See Appendix Tables 51-54). Cr ppm plant-Mn concentration in: Soil tmt Corn I Field Bean Tomato Corn II AuGres sand 0 87 67 101 79 200 127 30 110 126 400 36 NP 115 83 Roscommon sand 0 124 107 156 89 200 143 113 141 124 400 67 NP 186 159 Rubicon sand 0 134 89 321 145 200 258 311 313 184 400 276 107 562 329 Granby loamy sand 0 24 34 109 36 200 75 54 122 72 400 85 63 144 81 NP= no plant 59 Mn uptake under these conditions is generally significant only because it is a function of plant dry weight which sig- nificantly decreases. Therefore Mn uptake generally decreased (Appendix Tables 51-54). Fe, Cu, and Zn concentrations were not consistently affected by Cr additions and consequently uptake followed plant dry weight (Appendix Tables 55-66). Effects of Added Chromium on Soil pH and Extractability of Chromium, Zinc, Manganese, Iron and COpper As with the addition of Zn, a drop in soil pH with in— creasing Cr treatments was expected because of the hydrolysis 3 of water with the Cr+ ion forming Cr(OH)3 and H+. Because + . 2 ion. a of the higher charge on the Cr ion than on the Zn larger pH drop was expected on the Cr treated soils than on the Zn treated soil. Table 13. Summary of pH data on Cr-treated soils. (See Appendix Tables 67-68). pH change in soil under: . Cr Corn I & Corn II & $011 ' tm; Field Bean TgmaIQ___h AuGres sand 0 7.51 7.49 400 7.31 7.33 change 0.20 0.16 Roscommon sand 0 7.27 7.28 400 6.45 6.75 change 0.82 0.53 Rubicon sand 0 7.01 7.23 400 6.54 6.88 change 0.45 0.35 Granby loamy sand 0 7.40 7.43 400 7.00 7.14 change 0.40 0.29 60 Table 13 shows that there is always a significant decrease in pH with additions of Cr and that with the exception of AuGres sand the magnitude of the decrease was generally larger than for similar Zn treated soils (Table 6). The small change in the AuGres sand pH was unexpected and a ready explanation is not available. Rubicon sand, with its low C.E.C. of 3.9 meg per 100 9 soil, seems out of place in its ability to resist change. The coarse organic matter fraction makes this soil very well aerated and may be forming Cr 0 rather than Cr(OH)3 which 2 3 would have less effect on pH. Also the relatively high Mn content may be adsorbing the Cr+3. The fate of Cr+3 when added to a soil system has several possibilities. It can stay in solution, be adsorbed on the mineral and organic exchange complex or on the Mn and Fe hydrous oxide coating of soil particles, become chelated by an organic legand, or precipitate as sparingly or highly in- soluble compounds. Four extracting agents were used to look at each of the above possibilities: deionized water for the. fraction in solution; 1§_NH4OAc for the readily exchangeable fraction; 0.005M DTPA for the chelated and organically bound fraction; and 0.1N HCl for the tightly bound and precipitated fraction. No significant increase was detected in water soluble Cr at any treatment level on any soil although slight increases did sometimes occur (Table 14). This would indicate that there is no leaching problem involved in applying this level of Cr 61 Table 14. Summary of extractable Cr from Cr-treated soils. (See Appendix Tables 85-88). Cr ppm Cr extracted by: Soil tmt H20 1N_NH40Ac .OOSM DTPA .1u,HCl AuGres sand' 0 0 0 0 0 400 0.3 8.1 1.6 88.5 Roscommon sand 0 0 0 0 0 400 0 7.8 1.9 87.6 Rubicon sand 0 0 0 0 0 400 0 9.8 1.4 90.3 Granby loamy sand 0 0 0 0 0 400 0.1 4.9 1.3 67.4 0 = not detectable even on very sandy soils with neutral pH's. This also indi— cates the plants grown on these soils are being affected by some other form of Cr than that in solution. The significant increase in 1N.NH4OAc extractable Cr, 1 to 2% of that applied, indicates that some Cr remains in an exchangeable form. The AuGres, Roscommon and Rubicon sands are similar in 1N_NH4OAc Cr whereas Granby loamy sand is sig- nificantly lower. Bertrand and deWOlf (1968) used this ex- traction as an index for available Cr. In this study as 1E.NH OAc extractable Cr increases, toxicity symptoms become 4 more severe. The 0.005M_DTPA extractable fraction was very small, amounting to less than 0.5% of that added at the 400 ppm Cr level. By referring to Appendix Table 87 it is inter- esting to note that the amount of Cr available or able to be chelated by DTPA is satisfied at the 50 or 100 ppm Cr treat- ment level. There are several possibilities why this occurs. 3 DTPA may have only very limited capacity to chelate Cr+ and/ 3 or organic matter may not bind much Cr+ and/or the stability 62 3 of the organo-Cr+ complex may be much greater than that of the DTPA-Cr+3 complex. As will be discussed in more detail later, the increase of DTPA extractable Mn with increasing Cr treatment levels lends support to a very stable organo- Cr+3 complex. The 0.1N HCl extracted only 23% and 17% of the applied Cr on the Rubicon sand and the Granby loamy sand, respectively, at the highest treatment level and slightly higher amounts at lower treatment levels. This low recoverability indicates very stable Cr complexes have been formed. The influence of increasing Cr treatments on extractable Mn is shown in Table 15. The water extractable Mn fraction does not change appreciably. A similar significant increase in both lN_NH OAc and 0.005M DTPA extractable Mn indicates a 4 general displacement of Mn by the added Cr. This displace- ment could be from the organic fraction or possibly from the Mn hydrous oxides which coat the soil particle surfaces due to a lowering of the pH with increasing Cr treatment levels. The Cr treatments had little or no effect on 0°1§.HC1 extract- able Mn. The influence of increasing Cr levels on extractable Fe is just the reverse of that observed with Mn (Table 16). OAc and DTPA extractable Fe all de- The fact that H 0, NH 2 4 crease indicate an Fe-Cr complex is forming which is effec- tively making both Fe and Cr less available for plant uptake. The large surplus of Fe in these soils probably is the reason the plant-Fe content remains fairly constant (Table 2). 63 Table 15. Summary of extractable Mn from Cr-treated soils. (See Appendix Tables 89-92). Cr ppm Mn extracted by: Soil tmt H20 lflLNH4OAc .OOSM DTPA .l§_HCl AuGres sand 0 0 1.5 1.4 6.5 400 0.1 2.0 2.7 7.0 Roscommon sand 0 0 2.3 3.5 13.7 400 0.4 3.5 5.6 14.6 Rubicon sand 0 0 9.5 6.6 58.1 400 1.8 15.7 17.7 67.1 Granby loamy sand 0 0 0.9 1.2 18.8 400 0.6 1.2 2.1 16.5 0 = not detectable Table 16. Summary of extractable Fe from Cr-treated soils. (See Appendix Tables 93-96). Cr ppm Fe extracted by: Soil tmt 1120 1N NH40Ac .oosg DTPA .13 HCl AuGres sand 0 1.3 1.7 47.5 45.1 400 0.7 0.9 26.3 56.4 Roscommon sand 0 7.6 2.5 203 156 400 1.0 1.9 118 168 Rubicon sand 0 4.6 4.1 78 137 400 0.5 2.2 45 149 Granby loamy sand 0 7.8 3.3 208 283 400 1.1 2.8 156 260 There was little, if any, effect of increasing Cr treat~ ments on Zn and Cu extractions (Appendix Tables 69-84). Probable Soil-Plant Relations after Irrigation with Effluents Containing Zinc and Chromium The U.S. Army Corps of Engineers (1972) lists the "aver- age” Zn and Cr content of effluents to be 0.2 ppm for each ele- ment. Using an average effluent irrigation rate of 2 inches per week, 4.7 pounds of both Zn and Cr would be added per 64 acre per 52 spray-week year. This amounts to less than 2.4 ppm per acre-furrow-slice at the 2 inch application rate and less than 4.8 ppm per acre-furrow-slice at a 4 inch applica- tion rate. Using the silage dry weight for corn of 4,384 pounds per acre given by Morrison (1951) and the average Zn-plant content of 57 ppm for the control plants from Appendix Table l, .25 pounds of Zn would be removed per acre per year. This amounts to 5% of the Zn added at the 2 inch rate and 2.5% of that added at the 4 inch rate. There was no detectable Cr in the tops of plants grown at the lower Cr levels. Using instead the value of 0.02 ppm Cr given for sweet corn by Schroeder et a1. (1962), less than .0001 pound of Cr would be removed through cropping per acre per year. Over a fifty year period the 2 inch application rate would result in 225 pounds of both Zn and Cr being deposited per acre. Using the plant-Zn concentrations for the 0 and 100 ppm Zn treatment levels from Appendix Table 1, the amount of Zn removed by cropping would range between 12 and 62 pounds, for a net soil accumulation of 163 to 213 pounds. This would be an acceptable level for all but the most sandy soils grow— ing Zn-sensitive crops. There will essentially be no removal of Cr through cropping. Assuming a pH at or above neutrality, the level of 112 ppm (225 pounds per acre) Cr would be detri- mental to most crops growing on soils with little or no bind- ing capacity. On soils with fairly high organic matter and 65 clay contents this Cr level would probably not be available to plants. Actually, work by Leep (1974) and Bertrand and deWolf (1968) has shown this level of Cr to increase plant growth on selected soils. Not enough is known about the mechanism of Cr influence on plant growth or the removal of Cr from the available pool via fixation to more unavailable forms with time. If the effluent in question is from Grand Rapids, Michigan with an average of 0.8 ppm Zn and 2.5 ppm Cr, the disposal sit- uation changes drastically. At the 2 inch per week applica- tion rate, 18.7 pounds of Zn and 58.5 pounds of Cr would be added per acre per year. In only 10 years 187 pounds of Zn and 585 pounds of Cr would be added per acre. While this amount of Zn is still only approaching the toxic levels of this study, the nearly 300 ppm Cr has already exceeded by a large margin the level which caused serious growth reduction to all plants on all soils. Upon examination of Figures 5-8, it appears that the maximum allowable Cr accumulation in the soils studied is 50 to 100 ppm. Suggested Research Areas Most research concerning heavy metal applications to soils is carried out one metal at a time. In reality, efflu- ents cOntain combinations of metals. Some work should in- volve combinations of various metals at varying rates thus simulating actual effluents. A nutrient solution study looking for the mechanism of 66 Cr toxicity is needed. The fixation of Cr over time needs to be studied. The importance of hydrous oxides, especially of hydrous oxides of Mn because of their negative charge, should be in— vestigated in relation to waste disposal. A correlation study looking specifically for a predic- tion equation for metal binding based on soil properties such as C.E.C., clay type and quantity, organic matter content, Fe, Mn, and P contents, aeration and pH would be very useful. SUMMARY AND CONCLUSIONS Plant responses to Zn and Cr treatment were influenced by soil type, plant type and the ambient metal concentration. Placed in the order of their ability to reduce toxicity symp- toms in plants grown at high ambient Zn or Cr levels the soil types are: Granby loamy sand>Rubicon sand>Roscommon sand> AuGres sand. With the exception of Rubicon sand, this order represents decreasing C.E.C. and organic matter content. Rubicon sand had the lowest C.E.C. of the four soils studied. The ability of this soil to better neutralize the toxic effects of high metal concentrations is possibly due to the relatively high Mn hydrous oxide content and the well aerated condition of the soil. Corn and tomatoes appeared to be slightly more tolerant to high Zn or Cr concentrations than field beans. All plants on all soils exhibited significant growth reduction at the 100 ppm Cr treatment level. Although germination did occur, subsequent growth of corn and field beans at the 400 ppm Zn treatment level on AuGres sand was poor. The 400 ppm Cr level prevented growth of field beans on the AuGres and Roscommon sands and corn only grew about an inch. Seventy percent of the plants grown on 50 ppm Cr treated soils showed some dry weight reduction when compared to the controls. 67 68 Plant-Zn concentrations increased with increasing Zn treatment levels, the highest concentration occurring in plants on the AuGres and Roscommon sands and the lowest in plants on the Granby loamy sand. Increasing ambient soil-Zn levels pro— duced an increase in the plant-Mn content. Chromium in plant tissue was not detectable until the treatment level was high enough to produce extremely distressed plant conditions. In- creasing ambient soil-Cr levels generally caused a rise, then a lowering of the plant-Mn concentration. A possible explana- tion for this response to Cr is that the selectivity of the plasmalemma is reduced at lower Cr concentrations allowing for increased tissue concentration of Cr and Mn and that with fur- ther disruption of the plasmalemma movement across the membrane is reduced. Another possibility is the formation of an olate on the root surface reducing uptake of water and influx of passively absorbed ions. The extractability of Cr, Zn, Fe, Mn, and Cu from the various soils was dependent upon the extractant used, soil type and metal treatment. On the Zn treated soils deionized H 0,-1N NH OAc, 0.005M DTPA and 0.1N.HC1 extractable Zn in- 2 4 creased with increasing treatment level. The lower the buffer- 20 and NH4OAC ex- tractable Zn. The DTPA extractable Zn was the greatest in ing capacity of the soil the higher was the H the Granby loamy sand, followed by Roscommon, AuGres and Rubi- con sands, in that order. Water, NH4OAc and DTPA extractable Mn increased significantly with increasing rates of applied Zn indicating a general displacement of Mn from its bonding 69 sites by the applied Zn and/or a dissolution of Mn compounds due to a lowering of the pH by hydrolysis of the added Zn. There was a downward trend in the Fe extracted by H20 and NH OAc with increasing levels of applied Zn, possibly as a 4 result of Zn-Fe hydroxide c0precipitate. Extractable Cu was not significantly influenced by applied Zn. On the Cr treated soils no consistent amounts of Cr were extractable with H 0, even at the 400 ppm Cr treatment level. 2 Ammonium acetate extractable Cr increased linearly with addi- tional ambient soil-Cr levels, always amounting to 1-2% of that applied. The order of soils with the greatest NH4OAc extractable Cr at any treatment level was Rubicon sand>AuGres sand>Roscommon sand>Granby loamy sand. The DTPA extractable Cr was similar on all soils at all treatment levels except control, averaging 1.0 ppm and 1.5 ppm for the 50 and 400 ppm treatment levels, respectively. This indicates a very limited binding capacity of organic matter for Cr or a very stable Cr-organo complex from which Cr is not readily removed by DTPA. Less than 25% of the Cr at the 400 ppm level is re- coverable with 0.lN'HC1 indicating a rather stable, inert com- plex has been formed. Slightly higher amounts were extractable at lower treatment levels. Increasing Cr treatments increased 0, NH OAc and 2 4 DTPA. The Cr is probably displacing Mn from mineral and the Mn and decreased the Fe extractable with H organic matter exchange sites as well as lowering the pH through hydrolysis of the added Cr. A coprecipitate of Cr-Fe hydroxide is also probably forming. Chromium treatments had no appreciable 70 effect on Zn and Cu extractions. The leaching potential of applied Zn and Cr as measured by H20 and NH4OAc extractions indicate that appreciable amounts (1 ppm or more) of Zn were removed at the 200 and 50 ppm levels by H20 and NH4OAc, respectively. Water removed no appreciable amounts of Cr while NH OAc extracted 1 ppm or more at the 100 4 ppm Cr treatment level. APPENDIX .mdowumuwdmuu manna mo uwoum>o o£u mu o=Ho> guano .Nma I oxmumaxdwoa I uaooxdn.a I us hut I wagon mwoaa Ho>oa usuaumoua "Awo.v 9mg cum oma ~.c mow mmc o.a nmm can m. fine can m.o cow Hmm and m.m has new m.~ «SS wHN c.~ awn oau m.H ooN mmm oma m.o Hus «um m.m mac and o.~ swu HRH N.H omH «on omH 0.0 awn «Ga o.m Nwm mud H.N new mad m.a ooH owm mmH m.m nma «ma N.m awn «ma ¢.N mad nu n.H on qua we e.m oaa oq n.m Hoa mm m.~ me om e.a o uopxm: and u0d\w uom\wn and u09\w udew: and u0d\w uooxw: and nooxm and sum: ocoo uz mun xuaa oaoo us mun xuas oaoo oz Nun Jump oaoo us mun use tammxwamoa madman vamm coownsm can» aoaaouwom comm mouoa¢ an .mwcoauwvcoo masonaomum nova: wagon vmummuunuauu do many» momma vaofim an mxmums tam sowumuucmucou onus .usmama kuv uade no Hm>oH uaoaumouu can max» Adom mo uncommm .~ manna .ndowumufiaamu conga mo ownuo>w mnu aw o=Hm> gamma .wwm I oxmuqs .Nmm I ucooldm.a I us hut I mawommmmqau Hm>ma uauauwmua "Ano.v 9mg HamN can o.e ookm Ham a.~ mama «mm a.a o~oa “ma k.o cos mmwa ems ~.e Hana «Ne ~.m mNoH ado o.N «sod «no o.H cow Sana Ham ~.c NSOH mom ¢.m meH was H.m mma can a.a and oaHH mmN m.e whoa mwa k.m «flea mam ~.m fine Ham m.H cod knoa awa m.m ams and n.m cos ass k.~ HHS sea m.~ on «on so ~.n mam on m.m moa as m.~ med ms ¢.m o uom\m: and u0d\w uopxw: and uoaxw nadxw: and uooxw uoa\m: and uoamw and gums once u: was sum: once “3 sun ammo oaoo 6: sun sum: ucoo as emu use comm hamoa mncmuo boom nouandm pawn soaaoomom town mmuu=< 3N .wmcoauficcoo masonamwuw “was: wagon woummuuluoau so caouw H :uoo kn wxwuas tam cowumuucoucoo ocwu .uswama hut uamaa so Ho>oa unmaummuu cam wdhu Hwom mo muummmm .H manna 71 .maOHumoHHdwu manna mo wwmum>m mnu mH mus> comma .wauH u mxmums .on I 0600 .~.m I us who I mHHomemoao Hm>oH uawaummue "Amo.v QmH mHoq mac N.m qqmm «as m.HH mnmm omn o.m HmvH “mm q H ooq owwm mam m.m omwm Nun N.QH mwmm mum n.mH quH own o m com ome new o.m HmoN HHN o.NH mmwm mam o.HH ean Ham H ¢ omH oweH HRH m.m ommN HNN o.HH onmm emu m.NH new 0mm m N OOH HNHH NNH ~.o ommH cNH ~.NH HwHH NmH m.m com mm m m on Hum mm q.OH mow mm w.mH mmNH mHH o.HH mmq on m n o u0d\wn and uod\w uoa\wn and u0d\w uoa\wn and uod\m uod\wn_ and uoa\w and Hum: ocoo uB mun xudp oaou u3INMd xumb uaou oz hum Hum: ocoo us Mun use vcmm mamOH mncmuo tcmw cooHnsm comm coaaoumom puma mmuos< an .mmaOHquooo omsonooouw nouns mHHom voummuulucHu no naouw HH cuoo mp mHMuao can ooHumuucmocoo oaHn .uanma hut uamHm so Ho>0H unmaummuu vow odzu HHom mo muommmm .a mHAmH 72 .mGOHumoHHamu moan» mo mwmuo>w mnu mH maHm> comma .QNOH n mxmum: dmNH I ucoo ..m.z I as hut I mHHom macaw Hm>mH unmaummue "Amorv an oqm~ qu n.m mHSm omc q.m HHwH mmo n.~ New ooq m H ooq mqu mHm m.o oaqm me m.o nncm aoc q.m wow “Hm m N com ocmH mwm q.m «HwH How «.5 mHom Sow o.m omw mum m m omH HOHN omm m.o ooNH mmm m.o nmmH Nmm o.q ohm amH o H ooH omMH mum N.o oNSH mom N.m ¢HHH mum m.q wma mmH o m on mmm om m.m mmm mOH m.o mum cm m.m moH mm a N o uomxw: and uoa\w u0d\mn and u0d\w uoa\w: and u0d\w uoaxw: and uoa\w and Hum: oaoo u3 Nun sud: ucoo us awn xumb odoo u3 mun Hum: ocoo us mun use vamm mEMOH undone tcmm cooHnsm pawn soaaoumom vcmm mmuosd cu .mwaoHqucoo mmnozaomum wows: mHHom vmummuulosHN co csouw mmoumaou an meuda tam QOHumuucmocoo oaHN .uanms hub uamHa co Hm>oH unmaummuu tam md>u HHom mo muommmm .m oHan .maOHumuHHdou «was» no omnuo>m an» «H oaHu> gamma .NmN I deun: «mm I 0600 .R.H I a? hub I mHHom macaw Ho>oH uauauwous «Hwo.v an; mm mm ~.S on «Sm S.H Rmm Hmu m. RwN mNN a.o oOS RS RH m.m wwo HmN m.~ mmm RSH o.~ QHN mSH n.H com HRH RN m.o mam Ham m.m me MSH o.~ NRH nOH R.H omH Ra SH o.S mmw omm o.m NNm omH H.N ooH ca m.H CCH HmH HN m.R NRS omH ~.m emu RMH S.~ SNH Nw m.H on ma Sm o.m Ham mm m.m Sam RoH m.~ nHH Re o.H o u0d\wa and uoa\w uom\wn and uom\w oedxw: and uOARN uOARw: and uoaxw and Hum: ucoo us Nun sum: uaoo u3 who Hum: odou us Nun Mum: once as Run use vamm hamOH mncmuo damn dooHnsm pawn doaaoomom pawn mouosd nu .mmGOHuHoooo masoncwmuw Home: mHHon vmuamquUdHu do macaw manna vHon hp mxmum: tam coHumuudooaoo mmmamwama .uanoa Rut unuHm no HobmH uauauuuuu can omhu HHom mo nuomwmm .0 anma 73 .mnOHuuUHHaou woman no owmum>m may mH oSHmb nomad .mHN u «gonna .Ho I oaou .m.H I u: hut I mHHouxwwoau Hm>oH uaoaumuua “Awo.HIan cSm mm o.S SHOH wmm a.~ ROS nHN ¢.H OSH HOH R.o ooS SwH mS N.S Rom mSN ~.m omS mmH o.~ HRN oRH o.H oou RSH HS N.S moR mom S.m Rmm HRH H.m Nmm oRH ¢.H omH me mm m.S Ham wnH R.m RRm SmH R.m oww RnH w.H 00H mmH Sm R.m NRS wMH m.m NRm mmH R.~ on NHH a.~ on HSH mu R.m «MS SMH m.m SmN SNH m.~ mom Rm S.m o uom\w: and uom\w uon\wn and uon\w uOQRNn and uoa\w quxw: and uoaxm and sums once 63 sun suam, oaoo us mun sum: 0600 a: Run sump uaoo us Nun use wamm REMOH hncmuo vamm oOUHnam ndmm ooaaoumom Scum nmuua< aN .mmGOHqucoo 06:05amouw nova: mHHom wouwmquusHu no nBouw H auou Rn exquaa tam =0Humuucmocoo mumsmwcma .uanms hut udde so Ho>mH upmaummuu tam mahu HHom mo muuommm .m oHan .mGOHuonHdwu wounu Ho owwuo>w msu uH maHm> comma .mSHH u mHMumaIaRw u used .~.m I as HMS I mHHomemmaa HopmH usuaummua “Amo»v an mmm mm ~.m NmRm maw S.HH ommH RNN o.w com SSm S.H 90S mOS mR m.m OSmm Smm N.SH mNSN mmH R.mH NmR Smm o.m com RSm ow S.R Nana omH S.HH SNSH NMH o.HH Smm How H.S SSH SRm HS m.a OSmN HNN S.HH oRmH HHH m.~H mom SSH m.~ 00H omS SS N.m meH mnH ~.NH SSR SS m.a Smn SS m.m om mmm Sm S.0H NSmH mSH S.mH mam SS S.HH HmS mR m.R o uod\w: and uod\w u0d\w: and uoaxw uom\m: and wedxm uonxw: and u09\w and Hum: oaoo u3 awn Hum: oaou us hum sum: uaoo u3.Nun sums ucoo us mun use Scam Raon Rasmuu Scum cooHnsm Scam aoaaoumom Scum mmuos< an 74 .mmaOHuHSaoo monogamouw nova: mHHom wouwoquusHu do naouw HH :uoo an oxmuas Sam aOHumuuamoaoo mmmamwcma .uanoa Raw uade do HmpwH unmauwmuu Sam odau HHom mo muuommm .w mHSwH .m:0HuooHHdmn mounu mo ommuw>w wsu mH maHm> :uomm .mSm I mxmuma .SwH I oaou 4.m.z I as mwv I mHHom‘wmoam Hm>mH unmaummuh "Awo.u QmH SNS NR R.m SHSS SRR S.m SSm mmm R.~ SSS mSm m.H ooS Hmm Sm m.S mSSN mRm m.S SSHN SMS S.n SNHH wSm S.H com RSS mm S.m OSSN SSm ~.R SSRH Smm o.n SNHH mSm m.m omH MRS SSH m.S nmmH Son S.S NHo RSH S.S mmm SR~ m.H SSH SSS SS ~.S oHHN Rom «.R Rmm MHN m.S omN mm o.m om mmm mOH w.m mNmH Hmm m.S omw SSH m.m SSN HOH S.~ o uon\wn and uoa\w uoaxw: and uooxw uon\wn and uoa\w uOd\w: and u0d\m and fig 38 a: .95 36mm 88 as NS fig: 38 us Nun fig: 88 us .05 ”.8. 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SS S S.S SH S S.H SSS SRS SS S.S SSH S S.SH RSH HH R.SH SS SH S.S SSS SS R S.R SSS HS S.SH SS S S.HH SS SH H.S SSH SS S S.S RSS SS S.HH RSS HS S.SH SS SH S.S SSH HSH RH S.S SSS HS S.SH SSH RH S.S SS R S.S SS HSH SH S.SH SSH S S.SH SHS SS S.HH SS SH S.R S u0S\S: SSS u0S\S uoS\SS SSS u0S\w u0S\w: SSS u0S\w u0S\S: SSS SOwa HSS SSS: oSoo u: SSS xuSS oSoS u: SSS xuSS uSoS uajwyS SSSH oSoo u: SSS use SSSS SBSoH SSSSSS SSSS SooHSSS SSSS SoaaooSoM SSSS SSHSSS SN 78 .SSSOHuHSSoo SSSonSSSuS HSSS: SHHOS SSuSSquuSHu So Saoum HH Suoo SS SxSuSS SSS SoHuSuuSooSoo SSSSoo .SSSHSB SHS SSSHS So HS>SH uSmauSmuu SSS SSSu HHoS mo Suoommm .SH SHSSH .SSOHuSoHHSSu Sauna mo SSSHS>S SSS SH SSHS> SSSSS .S.z I wauSS ..S.z I USoo ..m.z I us SSS I SHHoSIwSoaS HS>SH uSSEuSSHH “HSva SSH SS SH R.S SSH SH S.S SS RH R.S SS SH S.H SSS SR HH S.S HSH SH S.S SS SH S.S SS SH S.S SSS SR SH S.S SSH SH S.R SS RH S.S HS SH S.S SSH SS SH S.S SSH SH S.S SR SH S.S RS SH S.H SSH SS SH S.S SSH SH S.R SS SH S.S SS SH S.S SS SS SH S.S RSH HS S.S RSH SH S.S SS SH S.S S u0S\Sn SSS uoS\S uoS\S: aSS umeS uomxwa SSS SOSRS uoSRmS aSS uoSRS SSS SSS: oSoS S3 SSS xuSS uSoo S3 SHS xuSm‘ oSoo SB SSS SSS: oSoS u3 RSS use SSSS SESoH SSSSHS SSSS SooHSSm SSSS Soaaoomom SSSS SSHSSS SN .SSSOHuHSSou SSSoSSmmuS HSSS: SHHom SSuSSquoSHS So Shouw SwouSaou SS mxSuSS SSS SoHuSuuSmoSoo SSSSou .uSSHSS SHS uSSHS So HS>SH uSmauSmuu SSS SSSS HHOS mo Suommmm .SH SHSSH 79 Table 17. Influence of zinc treatments on soil pH - first sampling prior to planting corn I and field beansa. Soils Soil Tmts AuGres Roscommon Rubicon Granby Zinc sand sand sand loamy sand ppm -- pH- ------------ 0 7.49 7.28 7.23 7.43 50 7.35 7.22 7.27 7.39 100 7.38 7.20 7.25 7.23 150 7.21 7.10 7.20 7.08 200 7.17 7.07 7.10 7.35 400 6.84 6.91 6.94 7.16 8Each value is the average of six replications. Table 18. Influence of zinc treatments on soil pH - second sampling prior to planting corn II and tomatoesa. Soils Soil Tmts AuGres Roscommon Rubicon Granby Zinc sand sand sand loamy ' sand ppm _ PH 0 7.51 7.27 7.01 7.40 50 7.37 7.11 7.08 7.46 100 7.28 7.06 7.02 7.39 150 7.18 6.98 7.01 7.10 200 7.12 6.87 6.86 7.36 400 6.79 6.70 6.65 7.14 LSD (.05) 0.14 0.17 0.11 0.22 aEach value is the average of six replications. 80 Table 19. Soil treatments and soil extractable metal concentrations for zinc-treated AuGres sand prior to cropping with corn I under «greenhouse conditions . Extracting Agents Zn 0 . 111 O . 005M 1N 0 . 11! 0 . 005g 1N Tmt HCl DTPA NH40Ac HZO HCl DTPA NHAOAc H20 ppm Zn ppm----*- Mn ppm --------- 0 3 1 <1 0.3 6.7 1.4 1.5 ND 50 25 13 4 0.3 7.1 1.7 1.6 0.1 100 59 31 11 0.5 7.3 2.0 2.0 0.1 150 94 44 20 0.8 7.2 2.1 2.4 0.3 200 152 65 37 1.0 6.6 2.1 3.0 0.3 400 356 155 132 6.6 7.6 3.5 4.7 1.6 LSD (.05) l3 l7 9 1.9 NS 0.7 0.5 0.7 Fe ppm--------- Cu ppm------- 0 45 49 1.3 1.4 0.6 0.1 0.4 ND 50 56 38 2.2 3.3 0.4 0.3 0.1 0.1 100 53 37 1.7 4.4 0.4 0.4 0.2 ND 150 53 34 2.0 4.1 0.4 0.3 0.1 0.1 200 51 35 0.9 3.2 0.4 0.2 0.1 ND 400 48 35 1.7 2.0 0.4 0.3 0.2 ND LSD (.05) 3 5 0.9 0.7 0.1 0.2 0.2 NS 8Each value is the average of three replications. ND = not detectable. Table 20. Soil treatments and soil extractable metal concentrations for zinc-treated Roscommon sand prior to cropping with corn I under greenhouse conditions . Extracting Agents S Zn 0 . 1g 0 . 005M 1N 0 . ll! 0 . 005M 1_N_ Tmt HCl DTPA NHaoAc H20 HCl DTPA NHAOAc H20 ppm Zn ppm--------- Mn ppm--------- 0 3 2 <1 0.3 12.9 3.3 2.0 ND 50 28 20 3 0.4 13.2 4.0 3.1 0.4 100 88 36 8 0.7 15.5 4.8 4.6 0.4 150 122 56 16 0.9 14.6 5.3 4.7 0.5 200 154 71 23 1.5 14.1 5.3 4.7 0.6 400 345 160 80 2.3 15.9 6.2 5.4 0.7 LSD (.05) 21 ll 5 0.3 2 1.3 1.1 0.1 Fe ppm ------- Cu pme- ----- - 0 161 201 2 7.1 0.4 0.3 0.1 0.1 50 170 119 4 22.5 0.4 0.4 0.2 ND 100 181 124 4 25.4 0.4 0.5 0.1 ND 150 184 132 3 23.8 0.4 0.3< 0.2 ND 200 171 105 3 24.4 0.4 0.3 0.1 ND 400 194 118 4 6.7 0.4 0.3 0.2 ND LSD (.05) 10 32 .8 4.3 NS 0.1 NS NS aEach value is the average of three replications. ND 8 not detectable. 81 Table 21. Soil treatments and soil extractable metal concentrations for zinc-treated Rubicon sand prior to cropping with corn I under greenhouse conditions . :Extracting Agents Zn 0 . IN 0 . 005M 1N O . IN 0. 005}! IN Tmt HCl DTPA NHAOAc H20 H01 DTPA NHAOAc H20 ppm Zn ppm— ------------------ Mn ppm—--------- 0 7 2 <1 0.3 63 7.8 11.5 ND 50 32 18 4 0.6 90 6.3 9.5 0.5 100 67 31 11 0.8 85 9.1 13.1 0.7 150 101 42 18 1.4 80 9.1 14.8 0.8 200 151 74 30 1.8 88 12.9 17.3 1.4 400 325 137 90 3.6 92 17.6 21.6 3.0 LSD (.05) 27 7 5 0.3 NS 2.8 4.4 0.6 Fe ppme ------- - Cu ppm-------— 0 140 81 3.4 4.4 0.5 0.2 0.2 0.3 50 198 81 4.4 14.4 0.5 0.4 0.2 0.3 100 230 81 3.5 12.3 0.5 0.4 0.2 0.1 150 235 72 4.0 11.4 0.5 0.2 0.2 0.1 200 234 73 3.9 6.8 0.5 0.3 0.1 0.1 400 236 73 3.9 6.8 0.5 0.2 0.2 ND LSD (.05) 20 NS NS 3.4 NS NS NS NS 8Each value is the average of three replications. ND I not detectable. Table 22. Soil treatments and soil extractable metal concentrations for zinc-treated Granby loamy 33nd prior to cropping with corn I under greenhouse conditions . Extracting Agents Zn 0 . 1N 0 . 005}! 191 0 . IN 0 . 005! 1}! Tmt HCl DTPA NHAOAc H20 HCl DTPA NH4OAc H20 ppm --------- Zn ppm—--------- ---------Mn ppm- ------- - 0 6 3 <1 0.3 18.7 1.2 0.8 ND 50 59 36 3 0.3 17.4 1.3 1.0 ND 100 95 66 8 0.5 19.0 1.3 1.0 0.1 150 149 99 12 0.7 18.4 1.4 0.8 0.1 200 173 124 22 0.8 17.5 1.3 1.1 0.1 400 376 239 66 1.5 17.9 1.8 1.1 0.1 LSD (.05) 14 20 3 0.2 NS 0.2 0.2 0.1 Fe ppm-----—---- Cu ppmh ------ 0 292 201 3 1 8.6 0.6 0.3 0.3 ND 50 318 192 5.3 16.1 0.5 0.4 0.5 ND 100 309 209 5.3 15.9 0.5 0.6 0.4 ND 150 268 211 4.6 11.7 0.5 0.6 0.3 0.1 200 297 207 2 8 12.6 0.5 0.4 0.2 0.1 400 294 196 3 1 8.9 0.5 0.4 0.2 ND LSD (.05) 23 NS 0 8 4.2 0 l 0.2 0.1 NS aEach value is the average of three replications. ND = not detectable. 82 Table 23. Soil treatments and soil extractable metal concentrations for zinc-treated AuGres sand prior to cropping with field beans under ggeenhouse conditions . Extracting Agents Zn 0 . lg 0 . 005g 1g 0 . 1g 0 . 005g lg Tmt HCl DTPA NHAOAc H20 HCl DTPA NHAOAc H20 ppm Zn ppm? ----------------- Mn ppm—--------- 0 3 <1 <1 0.3 6.1 1.4 1.5 ND 50 27 18 5 0.3 7.0 2.9 2.0 0.1 100 59 25 12 0.5 7.5 2.1 2.4 0.1 150 88 39 22 0.8 7.3 2.6 2.4 0.1 200 153 59 41 1.3 7.8 2.3 3.1 0.2 400 390 133 120 5.0 8.3 3.3 4.6 0.8 LSD (.05) 32 10 8 0.8 1.4 1.3 0.9 0.2 Fe ppm-- ------- Cu ppm---------- 0 48 46 2.1 1.2 0.5 0.1 0.1 0.2 50 55 54 2.2 3.2 0.4 0.2 0.1 ND 100 53 34 1.7 3.6 0.4 0.4 0.1 0.1 150 50 35 1.7 3.2 0.4 0.4 ND 0.1 200 54 33 1.7 3.8 0.4 0.3 0.1 ND 400 52 37 1.3 3.6 0.4 0.2 0.2 ND LSD (.05) 3 NS 0.7 1.8 NS 0.1 NS NS 8Each value is the average of three replications. ND 8 not detectable. Table 24. Soil treatments and soil extractable metal concentrations for zinc-treated Roscommon sand prior to cropping with field beans under greenhouse conditions . - Extracting Agents Zn 0 . 1g 0 . 005g 1g 0 . 1g 0. 005g 1g Tmt HCl DTPA NH4OAc H20 HCl DTPA NHQOAc H20 Ppm Zn ppm---------- Mn ppm- --------- 0 3 2 <1 0.6 14.4 3.7 2.5 ND 50 31 21 3 0.5 14.8 4.1 2.8 0.4 100 104 33 8 0.8 14.6 5.0 4.2 0.4 150 125 59 14 0.9 14.8 5.2 4.7 0.4 200 173 73 21 1.5 16.2 6.1 5.0 0.6 400 341 167 78 2.6 16.9 6.4 5.5 0.8 LSD (.05) 19 10 6 0.6 2.2 0.7 0.8 0.2 Fe ppm --------- Cu ppm ---------- 0 150 205 2.7 ND 0.4 0.3 0.2 ND 50 173 122 3.9 0.4 0.4 0.4 0.2 0.1 100 184 130 4.8 0.4 0.4 0.4 0.2 ND 150 186 123 3.3 0.4 0.4 0.4 0.1 ND 200 197 135 2.4 0.6 0.4 0.4 0.2 ND 400 202 124 3.9 0.8 0.4 0.2 0.1 0.1 LSD gggg) 21 33 0.5 9.3 NS 0.1 NS NS aEach value is the average of three replications. ND = not detectable. 83 Table 25. Soil treatments and soil extractable metal concentrations for zinc-treated Rubicon sand prior to cropping with field beans under greenhouse conditions . Extracting Agents Zn 0.lN_ 0.003! Mg 0.1N_ 0.005! 1N Tmt HCl DTPA NH40Ac H20 HCl DTPA NHAOAc H20 ppm —Zn ppm--------- ---------- Mn ppm ---------- 0 6 2 <1 0.5 53 5.4 7.6 ND 50 31 17 4 0.6 75 8.0 11.7 0.5 100 71 32 10 0.8 80 15.0 17.4 1.0 150 71 33 10 0.8 74 17.7 18.4 0.9 200 144 56 24 1.7 45 9.5 12.6 0.8 400 308 112 83 3.4 73 19.3 25.4 3.3 LSD (.05) 32 16 11 0.3 NS 4.7 7.3 1.0 Fe ppm—-—------~ Cu ppm— --------- 0 144 75 4.8 4.8 0.5 0.2 0.2 1.4 50 177 88 4.4 11.7 0.5 0.4 0.2 0.1 100 158 89 2.6 11.4 0.5' 0.3 0.2 0.1 150 155 68 4.4 10.8 0.5 0.2 0.2 ND 200 182 92 3.1 6.4 0.5 0.2 0.2 0.1 400 162 84 3.9 5.1 0.5 0.4 0.2 ND LSD (.05) 8 21 0.9 4.3 NS 0.1 NS NS 8Each value is the average of three replications. ND - not detectable. Table 26. Soil treatments and soil extractable metal concentrations for zinc-treated Granby loamy sand prior to crapping with field beans under greenhouse conditions . Extracting Agents Zn 0 . 1N 0. 005! IN 0 . IN 0. 005g; 1N Tmt HCl DTPA NH4OAc H20 H01 DTPA NHAOAc H20 ppm -Zn ppm— H; ppm ---------- 0 5 2 <1 0.6 18.9 1.2 1.0 ND 50 61 35 4 0.3 18.6 1.2 1.0 0.1 100 89 67 7 0.6 18.2 1.2 0.9 0.1 150 161 107 15 1.0 19.7 2.6 1.5 0.1 200 203 135 19 0.8 19.5 1.4 1.0 0.1 400 392 238 68 1.8 18.4 1.9 1.1 0.1 LSD (.05) 34 11 4 0.4 1.2 NS NS 0.1 Fe ppm-------- Cu ppm ---------- 0 275 216 3.5 7.0 0.6 0.2 0.2 ND 50 332 217 5.0 17.1 0.7 0.6 0.9 0.1 100 331 204 5.1 16.7 0.5 0.6 0.4 0.2 150 304 245 4.6 14.9 0.6 0.6 0.3 0.1 200 284 207 3.0 12.8 0.5 0.4 0.2 ND 400 287 210 2.4 13.2 0.5 0.6 0.2 ND LSD $.05) 23 NS 0.9 4.8 0.2 NS 0.2 0.2 8Each value is the average of three replications. ND = not detectable. 84 Table 27. Soil treatments and soil extractable metal concentrations for zinc-treated AuGres sand prior to cropping with tomatoes under greenhouse conditions . Extracting Agents Zn 0.1N. 0.0055 1N. 0.1N 0.003! 1N Tmt HCl DTPA NHAOAc H20 HCl DTPA NHAOAc H20 ppm Zn ppm--------- ---------Mn ppm ---------- 0 2 <1 <1 0.4 5.0 0.7 0.4 ND 50 15 7 2 0 4 7.6 1.8 0.6 0.2 100 49 25 6 0.8 7.2 2.3 0.9 0.2 150 83 52 13 0.8 7.2 2.2 1.9 0.1 200 114 78 20 1.0 8.1 3.0 2.4 0.2 400 284 181 84 3 7 7.2 3.8 3.1 0.4 LSD (.05) 25 7 5 0.2 1.1 0.6 0.4 0.1 - Fe ppm ---------- Cu ppm ---------- 0 44 36 1.7 3.3 0.7 0.2 0.3 0.2 50 42 35 3.1 4.1 0.7 0.2 0.2 ND 100 42 39 2.3 4.7 0.7 0.2 0.2 ND 150 41 38 1.9 4.3 0.7 ‘ 0.2 0.2 ND 200 41 44 2.1 3.2 0.7 0.2 0.2 ND 400 40 43 1.7 2.7 0.7 0.2 0.2 ND LSD (.05) 3 4 0.7 0.2 NS NS 0.1 NS 8Each value is the average of three replications. ND 3 not detectable. Table 28. Soil treatments and soil extractable metal concentrations for zinc-treated Roscommon sandaprior to cropping with tomatoes under greenhouse conditions . Extracting Agents Zn 0 . 1N 0 . 005g 1g 0 . IN 0 . 005g 1g Tmt HCl DTPA NH40Ac H20 H01 DTPA NHAOAc H20 ppm == Zn ppm- --------- Mn ppm— 0 3 1 <1 0.3 13.7 2.0 1.0 N 50 26 12 2 0 5 13.6 2.6 0.9 0. 100 65 34 4 0.8 13.2 3.7 1.4 0. 150 112 60 9 1.0 15.1 3.9 2.7 0. 200 139 69 15 1.1 15.8 5.6 3.7 0. 400 302 186 57 3 1 15.0 7.0 4.2 0. LSD (.05) 17 9 6 0 2 NS 0.8 0.9 0. Fe ppm— -------- ---------—Cu ppm- --------- 0 145 145 1.3 ND 0.7 0.4 ND ND 50 135 162 6.6 0.2 0. 0.4 0.1 ND 100 136 156 6.6 0.2 0.9 0.3 0.1 ND 150 140 145 6.2 0.2 0.9 0.4 0.2 ND 200 146 122 6.0 0.3 0.9 0.3 0.2 ND 400 140 122 7.0 0.5 0.9 0.3 0.2 ND LSD (.05) NS 32 0.4 6.0 NS 0.1 0.1 NS 3Each value is the average of three replications. ND = not detectable. 85 Table 29. Soil treatments and soil extractable metal concentrations for zinc-treated Rubicon sand prior to cropping with tomatoes underggreenhouse conditions . Extracting Agents - Zn 0 . IN 0. 005g 15 O . IN 0. 00531 IN Tmt HCl DTPA NH40Ac H20 HCl DTPA NHAOAc H20 ppm Zn ppm------—--- ---------- Mn ppm —————————— 0 5 1 <1 0.3 57 4.8 3.7 ND 50 35 7 2 0.9 83 8.5 4.3 0.5 100 59 22 4 1.1 70 10.9 7.1 0.8 150 73 40 5 1.1 81 10.3 6.0 0.? 200 125 48 10 1.9 44 6.8 5.0 0.7 400 365 141 35 3.7 83 19.5 16.6 2.7 LSD (.05) 24 9 2 0.3 26 3.5 3.2 0.3 Fe ppm---------- Cu ppm ---------- 0 129 70 2.2 6.5 0.7 0.3 0.2 0.1 50 166 64 4.3 24.2 1.2 0.3 0.1 ND 100 120 68 5.0 21.4 1.0 0.3 0.2 ND 150 136 100 4.8 22.2 1.1 0.3 0.2 0.1 200 159 94 4.8 22.8 1 1 0.3 0.2 0.1 400 147 100 4.8 19.5 1.1 0.3 0.2 ND LSD (.05) 18 19 0 8 3.7 0.2 NS NS NS 8Each value is the average of three replications. ND - not detectable. Table 30. Soil treatments and soil extractable metal concentrations for zinc-treated Granby loamy 83nd prior to cropping with tomatoes underggreenhouse conditions . Extracting Agents Zn 0.1N_ 0.005! 1§_ 0.1N. 0.005! LN Tmt HCl DTPA NHAOAc 320 HCl DTPA NHAOAc H20 ppm Zn ppm -------- ,----------Mn ppm ---------- 0 6 2 0.3 0.4 16.8 1.2 0.5 ND 50 28 26 2.3 0.5 17.1 1.0 0.2 0.1 100 105 53 4.7 0.7 19.4 1.0 0.3 0.1 150 157 98 11.2 1.0 20.8 2.3 0.6 0.1 200 201 111 12.7 1.2 21.2 1.0 0.3 0.1 400 400 235 32.8 2.0 21.4 1.4 0.3 0.2 LSD (.05) 13 28 4.2 0.3 1.3 NS NS 0.1 Fe pme--------- Cu ppm: 0 235 185 2.4 10.2 1.1 0.3 0.2 0.4 50 259 174 6.8 24.1 0.9 0.4 0.2 ND 100 263 172 5.0 25.2 0.9 0.3 0.2 ND 150 275 207 4.5 22.6 0.9 0.4 0.2 0.1 200 252 172 5.2 25.2 0.9 0.3 0.2 ND 400 268 154 5 4 22.8 0.9 0.4 0.2 ND LSD (.05) 25 NS 1 0 6.1 NS 0.1 NS 0.1 aEach value is the average of three replications. ND = not detectable; 86 Table 31. Soil treatments and soil extractable metal concentrations for zinc-treated AuGres sand prior to cropping with corn 11 under #greenhouse conditions . Extracting Agents Zn 0.1N_ 0.0053 1N_ 0.DN 0.005! 1N Tmt HCl DTPA NHAOAc H20 HCl DTPA NHAOAc H20 ppm —— Zn ppm--------- ----------Mn ppm 0 2 <1 <1 0.3 5.0 0.7 0.5 ND 50 13 6 1 0.4 6.3 1.6 0.5 0.2 100 40 27 4 0.6 6.6 1.3 0.8 0.1 150 75 45 9 0.7 6.9 2.0 1.8 0.2 200 105 67 16 1.0 6.7 2.1 1.2 0.1 400 263 165 80 3.5 6.5 3.3 2.7 0.3 LSD (.05) 25 11 3 0.5 1.4 0.4 0.4 0.1 ----------- Fe ppm Cu ppmr--------- 0 40 37 1.1 2.0 0.7 0.2 0.2 0.1 50 41 33 2.5 4.9 0.7 0.2 0.2 ND 100 43 33 2.3 4.0 0.7 0.2 0.2 ND 150 41 36 1.9 4.3 0.7 0.2 0.2 ND 200 42 36 1.9 2.8 0.7 0.2 0.1 ND 400 35 38 1.7 3.3 0.7 0.2 0.2 ND LSD (.05) 4 3 1.0 1.1 NS NS NS NS 8Each value is the average of three replications. ND = not detectable. Table 32. Soil treatments and soil extractable metal concentrations for zinc-treated Roscommon sandaprior to cropping with corn 11 under greenhouse conditions . --- Extracting Agents— -— Zn 0.1N 0.005! 1N 0.1N. 0.0055' 1N Tmt HCl DTPA NHAOAc H20 HCl DTPA NHAOAc H20 ppm Zn ppm --------- F ppm --------- 0 3 <1 <1 0.4 12.8 1.3 0.4 ND 50 3o 11 1 0.5 11.7 2.0 0.8 0.2 100 74 33 4 0.8 13.6 1.9 0.7 0.2 150 109 62 8 1 2 13.6 2.5 1.5 0.2 200 132 65 14 1 4 13.4 3.9 2.5 0.2 400 312 184 66 3 5 13.6 6.4 4.1 0.5 LSD (.05) 45 36 16 1.4 NS 2.0 1.1 0.3 Fe ppm-------- Cu ppm--------- o 140 112 1 o 17.9 0.7 0.4 ND 0.2 50 130 144 7.0 26.9 o 9 0.3 ND ND 100 132 129 6.4 29.3 0.9 0.4 0.1 ND 150 131 135 6.4 31.6 0.9 0.2 0.1 ND 200 134 98 6.4 28.9 0.9 0.3 0.2 ND 400 138 97 7.8 25.1 0.9 0.3 0.2 ND LSD (.951, NS 21 1 6 6.2 NS 0.1 0.2 NS 8Each value is the average of three replications. ND = not detectable. 87 Table 33. Soil treatments and soil extractable metal concentrations for zinc-treated Rubicon sand prior to crapping with corn 11 under greenhouse conditions . Extracting Agents Zn 0 . 1! 0 . oosg 1}! 0 . 11! 0 . 005! IN Tmt HCl DTPA NH40Ac H20 H01 DTPA NH40Ac H20 ppm Zn ppm------- . ppm ---------- 0 5 1 <1 0.3 69 5.6 3.7 ND 50 34 6 2 1.0 92 5.6 3.0 0.8 100 66 23 4 1.5 88 9.3 4.4 0.7 150 90 44 6 1.7 75 8.4 5.3 0.7 200 139 51 10 2 2 86 11.2 8.4 0.6 400 306 133 34 4.1 71 15.9 12.1 1.4 LSD (.05) 22 2 2 0.4 17 3.7 1.6 0.3 Fe ppm-------- Cu ppm ---------- 0 116 64 1 9 4.5 0.7 0.2 0.1 ND 50 190 45 4.6 29.2 1.1 0.3 0.2 ND 100 198 54 4.6 32.2 1.1 0.3 0.1 ND 150 199 74 5.0 29.9 1.1 0.3 0.2 0.1 200 182 83 4.6 26.9 1.1 0.3 0.2 ND 400 181 84 5.6 29.1 1.1 0.3 0.3 ND LSD (.05) 32 14 0 7 3.4 NS 0.1 0.1 NS 8Each value is the average of three replications. ND 8 not detectable. Table 34. Soil treatments and soil extractable metal concentrations for zinc-treated Granby loamy 33nd prior to cropping with corn 11 under greenhouse conditions . - Extracting Agents --- Zn O.1N_ 0.005g 1N 0.1N, 0.005!’ 1N Tmt HCl DTPA NHAOAc H20 HCl DTPA NH4OAc H20 ppm Zn ppm Mn ppm---------- 0 6 5 <1 0.9 19.2 1.7 0.8 ND 50 31 25 2 0.5 17.4 0.9 0.2 0.1 100 104 54 4 0.7 18.7 1.0 0.3 0.1 150 139 83 8 0.9 18.9 1.0 0.3 0.1 200 187 107 11 1.2 18.7 1.3 0.2 0.1 400 381 227 30 2.2 20.3 1.4 0.2 0.1 LSD (.05) 66 20 16 0.4 NS NS 0.5 0.1 —Fe ppm -------- Cu ppm 0 271 206 3.4 6.4 1.1 0.4 0.1 0.1 50 250 161 6 8 24.4 0.9 0.3 0.2 ND 100 243 155 4.0 20.3 0.9 0.3 0.2 0.1 150 252 163 5.0 22.2 0.9 0.3 0.2 ND 200 264 162 4.6 28.9 0.9 0.4 0.2 ND 400 272 151 5.6 26.9 0.9 0.3 0.2 ND LSD (.05) 18 28 1.3 5.4 NS NS NS NS 8Each value is the average of three replications. ND = not detectable. 88 Table 35. Effects of soil type and treatment level on H20 extractable zinc concentrations from zinc-treated soils under greenhouse conditionsa. Zn AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt PPm ppm Zn 0 0.3 0.4 0.4 0.5 0.4 50 0.3 0.5 0.6 0.3 0.4 100 0.5 0.7 0.8 0.6 0.6 150 0.8 0.9 1.1 0.9 0.9 200 1.2 1.5 1.8 0.8 1.3 400 5.9 2.5 3.5 1.6 3.3 LSD (:05): Treatment level among_soils 0.6;» Soils within tmt. 0.4 aEach value is the average of six replications. Table 36. Effects of soil type and treatment level on 1N_NH40Ac extract- able zinc concengrations from zinc-treated soils under green- house conditions . Zn AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt PPm ppm Zn 0 <1 <1 <1 <1 <1 50 4 3 4 3 4 100 12 8 10 7 9 150 21 15 14 14 16 200 39 22 27 20 27 400 126 79 87 67 89 LSD (.05): Treatment level among soils 6;, Soils within tmt. 4 aEach value is the average of six replications. Table 37. Effects of soil type and treatment level on 0.005M DTPA ex- tractable zinc concengrations from zinc-treated soils under 4g£eenhouse conditions . Zn AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt mm mm Zn 0 <1 2 2 2 2 50 16 20 17 35 22 100 28 35 31 67 37 150 42 57 37 103 60 200 62 72 65 130 82 400 144 164 125 239 168 LSD (.05): Treatment level among soils 11; Soils within tmt. 7 8Each value is the average of six replications. 89 Table 38. Effects of soil type and treatment level on 0.1N_HC1 extract- able zinc concentrations from zinc-treated soils under green- house conditions . Zn AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt ppm ppm Zn 0 3 3 6 6 4 50 26 30 31 60 37 100 59 96 69 92 79 150 91 123 96 155 114 200 153 164 148 188 163 400 373 343 317 384 354 LSD (.05): Treatment level among soils 21; Soils within tmt. l4 8Each value is the average of six replications. Table 39. Effects of soil type and treatment level on H20 extractable manganese concentrations from zinc-treated soils under Agreenhouse conditions . Zn AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy_sand within tmt ppm Ppm Mr- 0 0 0 0 0 0 50 0.1 0.4 0.5 1.0 0.3 100 0.1 0.4 0.9 1.0 0. 4 150 0.2 0.5 0.9 1.1 0. 4 200 0.3 0.6 1.1 1.1 0.5 400 1.4 0.7 3.2 1.1 1.3 LSD (.05): Treatment level among soils 0.5; Soils within tmt. 0. 3 3Each value is the average of six replications. Table 40. Effects of soil type and treatment level on 1N NH40Ac ex- tractable manganese concentrations from zinc-treated soils under greenhouse conditions . Zn AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt PPm ppm Mn 0 1.5 2.3 9.5 0.9 3.6 50 1.8 3.0 10.6 1.0 4.1 100 2.2 4.4 15.3 1.0 5.7 150 2.4 4.7 16.6 1.1 6.2 200 3.0 4.9 15.2 1.1 6.0 400 4.6 5.4 23.5 1.1 8.6 LSD (.05): Treatment level among soils 2.5; Soils within tmt. l 5 aEach value is the average of six replications. 90 Table 41. Effects of soil type and treatment level on 0.005! DTPA ex- tractable manganese concentgations from zinc-treated soils under greenhouse conditions . Zn AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt PPm ppm Mn 0 1.4 3.5 6.6 1.2 3.2 50 2.3 4.1 7.2 1.3 3.7 100 2.1 4.9 12.0 1.2 5.1 150 2.4 5.3 13.4 2.0 5.7 200 2 2 5.7 11.2 1.3 5.1 400 3.2 6.3 18.4 1.8 7.4 LSD 1.05): Treatment level amongfsoils 1.9;g Soils within tmt. 1.2 aEach value is the average of six replications. Table 42. Effects of soil type and treatment level on 0.1N_HC1 extract- able manganese concengrations from zinc-treated soils under greenhouse conditions . Zn AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt PPm ppm Mn _ ~ 0 6.5 13.7 58.1 18.8 24.2 50 7.1 14.0 82.8 18.0 30.5 100 7.4 15.0 82.8 18.6 30.9 150 7.2 14.7 76.9 19.0 29.5 200 7.2 15.2 66.4 18.5 26.8 400 8.0 16.4 82.4 18.2 27.1 LSD (.05): Treatment level among soils 15.6; Soils within tmt. NS aEach value is the average of six replications. Table 43. Effects of soil type and treatment level on H20 extractable iron concentrations from zinc-treated soils under green- house conditions . Zn AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt PPm ppm Fe 0 1.3 7.6 4.6 7.8 5.3 50 3.3 23.6 13.1 16.6 14.1 100 4.0 25.8 11.9 16.3 14.5 150 3.6 21.9 11.1 13.3 12.5 200 3.5 25.7 6.6 12.7 12.1 400 2.8 8.4 6.0 11.1 7.1 LSD (.05): Treatment level amongssoils 4.2; Soils within tmt. 2.6 8Each value is the average of six replications. 91 Table 44. Effects of soil type and treatment level on 1N_NH40Ac extract— able iron concengrations from zinc-treated soils under green- house conditions . Zn AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt PPm ppm Fe 0 1.7 2.5 4.1 3.3 2.9 50 2.2 4.2 4.4 5.2 4.0 100 1.7 4.3 3.0 5.3 3.6 150 1.9 2.9 4.2 4.5 3.4 200 1.3 2.7 3.5 2.9 2.6 400 1.5 4.0 3.9 2.8 3.0 LSD (.051; Treatment level among soils 0.7; Soils within tmt. 0.4 8Each value is the average of six replications. Table 45. Effects of soil type and treatment level on 0.005! DTPA ex- tractable iron concengrations from zinc-treated soils under 4greenhouse conditions . Zn AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt ppm ppm Fe 0 48 203 78 208 135 50 46 121 84 204 114 100 36 127 85 207 114 150 35 127 70 228 115 200 34 120 83 207 111 400 36 121 78 203 110 LSD (.05): Treatment level among soils 21; Soils within tmt. 13 aEach value is the average of six replications. Table 46. Effects of soil type and treatment level on 0.1N-8C1 extract- able iron concensrations from zinc-treated soils under green- house conditions . 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oaoaoaona ”Amo.v omo oo mo o.m om mo m.N mo mo N.o No mo o.o ooo om mo o.m No oo o.N NN oo o.o oN oo o.N ooN No mo m.o mo oo o.o mo mo o.m No o m.o ooo omo mo o.N NNo oo o.N oN oN N.m mo oo m.o om mo mo o.m NNo oN m.o Noo mo m.m mN oo o.N o ooo\on Boo ooo\m ooon: Boo oooN» ooo\w: aoo oooxo ooo\on Boo oome Boo omo: 6:60 “3 Non ooo: coco oz zno ooo: uaoo as zoo zoo: oaoo as one use ocao zaaoo zcaano oaao ooooo:z oaao aosaoomoz oaaa aono:< no .amaoooooaoo oo:ocaoonw noon: moooo oooaonuIa:osonco co :sonw ooooaaou zc ooouo: ooo coooanocoocoo nooooo .ocwoos zno ocaoo co oo>oo ocoaoaono oca oozo oooa mo oooommo .mo oooaa 102 Table 67. Influence of chromium treatments on soilapH - first sampling prior to planting corn 1 and field beans . Soils Soil Tmts AuGres Roscommon Rubicon Granby Chromium sand sand sand loamy sand PPm PH 0 7.49 7.28 7.23 7.43 50 7.42 7.21 7.18 7.41 100 7.42 7.11 7.09 7.35 200 7.37 6.98 7.08 7.25 400 7.33 6.75 6.88 7.14 LSD (.05) 0.09 0.33 0.13 0.10 aEach value is the average of six replications. Table 68. Influence of chromium treatments on soil pH - second sampling a prior to planting corn II and tomatoes . Soils Soil Tmts AuGres Roscommon Rubicon Granby Chromium sand sand sand loamy sand ppm PH 0 7.51 7.27 7 01 7.40 50 7.38 7.14 6.95 7.47 100 7.45 7.04 6.95 7.39 200 7.38 6.75 6 83 7 19 400 7.31 6.45 6.54 7 00 LSD (.05) 0.14 0.18 0.20 0.25 8Each value is the average of six replications. 103 Table 69. Soil treatments and soil extractable metal concentrations for chromium-treated AuGres sand prior to cropping with corn I under greenhouse conditionsa. Extracting Agents Cr 0.1N 0.005M 1N 0.1N 0.005! 1N Tmt HCl DTPA NH4OAc H20 HCl DTPA NHAOAc H20 ppm Cr ppm- ------------------ Zn ppm --------- 0 ND ND ND ND 2.7 1.0 0.5 0 3 50 19 1.2 0.8 ND 2.6 1.3 0.5 0 3 100 33 1.5 1.9 ND 3.4 1.7 0.5 0 4 200 55 1.7 4.1 ND 3.5 1.6 0.5 0 3 400 89 1.5 7.4 ND 3.0 2.4 0.5 0 6 LSD (.05) 6 0.4 1.7 NS NS NS NS NS ----------- Mn ppm ----------Fe ppm-—-——---- 0 6.7 1.4 1.5 ND 45 49 1.3 1.4 50 6.8 1.8 1.5 ND 46 36 1.4 1.1 100 7.2 2.1 2.0 ND 45 36 1.1 2.4 200 7.3 2.1 1.8 0.2 50 33 0.7 1.2 400 6.9 3.3 2.0 0.1 55 28 0.7 1.1 LSD (.05) NS 0.8 NS NS 4 8 NS 1.3 Cu ppm— --------- 0 O 6 0.1 0.4 ND 50 O 4 0.1 0.2 ND 100 0.4 0.1 0.1 ND 200 0.4 0.2 0.2 0.2 400 0.4 0.2 0.1 0.1 LSD (.05)0.l NS 0.3 NS aEach value is the average of three replications. ND = not detectable. 104 Table 70. Soil treatments and soil extractable metal concentrations for chromium-treated Roscommon sand prior to cropping with corn 1 under greenhouse conditions . Extracting Agents Cr 0.l_N_ 0.005M IE 0.1}! 0.005! 1N, Tmt HCl DTPA NHAOAc H20 HCl DTPA NH40Ac H20 ppm Cr ppm— -------- ----------Zn pme-------- 0 ND ND ND ND 3.2 1.6 0.4 0.3 50 18 1.0 0.6 ND 3.2 1.6 0.4 0.2 100 37 1.2 1.3 ND 3.0 1.7 0.4 0.4 200 60 1.7 2.8 ND 2.9 1.8 0.4 0.3 400 92 1.6 6.1 ND 3.7 2.3 0.5 0.6 LSD (.05) 5 0.4 0.7 NS NS 0.6 NS 0.2 Mn ppm ---------- ----—-----Fe ppmr -------- 0 12.9 3.3 2.0 ND 161 201 2.4 7.1 50 13.7 3.6 2 2 ND 164 176 1.8 6.1 100 14.1 4.3 2.5 ND 160 155 1.8 4.1 200 14.5 4.6 2.8 ND 164 126 1.1 0.9 400 14.6 5.6 3.2 0.7 165 108 1.6 1.1 LSD (.05)l.5 0.9 0 9 0.6 NS 32 0.4 4.4 on pp --------- 0 0.4 0.3 0.1 0.1 50 0.4 0.2 0.1 0.1 100 0.4 0.2 0.1 0.2 200 0.4 0.2 0.2 0.2 400 0.4 0.2 0.3 ND LSD (.05) NS NS NS NS 8Each value is the average of three replications. ND = not detectable. .105 Table 71. Soil treatments and soil extractable metal concentrations for chromium-treated Rubicon sand prior to cropping with corn I under greenhouse conditionsa. Extracting Agents -- Cr 0 . 111 0 . 005M 1N 0 . 1N 0 . 00531 IN Tmt HCl DTPA NH40Ac 320 HCl DTPA NHAOAc H20 ppm Cr ppm ----—-----Zn ppm--—------- 0 ND ND ND ND 6.7 2.2 0.7 0.3 50 23 1.3 1.7 ND 7.3 2.9 0.7 0.4 100 37 1.3 3.4 ND 7.6 3.5 0.8 0.4 200 61 1.3 5.6 ND 7.6 3.9 0.9 0.4 400 95 1.2 12.5 ND 9.3 4.8 1.9 0.5 LSD (.05) 4 0.4 0.7 NS 1.5 1.2 NS NS Mn ppm ---------- Fe ppm 0 63 7.7 11.5 ND 140 81 3.4 4.4 50 67 9.1 12.3 ND 140 88 3.1 1.1 100 69 14.0 14.7 0.1 147 68 3.3 1.5 200 59 15.2 14.2 0.6 152 59 2.3 0.8 400 74 17.4 17.1 2.3 167 51 2.5 ND LSD (.05) NS 5.0 4.6 1.9 19 13 NS 1.9 Cu ppm 0 0.5 0.2 0.2 0.3 50 0.6 0.2 ND 0.1 100 0.5 0.2 0.3 0.3 200 0.5 0.2 0.2 D 400 0.5 0.2 ND ND LSD (.05) NS NS 0.2 NS aEach value is the average of three replications. ND = not detectable. 106 Table 72. Soil treatments and soil extractable metal concentrations for chromium-treated Granby loamy sandaprior to cropping with corn 1 under greenhouse conditions . Extracting Agents ___ Cr 0 . IN 0 . 005M 1N 0 . 1}! 0 . 005! 11! Tmt HCl DTPA NHAOAc H20 HCl DTPA NHAOAc H20 ppm Cr ppm Zn ppm --------- 0 ND ND ND ND 5.6 2.5 0.5 0.3 50 12 0.5 0.5 ND 5.7 2.6 0.5 0.3 100 27 0.9 1.2 ND 5.2 2.3 0.6 0.3 200 46 1.0 2.3 ND 5.6 2.4 0.4 0.4 400 72 1.3 5.6 ND 8.2 4.3 0.5 0.5 LSD (.05) 8 0.3 1.8 NS NS NS 0.1 NS Mn ppm --------- Fe ppm 0 18.7 1.2 0.8 ND 292 201 3 l 8.6 50 17.5 1.1 0.7 ND 282 208 3.3 5.3 100 16.8 1.4 0.7 ND 260 181 2.6 4.7 200 16.6 1.4 0.9 ND 255 194 2 2 1.7 400 16.6 2.1 1.4 ND 261 157 2 7 0.1 LSD (.05) NS 0.9 0.7 NS 32 44 NS 2.4 v0 PPm—“ 0 0.6 0.3 0.3 ND 50 0.6 0.3 0.1 0.1 100 0.7 0.3 0.1 ND 200 0.7 0.3 0.3 0.1 400 0.6 0.4 0.2 ND LSD (.05) NS NS NS NS 3Each value is the average of three replications. ND = not detectable. 107 Table 73. Soil treatments and soil extractable metal concentrations for chromiumztreated AuGres sand prior to cropping with field beans under greenhouse conditions . Extracting Agents Cr 0 . 1N 0 . OOSN IN 0 . 1N 0 . 005_M_ 1N Tmt HCl DTPA NH40Ac H20 HCl DTPA NHAOAc H20 ppm Cr ppm ------- Zn ppmr—------- 0 ND ND ND ND 2.5 0.8 0.5 0.3 50 20 1.2 0.5 0.2 2.4 0.9 0.4 0.4 100 33 1.8 2.2 0.2 2.3 0.9 0.4 0.4 200 57 1.6 4.1 ND 2.7 0.9 0.4 0.5 400 88 1.6 8.9 0.7 2.7 1.3 0.5 0.5 LSD (.05) 7 0.3 1.7 NS NS 0.4 NS NS - Mn ppm ---------Fe ppm 0 6.1 1.4 l 5 ND 48 46 2.1 1.3 50 5.8 1.5 1 7 ND 52 37 2 5 0.7 100 6.6 1.7 1.8 ND 49 37 1.3 0.1 200 7 1 1.6 1.5 ND 52 26 1.5 0.8 400 7 l 2.0 2.0 ND 58 25 1.1 0.3 LSD (.05) 0.9 NS NS NS 5 11 NS NS UU ppm 0 0.5 0.1 0.1 0.2 50 0.5 0.1 0.1 ND 100 0.4 0.1 0.1 ND 200 0.4 0.2 0.1 ND 400 0.4 0.2 0.1 ND LSD (.05) 0.1 NS NS NS 3Each value is the average of three replications. ND - not detectable. 108 Table 74. Soil treatments and soil extractable metal concentrations for chromium-treated Roscommon sand prior to cropping with field beans under greenhouse conditionsa. — —Extracting Agents- Cr 0.1N. 0.003! 1N. O.LN 0.00flN 1N Tmt H01 DTPA NHAOAc H20 HCl DTPA NH40Ac H20 ppm Cr ppm ---------- 2n ppm--------- 0 ND ND ND ND 2.8 1.6 0.5 0.6 50 19 1.1 0.5 ND 3.0 1.6 0.4 0.3 100 33 1.5 1.5 ND 3.2 1.5 0.4 0.5 200 60 2.0 4.4 0.2 3.3 1.9 0.4 0.5 400 83 2.2 9.5 ND 3.0 1.8 0.3 0.5 LSD (.05) 6 0.4 0.8 NS NS NS NS NS Mn ppm -------- Fe ppm 0 14.4 3.7 2.5 ND 150 205 2.7 8.0 50 13.2 3.9 2.7 ND 154 181 2.6 13.6 100 13.3 4.4 3.0 ND 155 157 2.8 4.5 200 15.6 4.9 3.6 ND 168 148 2.8 3.2 400 14.7 5.5 3.8 .2 172 129 2.4 0.9 LSD (.05) 2.0 1.1 0.9 . 16 44 NS 8.7 Cu ppm 0 0.4 0.3 0.2 ND 50 0.4 0.3 0.1 ND 100 0.4 0.2 ND 0.2 200 0.4 0 2 0.1 ND 400 0.4 0.2 0.1 0.1 LSD (.05) NS NS NS NS aEach value is the average of three replications. ND = not detectable. 109 Table 75. Soil treatments and soil extractable metal concentrations for chromium-treated Rubicon sand prior to cropping with field beans under greenhouse conditions . Extracting Agents Cr 0 . 1N 0 . OOSN 1N 0 . IN 0 . OOSN 1N Tmt HCl DTPA NH40Ac H20 H01 DTPA NH40Ac H20 ppm Cr ppm-------- ---------- Zn ppmz- -------- 0 ND ND ND ND 6.0 1.5 0.5 0.5 50 22 1.1 1.2 ND 5.1 1.7 0.4 0.4 100 40 1.8 3.2 ND 5.7 2.0 0.5 0.2 200 62 1.6 5.5 0.3 6.6 2.1 0.6 0.4 400 86 1.5 7.1 ND 7.0 2.8 1.5 0.6 LSD (.05) 3 0.2 1.5 NS NS NS NS 0.3 Mb ppm -------- - -------- Fe pme------- 0 53 5.4 7.6 ND 144 75 4.8 4.8 50 45 8.0 9.6 0.1 140 75 3.9 1.5 100 49 11.3 11.9 0.1 135 74 3.7 1.5 200 66 15.0 13.7 0.3 139 54 3.0 0.4 400 61 18.0 14.4 1.4 131 38 2.1 1.1 LSD (.05) NS 7.6 NS 0.6 NS 13 2.3 2.1 -- Cu ppm--------- 0 0 5 0.2 0.2 1.4 50 0.5 0.2 0.2 ND 100 0.6 0.2 0.3 0.4 200 0.5 0.2 0.2 ND 400 0.5 0.2 ND ND LSD (.05) NS NS 0.3 NS 8Each value is the average of three replications. ND = not detectable. 110 Table 76. Soil treatments and soil extractable metal concentrations for chromium-treated Granby loamy sand prior to cropping with field beans under greenhouse conditionsa. Extracting Agents Cr 0. IN 0 . OOSN 1N 0 . IN 0 . OOSN 1N Tmt HCl DTPA NH40Ac H20 HCl DTPA NHAOAc H20 ppm Cr ppm — -------- Zn ppmr--------- 0 ND ND ND ND 5.4 2.4 0.4 0.6 50 13 0.5 0.7 ND 5.8 2.7 0.4 0.4 100 24 0.8 1.1 ND 5.2 2.6 0.4 0.4 200 39 1.0 2.1 ND 5.6 2.5 0.3 0.2 400 63 1.3 4.2 0.1 5.3 2.3 0.3 0.3 LSD (.05) 4 0.2 0.5 NS NS NS NS NS ----------- Mn ppm ---------Fe ppmo 0 18.9 1 2 1.0 ND 275 216 3.5 7.0 50 19.1 1.1 0.9 ND 300 211 3.9 4.6 100 17.2 1.2 1.5 0.2 258 199 3.4 5.1 200 17.3 1.3 1.1 ND 269 181 3.2 4.8 400 16.3 2.0 0.9 ND 258 155 2.9 2.1 LSD (.05) 1.0 0.3 NS NS 29 37 NS 3.5 Cu ppm 0 0.6 0.2 0.2 ND 50 0.7 0.3 0.1 0.2 100 0.7 0.2 0.2 0.3 200 0.7 0.2 0.2 ND 400 0.6 0.3 0.2 0.3 LSD (.05) NS NS NS NS 3Each value is the average of three replications. ND = not detectable. 111 Table 77. Soil treatments and soil extractable metal concentrations for chromium-treated AuGres sand prior to cropping with tomatoes under greenhouse conditionsa. Extracting Agents Cr 0 . 1N 0 . 005N 1N 0 . 1N 0 . OOSN 1N Tmt HCl DTPA NH40Ac H20 H01 DTPA NHAOAc H20 ppm Cr ppm -------- ----------Zn ppm------- 0 ND ND ND ND 1.8 0.8 0.2 0.4 50 21 0.9 0.3 0.1 1.8 0.7 0.2 0.4 100 35 1.1 0.8 0.1 1.7 0.6 0.3 0.3 200 51 1.6 1.9 ND 1.7 0.7 0.2 0.2 400 98 1.5 3.4 0.1 2.0 0.8 0.3 0.4 LSD (.05) 8 0.1 0.8 NS NS NS NS NS Mn ppm------- ---------Fe ppm --------- 0 5.0 0.7 0.4 ND 44 36 1.7 3.3 50 4.7 0.7 0.6 ND 44 37 1.3 3.8 100 5.1 1.0 0.7 ND 42 24 0.7 2.6 200 4.6 1.0 0.6 0.1 40 31 0.8 2.1 400 5.2 1.5 0.9 0.5 51 24 0.9 0.5 LSD (.05) NS 0.2 NS 0.2 . 6 6 NS 1.6 Cu ppm--——----— 0 0.7 0.2 0.3 0.2 50 0.7 0.2 0.1 0.2 100 0.7 0.2 0.1 ND 200 0.7 0.2 0.1 0.2 400 0.7 0.2 0.1 0.4 LSD (.05) NS NS NS NS 3Each value is the average of three replications. ND = not detectable. 112 Table 78. Soil treatments and soil extractable metal concentrations for chromium-treated Roscommon sand prior to cropping with tomatoes under greenhouse conditions . Extracting Agents Cr 0 . 1N 0 . OOSN 1N 0 . 1N 0 . OOSN 1N Tmt HCl DTPA NH40Ac HZO HCl DTPA NHAOAc H20 ppm Cr ppm ----------------- Zn ppm --------- 0 ND ND ND ND 2 9 1.1 0.3 0.3 50 18 0.6 0.1 ND 3.0 1.1 0.4 0.4 100 34 1.2 0.7 ND 3.3 1.3 0.3 0.2 200 51 2.1 1.6 ND 2 7 1.2 0.4 0.3 400 82 2.3 3.3 0.3 3 0 1.5 0.3 0.4 LSD (.05) 10 0.3 0. NS NS 0.2 NS 0.1 Mn ppm-—--——--- —--------Fe ppmr-----—- 0 13.7 2.0 1.0 ND 145 145 1.3 14.5 50 13.1 1.8 1.1 ND 141 131 2.0 13.4 100 12.7 2.3 1.2 ND 141 137 1.2 14.8 200 11.6 4.0 1.9 ND 140 134 1.1 8.8 400 11.3 6.6 3.1 0.4 145 123 0.5 2.7 LSD (.05) NS 1.1 0.7 NS NS NS NS 4.9 Cu ppmr -------- 0 0.7 0.4 ND ND 50 0.7 0.4 0.1 0.1 100 007 004 001 001 200 0.7 0.3 0.1 ND 400 0.7 0.3 0.1 0.2 LSD (.05) NS 0.1 NS NS 8Each value is the average of three replications. ND = not detectable. 113 Table 79. Soil treatments and soil extractable metal concentrations for chromium-treated Rubicon sagd prior to cropping with tomatoes under greenhouse conditions . —- Extracting Agents Cr 0.1N o. oosN 1N 0.1N o. oosg 1N Tmt HCl DTPA NH40Ac H20 H01 DTPA NHAOAc H20 ppm Cr ppm ---------Zn ppm 0 ND ND ND ND 4.6 1.2 0.5 0.3 so 21 0.8 0.5 ND 4.4 1.2 0.4 0.4 100 39 0.9 1.4 0.1 4.9 1.3 0.4 0.4 200 67 1.5 3.3 ND 5.7 1.5 0.5 0.3 400 92 2.0 4.9 ND 6.8 2.6 0.5 0.4 LSD (.05) 15 0.4 0.6 NS NS 0.7 NS NS ----------- Mn ppm ----------Fe ppm 0 57 4.8 3.7 ND 129 70 2.2 6.5 50 49 4.8 3.9 ND 117 72 2.2 8.2 100 74 8.6 5.7 0.3 123 61 2.1 5.5 200 72 9.2 6.3 0.6 127 62 2.1 3.0 400 83 17.2 9.3 1.4 127 52 1.2 0.3 LSD (.05) NS 6.5 4.1 0.3 NS 18 0.7 4.8 Cu ppm-------- 0 0.7 0.3 0.2 0.1 50 0.7 0.2 0.2 0.1 100 0.7 0.2 0.1 0.1 200 0.7 0.2 D ND 400 0.7 0.2 0.1 ND LSD (.05) NS 0.1 NS NS 3Each value is the average of three replications. ND = not detectable. 114 Table 80. Soil treatments and soil extractable metal concentrations for chromiumrtreated Granby loamy sand prior to cropping with tomatoes under greenhouse conditionsa. Extracting Agents Cr 0 . 1N 0 . OOSN 1N 0 . 1N 0 . OOSN 1N Tmt HCl DTPA NH40Ac H20 HCl DTPA NH4OAc H20 ppm Cr ppm-------- ---------Zn ppm --------- 0 ND ND ND ND 5.5 2.4 0.3 0.4 50 14 0.6 0.1 ND 7.3 2.4 0.4 0.3 100 28 0.6 0.5 ND 6.0 2.2 0.4 0.3 200 47 1.2 1.0 ND 6.1 2.3 0.5 0.2 400 75 1.0 1.8 ND 6.8 2.2 0.3 0.4 LSD (.05) 9 0.1 0.7 NS NS NS NS NS == Mn ppm ------- Fe ppmr— ------- 0 16.8 1.2 0.5 ND 235 185 2.4 10.2 50 18.4 1.1 0.6 ND 238 210 2.3 12.2 100 16.4 1.1 0.4 ND 230 186 2.5 20.6 200 16.9 1.2 0 5 ND 232 174 2.3 9.2 400 16.2 1.7 0.6 ND 232 138 2.6 3.3 LSD (.05) 1.5 NS NS NS NS 35 NS 9.5 Cu pme------ 0 l 1 0.3 0.2 0.4 50 0.9 0.4 0.1 0.3 100 0.9 0.3 ND 0.1 200 0.9 0.3 0.2 0.2 400 0.9 0.2 0.1 0.3 LSD (.05) NS 0.1 NS NS 3Each value is the average of three replications. ND 8 not detectable. 115 Table 81. Soil treatments and soil extractable metal concentrations for chromium-treated AuGres sand prior to cropping with corn 11 under greenhouse conditionsa. Extracting Agents -—- Cr 0 . IN 0 . OOSN 1N 0 . IN 0 . OOSN 1N Tmt HCl DTPA NH40Ac H20 H01 DTPA NHAOAc H20 ppm Cr ppmz -------- --------Zn ppm------—-- 0 ND ND ND ND 1.5 0.8 0.3 0.3 50 18 1.0 1.0 ND 1.6 0.5 0.3 0.3 100 31 1.3 0.7 ND 1.6 0.6 0.3 0.5 200 57 1.7 2.1 0.2 1.6 0.7 0.3 0.3 400 90 1.4 3.0 0.3 1.8 0.7 0.3 0.3 LSD (.05) 9 0.2 1.3 NS NS NS NS NS Mn ppm-------- ---------Fe ppm-- ----- 0 5.0 0.7 0.5 ND 36 37 1.1 2.0 50 5.5 0.9 0.8 ND 39 35 1.3 1.4 100 5.0 0.9 2.2 ND 37 32 0.6 0.5 200 4.7 1.3 0.9 ND 42 27 1.0 1.2 400 4.5 1.5 0.9 ND 47 22 0.6 0.7 LSD (.05) NS 0.3 NS NS 7 6 NS NS Cu ppm- ------ 0 0.7 0.2 0.2 0.1 50 0.7 0.2 0.1 ND 100 0.7 0.3 0.1 ND 200 0.7 0.2 0.1 0.1 400 0.7 0.2 0.1 ND LSD (.05) NS NS NS NS aEach value is the average of three replications. ND - not detectable. 116 Table 82. Soil treatments and soil extractable metal concentrations for chromium-treated Roscommon sand prior to cropping with corn 11 under greenhouse conditionsa. Extracting Agents Cr 0 . 1N 0. OOSN 1N 0 . IN 0 . OOSN 1N Tmt HCl DTPA NH40Ac H20 H01 DTPA .fiEAOAc H20 ppm Cr ppm--------- ---------Zn ppmr--------- 0 ND ND ND ND 3.0 0.9 0.3 0.4 50 19 0.6 ND ND 2.4 1.0 0.3 0.3 100 34 1.2 0.7 0.1 2.7 1.1 0.3 0.4 200 53 1.9 1.2 0.1 2.6 1.1 0.4 0.4 400 83 1.9 2.4 ND 2.7 1.4 2.2 0.5 LSD (.05) 12 0.3 0.8 NS NS 0.3 NS NS Mn ppm -------- --------Fe ppm --------- 0 12.8 1.3 0.4 ND 140 112 1.0 17.9 50 11.7 1.6 0.7 ND 136 115 1.6 12.3 100 12.2 1.3 0.6 ND 131 98 1.5 10.5 200 10.9 2.4 1 0 0.2 133 93 1.2 4.7 400 10.3 5.6 2.4 0.1 135 90 0.7 0.8 LSD (.05) NS 0.7 0.5 NS NS 21 NS 5.7 Cu ppmz-----—-- 0 0.7 0.4 ND 0.2 50 0.7 0.4 0.2 0.2 100 0.7 0.4 ND 0.1 200 0.7 0.3 0.1 ND 400 0.7 0.2 0.2 0.1 LSD (.05) NS NS NS NS aEach value is the average of three replications. ND = not detectable. 117 Table 83. Soil treatments and soil extractable metal concentrations for chromiumztreated Rubicon sagd prior to cropping with corn 11 under greenhouse conditions . I Extracting Agents Cr 0 . IN 0 . OOSN 1N 0 . 1N 0 . OOSN 1N Tmt HCl DTPA NH40Ac H20 HCl DTPA NHAOAc H20 ppm Cr ppm -------------- Zn ppm 0 ND ND ND ND 5.1 1.3 0.5 0.3 50 21 0.6 0.6 ND 8.2 1.4 1.1 0.2 100 36 1.2 1.8 ND 6.1 1.7 0.5 0.3 200 64 1.9 2.0 ND 5.9 1.7 1.0 0.3 400 94 2.0 3.6 ND 7.5 2.5 0.8 0.4 LSD (.05) 10 0.4 0.7 NS NS NS NS NS Mn ppmr ------ -—------Fe ppm - 0 69 5.6 3.7 ND 116 64 1.9 4.5 50 68 7.5 4.4 ND 114 62 2.1 3.5 100 79 7.0 4.0 ND 120 59 2.6 2.0 200 80 8.7 4.7 0.4 134 53 1.5 1.7 400 84 14.1 8.4 0.2 133 45 1.8 1.1 LSD (.05) 13 3.6 1.4 NS 16 6 NS 1.9 Cu ppm—-------- 0 0.7 0.2 0.1 ND 50 0.8 0.2 0.1 ND 100 0.7 0.2 0.2 0.1 200 0.7 0.2 0.1 0.2 400 0.7 0.2 0.2 0.1 LSD (.05) 0.1 NS NS NS 3Each value is the average of three replications. ND = not detectable. 118 Table 84. Soil treatments and soil extractable metal concentrations for chromium-treated Granby loamy sand prior to cropping with corn II under greenhouse conditionsa. Extracting Agents ‘ __— Cr 0 . 1N 0 . OOSN IN 0 . 1N 0 . OOSN 1N Tmt HCl DTPA NHAOAc H20 HCl DTPA NH40Ac H20 ppm Cr ppm— ------------------- Zn ppm ---------- 0 ND ND ND ND 5.9 2.7 0.3 0.9 50 16 0.6 0.2 ND 5.9 2.3 0.4 0.3 100 32 0.8 0.4 ND 5.8 2.1 0.4 0.4 200 50 1.2 0.5 ND 5.7 2.2 0.5 0.3 400 79 1.1 1.5 ND 6.1 2.7 0.4 0.5 LSD (.05) 6 0.2 0.7 NS NS NS NS NS Mn ppm— -------------- Fe ppm 0 19.2 1.7 0.8 ND 271 206 3.4 6.4 50 17.5 1.1 0.5 ND 256 191 2.1 8.5 100 16.8 1.1 0.5 ND 225 171 2.2 7.1 200 16.3 1.2 ,0.4 ND 225 161 2.0 3.2 400 16.0 1.5 0.7 ND 230 134 1.9 2.0 LSD (.05) 2.1 NS NS NS 20 26 NS NS __Cu ppm-_—__---- 0 1.1 0.4 0.1 0.1 50 0.9 0.4 0.2 0.1 100 0.9 0.3 0.1 0.1 200 0.9 0.3 ND 0.2 400 0.9 0.2 0.1 ND LSD (.05) NS 0.1 NS NS aEach value is the average of three replications. ND - not detectable. 119 Table 85. Effects of soil type and treatment level on H20 extractable chromium concentrations from chromium-treated soils under greenhouse conditionsa. Cr AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt ppm ppm Cr ——— 0 ND ND ND ND ND 50 0.1 ND ND ND ND 100 0.1 ND ND ND ND 200 ND 0.1 0.2 ND 0.1 400 0.3 ND ND 0.1 0.1 LSD (.051; Treatment level amogg soils NS; Soils within tmt. NS aEach value is the average of six replications. ND = not detectable. Table 86. Effects of soil type and treatment level on 1N NH40Ac extract- able chromium concentrationg from chromium-treated soils under greenhouse conditions . Cr AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt ppm ———me Cr 0 ND ND ND ND ND 50 0.6 0.5 1.5 0.6 0.8 100 2.1 1.4 3.3 1.1 2.0 200 4.1 3.6 5.6 2.2 3.8 400 8.1 7.8 9.8 4.9 7.7 LSD (.05): Treatment level among soils 1.2;, Soils within tmt. 0.8 3Each value is the average of six replications. ND - not detectable. Table 87. Effects of soil type and treatment level on 0.003N DTPA ex- tractable chromium concentrations from chromiumrtreated soils under greenhouse conditionsa. Cr AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt ppm ppm Cr 0 ND ND ND ND ND 50 1.2 1.1 1.2 0.5 1.0 100 1.6 1.3 1.6 0.8 1.3 200 1.7 1.9 1.6 1.0 1.5 400 1.6 1.9 1.4 1.3 1.5 LSD (.05): Treatment level among soils 0.3;, Soils within tmt. 0.2 8Each value is the average of six replications. ND 8 not detectable. 120 Table 88. Effects of soil type and treatment level on 0.1N_HCl extract- able chromium concentrationg from chromiumrtreated soils under greenhouse conditions . Cr AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt PPIn PPm Cr 0 ND ND ND ND ND 50 19 19 22 12 18 100 33 35 39 26 33 200 56 60 61 42 55 400 89 88 90 67 83 LSD (305): Treatment level among soils 4;, Soils within tmt. 3 8Each value is the average of six replications. ND - not detectable. Table 89. Effects of soil type and treatment level on H20 extractable manganese concentrations from chromium-treated soils under greenhouse conditions“. Cr AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamyisand within tmt ppm Ppm Mn 0 ND ND ND ND ND 50 ND ND 0.1 ND ND 100 ND ND 0.1 0.1 0.1 200 ND ND 0.5 ND 0.1 400 0.1 0.4 1.8 ND 0.6 LSD (.051; Treatment level amomg soils 0.5;» Soils within tmt. 0.3 aEach value is the average of six replications. ND - not detectable. Table 90. Effects of soil type and treatment level on 1N NH40Ac extract- able manganese concentratiogs from chromium-treated soils under greenhouse conditions . Cr AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt PPm ppm Mn ——__ 0 1.5 2.3 9.5 0.9 3.6 50 1.6 2.5 10.9 0.8 3.9 100 1.9 2.8 13.3 1.1 4.8 200 1.7 3.2 14.0 1.0 5.0 400 2.0 3.5 15.7 1.2 5.6 LSD (.05): Treatment level amomg soils 2.5; Soils within tmt. 1.7 3Each value is the average of six replications. 121. Table 91. Effects of soil type and treatment level on 0.005N DTPA ex- tractable manganese concentrations from chromium-treated soils under greenhouse conditionsa. Cr AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt PPIn ppm Mn ________ 0 1.4 3.5 6.6 1.2 3.2 50 1.6 3.8 8.6 1.1 3.8 100 1.9 4.4 12.7 1.3 5.1 200 1.9 4.7 15.1 1.4 5.8 400 2 7 5. 17.7 2.1 7.0 LSD (.05): Treatment level amomgNSOils 2.8; Soils within tmt. 1.8 aEach value is the average of six replications. Table 92. Effects of soil type and treatment level on 0.1N_HCl extract- able manganese concentratiogs from chromiumztreated soils under greenhouse conditions . Cr AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt PPm ppm Mn 0 6.5 13.7 58.1 18.8 24.2 50 6.3 13.4 55.6 18.3 23.4 100 6.9 13.7 58.9 17.0 23.6 200 7.2 15.1 62.2 17.0 25.3 400 7.0 14.6 67.1 16.5 26.3 LSD (:05): Treatment level amomg soils NS; Soils within tmt. NS 8Each value is the average of six replications. Table 93. Effects of soil type and treatment level on H20 extractable iron concentrations from chromium-treated soils under green- house conditionsa. Cr AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt ppm ppm Fe — -- 0 1.3 7.6 4.6 7.8 5.3 50 0.9 9.8 1.3 4.9 4.2 100 1.3 4.3 1.5 4.9 3.0 200 1.1 2.1 0.6 3.2 1.7 400 0.7 1.0 0.5 1.1 0.8 LSD (.05): Treatment level amomg soils 2.8;; Soils within tmt. 1.9 8Each value is the average of six replications. 122 Table 94. Effects of soil type and treatment level on 1N_NH40Ac extract- able iron concentrations from chromium-treated soils under greenhouse conditions“. Cr AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt ppm Pm Fe 0 1.7 2.5 4.1 3.3 2.9 50 1.9 2.2 3.5 3.6 2.8 100 1.1 2.3 3.5 3.0 2.5 200 1.1 2.0 2.7 2.7 2.1 400 0.9 l. 2.2 2.8 2.0 LSD (.05): Treatment level among soils NS; Soils within tmt. 0.8 aEach value is the average of six replications. Table 95. Effects of soil type and treatment level on 0.005N DTPA ex- tractable iron concentrations from chromium-treated soils under greenhouse conditionsa. Cr AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt PPIn ppm Fe 0 48 203 78 208 134 50 36 178 82 209 126 100 37 156 71 190 113 200 29 137 57 187 103 400 26 118 45 156 86 LSD (.05): Treatment level among soils 23; Soils within tmt. 15 aEach value is the average of six replications. Table 96. Effects of soil type and treatment level on 0.1N_HCl extract- able iron concentratigns from chromiumrtreated soils under greenhouse conditions . Cr AuGres Roscommon Rubicon Granby Means Tmt sand sand sand loamy sand within tmt PPm ppm Fe 0 45 156 137 283 157 50 49 159 140 291 160 100 47 158 141 259 151 200 51 166 145 262 156 400 56 168 149 260 158 LSD (.05): Treatment level amomg soils 14; Soils within tmt. 10 8Each value is the average of six replications. LIST OF REFERENCES LIST OF REFERENCES Adrian, W. J. 1973. A comparison of a wet pressure digestion method with other commonly used wet and dry-ashing methods. Analyst. 98:213-216. Agricultural Economics Department, Michigan State University, East Lansing, Michigan. May 1970. The utilization of effluent from domestic and industrial wastes for agri- cultural irrigation -- Muskegon County, Mich. Prelim- inary report. Allen, S. E. and G. L. Terman. 1966. Response of maize and sudan grass to zinc in granular macronutrients. gm G. V. Jacks (ed.) Int. Soc. Soil Sci. Trans. Comm. II, IV:255-266. Aberdeen, Scotland. Alloway, W. H. 1968. Agronomic controls over environmental cycling of trace elements. Advance. Agron. 20:235-274. Ambler, J. E. and J. C. Brown. 1969. Cause of differential susceptibility to zinc deficiency in two varieties of navy beans (Phaseolus vulgaris L.). Agron. J. 61:41- 43. Ambler, J. E., J. C. Brown and H. G. Gauch. 1970. Effect of zinc on translocation of iron in soybean plants. Plant Physiol. 46:320-323. Argaman, Y. and C. L. Weddle. 1973. The fate of heavy metals in physical-chemical treatment processes. Bechtel Cor- poration, San Francisco, Ca. Arnon, D. I. 1937. Ammonium and nitrate nutrition of barley at different seasons in relation to hydrogen-ion con- centration, manganese, copper, and oxygen supply. Soil Sci. 44:91-121. Bange, G. G. J. and R. Overstreet. 1960. Some observations on absorption of cesium by excised barley roots. Plant Physiol. 35:605-608. Barber, D. A. and H. V. Koontz. 1963. Uptake of dinitrophenol and its effect on transpiration and calcium accumulation in barley seedlings. Plant Physiol. 38:60-65. 123 124 Bauer, J. W. and D. E. Matsche. 1973. Large wastewater irri- gation systems: Muskegon County, Michigan, and Chicago Metropolitan Region. pp. 345-363. $2.W- E. Sopper and L. T. Kardos (ed.) Recycling treated municipal waste- water and sludge through forest and cropland. Pennsylvania State University. University Park, Pa. Beckwith, R. S. 1959. Titration curves of soil organic matter. Nature. 184:745-746. Berrow, M. L. and J. Webber. 1972. Trace elements in sewage sludges. J. Sci. Fd. Agric. 23:93-100. Bertrand, D. and A. deWolf. 1968. Necessite de loligo-element chrome pour la culture de la pomme de terre. Requirement for the trace element chromium in the growth of potatoes. C.R. Sci., Ser. D. 266:1494-1495. Bingham, F. T., A. L. Page and J. R. Sims. 1964. Retention of Cu and Zn by H-Montmorillonite. Soil Sci. Soc. Amer. Proc. 28:351-354. Blakeslee, P. A. 1973. Monitoring consideration for municipal wastewater effluent and sludge application to the land. pp. 183-198. In Proc. joint conf. on recycling municipal sludges and effluents on land. July 9-13, Champaign, Ill. Natl. Assoc. of State Univ. and Land Grant Colleges, Washington, D.C. Boawn, L. C., F. G. Viets, Jr., C. L. Crawford and J. L. Nelson. 1960. Effect of nitrogen carrier, nitrogen rate, zinc rate, and soil pH on zinc uptake by sorghum, potatoes, and sugar beets. Soil Sci. 90:329-337. Bouwer, H. 1973. Renovating secondary effluent by ground- water recharge with infiltration basins. pp. 164-175. mm W. E. Sopper and L. T. Kardos (ed.) Recycling treated . municipal wastewater and sludge through forest and crop- land. Pennsylvania State University Press, College Park, Pa. Bouwer, H. and R. L. Chaney. 1974. Land treatment of waste- water. Misc. paper. Bowen, J. E. 1969. Absorption of copper, zinc and manganese by sugarcane leaf tissue. Plant Physiol. 44:255-261. Broda, E. 1965. Mechanism of uptake of trace elements by plants (experiments with radio zinc). In Isotope ra- diation soil-plant nutr. Studies-ProceEdings of a Symv posium, Ankara. pp. 207-215. 125 Brouwer, R. 1965. Ion absorption and translocation in plants. Annu. Rev. Plant Physiol. 16:241-266. Brown, A. L. 1950. Zinc relationships in Aiken Clay loam. Soil Sci. 69:349-358. Brown, A. L., J. Quick and J. L. Eddings. 1971. A comparison of analytical methods for soil zinc. Soil Sci. Soc. Amer. Proc. 35:105-107. Bruland, K. W., K. Bertine, M. Koide and E. D. Goldberg. 1974. History of metal pollution in southern California coastal zone. Environ. Sci. Technol. 8:425-432. Cannon, H. L. 1960. Botanical prospecting for ore deposits. Science. 132:591-598. Chaney, R. L. 1973. Crop and food chain effects of toxic ele- ments in sludges and effluents. pp. 129-141. In Proc. joint conf. on recycling municipal sludges and Effluents on land. July 9-13, Champaign, Ill. Natl. Assoc. State Univ. and Land Grant Colleges, Washington, D.C. Chaney, R. L., J. C. Brown and L. O. Tiffin. 1972. Obliga- tory reduction of ferric chelates in iron uptake by soy- beans. Plant Physiol. 50:208-213. Chapman, H. D. 1965. Cation-exchange capacity. Em C. A. Black (ed.) Methods of soil analysis. Agronomy. 9:891-901. Chapman, H. D. 1967. Plant analysis values suggestive of nutrient status of selected crops. £2 Soil testing and plant analysis. Part 2. SSSA Special Publ. Series No. 2. Soil Sci. Soc. of Amer. Inc., Madison, Wis. Chaudhry, F. M. and J. F. Loneragan. 1972. Zinc absorption by wheat seedlings: II. Inhibition by hydrogen ions and by micronutrient cations. Soil Sci. Soc. Amer. Proc. pp. 327-331. Cotton, F. A. and G. Wilkinson. 1972. Advanced inorganic chemistry. Interscience Publishers, New York. Cropper, J. B. 1969. Greenhouse studies on nutrient uptake and growth of corn on sludge-treated soils. M.S. Thesis. University of Illinois, Urbana. Day, P. R. 1965. Particle fractionation and particle-size analysis. In C. A. Black (ed.) Methods of soil analysis. Agronomy. §?545-567. DeKock, P. C. 1956. Heavy metal toxicity and iron chlorosis. Ann. Bot. (London) N.S. 20:133-141. 126 DeMumbrum, L. E. and M. L. Jackson. 1956A. Copper and zinc exchange from dilute neutral solutions by soil colloidal electrolytes. Soil Sci. 81:353-357. DeMumbrum, L. E. and M. L. Jackson. 1956B. Infrared absorption evidence on exchange reaction mechanism of copper and zinc with layer silicate clays and peat. Soil Sci. Amer. Proc. 20:334-337. DeMumbrum, L. E. and M. L. Jackson. 1957. Formation of basic cations of copper, zinc, iron, and aluminum. Soil Sci. Soc. Amer. Proc. 21:662. Dolar, S. G., D. R. Keeney and L. M. Walsh. 1971. Availability of Cu, Zn, and Mn in soils. III. Predictability of plant uptake. J. Sci. Food Agr. 22:282-286. Elgabaly, M. M. 1950. Mechanism of zinc fixation by colloidal clays and related minerals. Soil Sci. 69:167-174. Elgabaly, M. M., H. Jenny and R. Overstreet. 1943. Effect of type of clay mineral on the uptake of zinc and potassium by barley roots. Soil Sci. 55:257-263. Elgawhary, S. M., W. L. Lindsay and W. D. Kemper. 1970. Effect of complexing agents and acids on the diffusion of zinc to a simulated root. Soil Sci. Soc. Amer. Proc. 34:211- 214. Ellis, B. G. 1965. Zinc deficiency, response and suscepti- bility. Crops and Soils. 18(1):13. Ellis, B. G., A. E. Erickson, B. D. Knezek and A. R. Wolcott. 1972. Impact of wastewater on soils. Technical Report No. 30, Institute of Water Research, Michigan State University, East Lansing, Mich. Ellis, B. G. and B. D. Knezek. 1972. Adsorption reactions of micronutrients in soils. pp. 59-78. £2.J- J. Mortvedt (ed.) Micronutrients in agriculture. Soil Sci. Soc. of Amer. Inc., Madison, Wis. Findenegg, G. and E. Broda. 1965. Mechanism of uptake of trace elements by plant roots. Nature. 208:196-197. Follet, R. H. and W. L. Lindsay. 1971. Changes in DTPA- extractable zinc, iron, manganese and copper in soils following fertilization. Soil Sci. Soc. Amer. Proc. 35:600-602. Fried, M. and H. Broeshart. 1967. The soil-plant system. Academic Press, New York. 127 Gauch, H. G. 1972. Inorganic plant nutrition. Dowden, Hutchinson and Ross, Inc., Stroudsberg, Pa. Geering, H. R. and J. F. Hodgson. 1969. Micronutrient cation complexes in soil solution: III. Characterization of soi} solution ligands and their complexes with Zn+2 and Cu+ . Soil Sci. Soc. Amer. Proc. 33:54-59. Geraldson, C. M., G. R. Klacan and O. A. Lorenz. 1973. Plant analysis as an aid in fertilizing vegetable crOps. 1m L. M. Walsh and J. D. Beaton (ed.) Soil testing and plant analysis. Soil Sci. Soc. of Amer. Inc., Madison, Wis. Gieseking, J. E. and H. Jenny. 1936. Behavior of polyvalent cations in base exchange. Soil Sci. 42:273-280. Gilbey, D. J., K. D. Greathead and J. W. Gartell. 1970. Copper requirements for southeastern wheatbelt. J. Agr. west. Aust. 11:70-72. Haas, A. R. C. and J. N. Brusca. 1961. Effects of chromium on citrus and avocado grown in nutrient solutions. Calif. Agr. lS(2):10-11. Henry, C. D., R. E. Moldenhauer, L. E. Engelbert and E. Truog. 1954. Sewage effluent disposal through crop irrigation. Sewage and Industrial Wastes. 26:123-133. Hewitt, E. J. 1953. Metal interrelationships in plants: I. Effect of some metal toxicities on sugar beet, tomato, oat, potato, and marrowstem kale grown in sand culture. J. Exp. Bot. 4:59-64. Hiatt, A. J. and R. H. Lowe. 1967. Loss of organic acids, amino acids, K, and C1 from.barley roots treated an- aerobically and with metabolic inhibitors. Plant Physiol. 42:1731-1736. Himes, F. L. and S. A. Barber. 1957. Chelating ability of soil organic matter. Soil Sci. Soc. Amer. Proc. 21: 368-373. Hodgson, J. F. 1963. Chemistry of the micronutrient elements in soils. Advance. Agron. 15:119-159. Hodgson, J. F., W. L. Lindsay and J. F. Trierweiler. 1966. Micronutrient cation complexing in soil solution: II. Complexing of zinc and copper in displaced solution from calcareous soils. Soil Sci. Soc. Amer. Proc. 30:723-726. Hunter, J. G. and O. Vergnano. 1953. Trace element toxicities in oat plants. Ann. Appl. Biol. 40:761-767. 128 Irving, H. and R. J. P. Williams. 1948. Order of stability of metal complexes. Nature. 162:746-747. Isaac, R. A. and J. D. Kerber. 1971. Atomic absorption and flame photometry:techniques and uses in soil, plant, and water analysis. pp. 17-37. £m_L. M. Walsh (ed.) Instru- mental methods for analysis of soils and plant tissue. Soil Sci. Soc. of Amer. Inc., Madison, Wis. Jackson, T. L., J. Hay and D. P. Moore. 1967. The effect of Zn on yield and chemical composition of sweet corn in the Willamette Valley. Proc. Amer. Soc. Hort. Sci. 91:462-471. Jacobson, L., R. L. Hannapel and D. P. Moore. 1958. Non metabolic uptake of ions by barley roots. Plant Physiol. 33:278-282. Jamison, V. C. 1943. The effect of particle size of copper and zinc source materials and of excessive phosphates upon the solubility of copper and zinc in a Norfolk fine sand. Soil Sci. Soc. Amer. Proc. 8:323-326. Jenne, E. A. 1968. Controls on Mn, Fe, Co, Ni, Cu, and Zn concentrations in soils and water: the significant role of hydrous Mn and Fe oxides. pp. 337-387. 19 R. F. Gould (ed.) Trace inorganics in water. Advances in Chemistry Series 73, American Chemical Society, Washington, D.C. Jenny, H. 1966. Pathways of ions from soil into root accord- ing to diffusion models. Plant Soil. 25:265-289. Jones, J. B., Jr. 1967. Interpretation of plant analysis for several agronomic crops. pp. 49-58. mm Soil testing and plant analysis. Part 2. SSSA Special Publ. Series No. 2. Soil Sci. Soc. of Amer. Inc., Madison, Wis. Judy, W. H. 1967. Zinc availability from soil applied zinc sulfate and zinc EDTA. Ph.D. Thesis. Michigan State University, East Lansing, Mich. Kardos, L. T. and W. E. Sopper. 1973. Renovating of municipal wastewater through land disposal by spray irrigation. pp. 148-163. 22 W. E. Sopper and L. T. Kardos (ed.) Recycling treated municipal wastewater and sludge through forest and cropland. Pennsylvania State University Press, University Park, Pa. Keefer, R. F., R. N. Singh, D. J. Horvath and P. R. Henderlong. 1972. Response of corn to time and rate of phosphorus and zinc application. Soil Sci. Soc. Amer. Proc. 36: 628-632. 129 Khanna, S. S. and F. J. Stevenson. 1962. Metallo-organic complexes in soil: I. Potentiometric titration of some soil organic matter isolates in the presence of tran- sition metals. Soil Sci. 93:298-305. Krauskopf, K. B. 1972. Geochemistry of micronutrients. pp. 7-40. gm J. J. Mortvedt (ed.) Micronutrients in agriculture. Soil Sci. Soc. of Amer. Inc., Madison, Wis. Labanauskas, C. K., L. H. Stolzy and M. F. Handy. 1972. Con- centrations and total amounts of nutrients in citrus seedlings (Citrus sinensis Osbeck) and in soil as in- fluenced by differential soil oxygen treatments. Soil Sci. Soc. Amer. Proc. 36:454-457. Lagerwerff, J. V. and D. L. Brower. 1973. Exchange adsorption or precipitation of lead in soils treated with chlorides of aluminum, calcium and sodium. Soil Sci. Soc. Amer. Proc. 37:11-13. ' Laties, G. G. 1969. Dual mechanisms of salt uptake in re- lation to compartmentation and long distance transport. Annu. Rev. Plant Physiol. 20:89-116. Lee, C. R. and G. R. Craddock. 1969. Factors affecting plant growth in high-zinc medium: II. Influence of soil treatments on growth of soybeans on strongly acid soil containing zinc from peach sprays. Agron. J. 61:565- 567. Lee, C. R. and N. R. Page. 1967. Soil factors influencing the growth of cotton following peach orchards. Agron. J. 59:237-240. Leep, R. H. 1974. Effect of soil heavy metal contamination upon growth and nutrient composition of corn. Ph.D. Thesis. Michigan State University, East Lansing, Mich. Leep, R. H. and B. D. Knezek. 1973. Effect of soil heavy metal contamination upon plant growth and nutrient com- position. Paper submitted to T.V.A. through Project Mich. 1137. Lessman, G. M. 1967. Zinc-phosphorus interactions in Phaseolus vulgaris. Ph.D. Thesis. Michigan State Uni- versity, East Lansing, Mich. Lindsay, W. L. 1972. Inorganic phase equilibria of micro- nutrients in soils. pp. 41-57. In J. J. Mortvedt (ed.) Micronutrients in agriculture. Soil Sci. Soc. of Amer. Inc., Madison, Wis. 130 Lindsay, W. L. 1973. Inorganic reactions of sewage wastes with soils. pp. 91-96. mm Proc. joint conf. on re- cycling municipal sludges and effluents on land. July 9-13, Champaign, Ill. Natl. Assoc. State Univ. and Land Grant Colleges, Washington, D.C. Lindsay, W. L. and W. A. Norvell. 1969A. Development of a DTPA micronutrient soil test. Agron. Abstracts. p. 84. Lindsay, W. L. and W. A. Norvell. 1969B. Equilibrium rela- tionships of 2n+2, Fe+3, Ca+2, and 3+ with EDTA and DTPA in soils. Soil Sci. Soc. Amer. Proc. 33:62-68. Lingle, J. C., L. 0. Tiffin and J. C. Brown. 1963. Iron uptake-transport of soybeans as influenced by other cations. Plant Physiol. 38:71-76. Lopez, P. L. and E. R. Graham. 1970. Isotopic exchange studies of micronutrients in soil. Soil Sci. 110:24-30. Lyon, G. L., P. J. Peterson and R. R. Brooks. 1969. Chromium- 51 transport in the xylem sap of Leptospermum scoparium (Manuka). N.Z. J. Sci. 12:541-545. Maas, E. V. 1969. Calcium uptake by excised maize roots and interactions with alkali cations. Plant Physiol. 44: 985-989. Maas, E. V., D. P. Moore and B. J. Mason. 1968. Manganese absorption by excised barley roots. Plant Physiol. 43: 527-530. Mallory, E. C., Jr. 1968. A thioacetamide-precipitation pro- cedure for determining trace elements in water. pp. 281- 295. $2 R. F. Gould (ed.) Trace inorganics in water. Advances in Chemistry Series 73. American Chemical Society, Washington, D.C. Martens, D. C., G. C. Chesters and L. A. Peterson. 1966. Factors controlling the extractability of soil zinc. Soil Sci. Soc. Amer. Proc. 30:67-69. McBride, M. B. and M. M. Mortland. 1974. Copper (II) inter- actions with montmorillonite: evidence from physical methods. Soil Sci. Soc. Amer. Proc. 38:408-415. Mertz, W. 1969. Chromium occurrence and function in biological systems. Physiol. Rev. 49(2):163-239. Misra, S. G. and R. C. Tiwari. 1966. Retention and release of copper and zinc by some Indian soils. Soil Sci. 101: 465-471. 131 Mitchell, J. 1932. The origin, nature and importance of soil organic constituents having base exchange properties. J. Am. Soc. Agron. 24:256-275. Moore, D. P. 1972. Mechanisms of micronutrient uptake by plants. pp. 171-198. £2 J. J. Mortvedt (ed.) Micro- nutrients in agriculture. Soil Sci. Soc. of Amer. Inc., Madison, Wis. Morrison, F. B. 1951. Feeds and feeding. Morrison Publish- ing Company, New York. Mortensen, J. L. 1963. Complexing of metals by soil organic matter. Soil Sci. Soc. Amer. Proc. 27:179-186. Muir, J. W., J. Logan and C. J. Brown. 1964. The mobilization of iron by aqueous extracts of plants: II. Capacities of the amino-acid and organic-acid fractions of a pine- needle extract to maintain iron in solution. J. Soil Sci. 15:226-237. Murrmann, R. P. and F. R. Koutz. 1972. Role of soil chemical processes in reclamation of wastewater applied to land. pp. 48-76. £m_Wastewater management by disposal on land. U.S. Army Corps of Engineers, Cold Regions Re- search and Engineering Laboratory, Hanover, New Hampshire. Nelson, J. L. and S. W. Melsted. 1955. The chemistry of zinc added to soils and clays. Soil Sci. Soc. Amer. Proc. 19:439-443. Norvell, W. A. 1972. Equilibria of metal chelates in soil solution. pp. 115-138. l2 J. J. Mortvedt (ed.) Micro- nutrients in agriculture. Soil Sci. Soc. of Amer. Inc., Madison, Wis. Norvell, W. A. and W. L. Lindsay. 1970. Lack of evidence for ZnSi03 in soils. Soil Sci. Soc. Amer. Proc. 34:360-361. Pavel, L. 1959. Humic substances: IV. Water-soluble metal chelates formed from the dark colored fulvic acid fraction from peat. Sborn. cs1. Akad. Zemed. Ved. 32:639-650. (of. Soils Fert. 22:2604. 1959). Peech, M. 1947. Availability of ions in light sandy soils as affected by soil reaction. Soil Sci. 51:473-486. Perkins, H. F. 1970. A rapid method of evaluating the zinc status of coastal plain soils. Soil Sci. Plant Anal. 1:35. Polson, D. E. and M. W. Adams. 1970. Differential response of navy beans (Phaseolus vulgaris L.) to zinc: I. 132 Differential growth and elemental composition at ex- cessive zinc levels. Agron. J. 62:557-560. Pound, C. E. and R. W. Crites. 1973. Characteristics of municipal effluents. pp. 49-61. £m_Proc. joint conf. on recycling municipal sludges and effluents on land. July 9-13, Champaign, Ill. Natl. Assoc. State Univ. and Land Grant Colleges, Washington, D.C. Pratt, P. F. 1965. Digestion with hydrofluoric and perchloric acids for total potassium and sodium. £2 C. A. Black (ed.) Methods of soil analysis. Agronomy. 9:1019-1021. Amer. Soc. of Agron., Madison, Wis. ‘ j Pratt, p. F. 1966. Chromium. pp. 136-141. mm H G. Chapman (ed.) Diagnostic criteria for plants and soils. Univer- sity of California Div. of Agr. Sci., Riverside, Can Randhawa, W. S. and F. E. Broadbent. 1965A. Soil organic, matter - metal complexes: 5. Reactions of zinc with model compounds and humic acid. Soil Sci. 99:295-300. Randhawa, W. S. and F. E. Broadbent. 19653. Soil organic matter - metal complexes: 6. Stability constants of zinc humic acid complexes at different pH values. Soil Sci. 99:362-366. Reddy, M. R. and H. F. Perkins. 1974. Fixation of zinc by clay minerals. Soil Sci. Soc. Amer. Proc. 38:229-231. Rosell, R. A. and A. Ulrich. 1964. Critical zinc concentra- tions and leaf minerals of sugar beet plants. Soil Sci: 97:122-157. Sauchelli, V. 1969. Trace elements in agriculture. Van Nostrand Reinhold Company, New York. Schmid, W. E., H. P. Haag and E. Epstein. 1965. Absorption of zinc by excised barley roots. Physiol. Plant. 18: 860-869. Schnitzer, M. and S. I. M. Skinner. 1966. Organo-metalic inggractions 12 soils: 5. Stability constants of Cu++-, Fe -, and Zn - fulvic acid complexes. Soil Sci. 102: 361-365. Schroeder, H. A. 1967. Cadmium, chromium, and cardiovascular disease. Circulation. 35:570-581. Schroeder, H. A., J. J. Balassa and I. Tipton. 1962. Abnormal trace metals in man-chromium. J. Chron. Dis. 15:1941- 1964. 133 Sharpless, R. G., E. F. Wallihan and F. F. Peterson.~ 1969. Retention of zinc by some arid zone soil material treated with zinc sulfate. Soil Sci. Soc. Amer. Proc. 33:901- 904. Soane, B. D. and D. H. Saunder. 1959. Nickel and chromium toxicity of serpentine soils in southern Rhodesia. Soil Sci. 88:322-330. Spence, D. H. N. and A. E. Millar. 1963. An experimental study of the infertility of a Shetland serpentine soil. J. Ecol. 51:333-343. Stanton, D. A. and R. Du T. Burger. 1967. Availability to plants of zinc sorbed by soil and hydrous iron oxides. Geoderma. 1:13-17. Swaine, D. J. and R. L. Mitchell. 1960. Trace element dis- tribution in soil profiles. J. Soil Sci. 11:347-368. Tiffin, L. O. 1972. Translocation of micronutrients in plants. pp. 199-229. £m_J. J. Mortvedt (ed.) Micro- nutrients in Agriculture. Soil Sci. Soc. of Amer. Inc., Madison, Wis. Traynor, M. F. and B. D. Knezek. 1974. Effects of nickel and cadmium contaminated soils on nutrient composition of corn plants. pp. 83-87. £m_D. D. Hemphill (ed.) Trace substances in environmental health. Univ. of Missouri, Columbia, Mo. Truog, E. 1946. Soil reaction influence on availability of plant nutrients. Soil Sci. Soc. Amer. Proc. 11:305-308. Turner, M. A. and R. H. Rust. 1971. Effects of chromium on growth and mineral nutrition of soybeans. Soil Sci. Soc. Amer. Proc. 35:755-758. Udo, E. J., H. L. Bohn and T. C. Tucker. 1970. Zinc adsorp- tion by calcareous soils. Soil Sci. Soc. Amer. Proc. 34:405-407. United States Army Corps of Engineers. 1972. Wastewater management by disposal on land. Cold Regions Research and Engineering Laboratory, Hanover, New Hampshire. United States Public Health Service. 1965. Interaction of heavy metals and biological sewage treatment processes. Public Health Service Publication No. 999-WP-22. Vergnano, 0. 1959. Phosphorus nutrition in the presence of minor nutrients and toxic elements in soil. Agrochimica. 3:262-269. 134 Viets, F. G., Jr. and L. C. Boawn. 1965. Zinc. 32 C. A. Black (ed.) Methods of soil analysis. Agronomy. 9:1090-1101. Amer. Soc. of Agron. Inc., Madison, Wis. Viets, F. G., Jr. and W. L. Lindsay. 1973. Testing soils for zinc, copper, manganese and iron. pp. 153-172. £2 L. M. Walsh and J. D. Beaton (ed.) Soil testing and plant analysis. Soil Sci. Soc. of Amer. Inc., Madison, Wis. Walker, R. B. and R. Grover. 1957. Absorption of chromium as related to iron supply. Plant Physiol. 32:Supp. 23. Wallace, A. 1963. Role of chelating agents on the availability of nutrients to plants. Soil Sci. Soc. Amer. Proc. 27: 176-179. Warncke, D. D. and S. A. Barber. 1973. Diffusion of zinc in soils: III. Relation to zinc adsorption isotherms. Soil Sci. Soc. Amer. Proc. 37:355-358. Warnock, R. E. 1970. Micronutrient uptake and mobility within corn plants (Zea mays L.) in relation to phosphorus-in- duced zinc deficiency. Soil Sci. Soc. Amer. Proc. 34: 765-769. Warrington, K. 1946. Molybdenum as a factor in the nutrition of lettuce. Ann. Appl. Biol. 33:249-254. Watanabe, F. S., W. L. Lindsay and S. R. Olsen. 1965. Nutrient balance involving phosphorus, iron, and zinc. Soil Sci. Soc. Amer. Proc. 29:562-565. Wear, J. I. 1956. Effect of soil pH and calcium on uptake of zinc by plants. Soil Sci. 81:311-315. Wilkinson, H. F. 1972. Movement of micronutrients to plant roots. pp. 139-169. lm_J. J. Mortvedt (ed.) Micronutrients in agriculture. Soil Sci. Soc. of Amer. Inc., Madison, Wis. Young, D. R., C. S. Young and G. E. Hlavka. 1973. Sources of trace metals from highly urbanized southern California to the adjacent marine ecosystem. £m_Cycling and control of metals. Proceedings of an environmental resource con- ference, National Environmental Research Center, Cincinnati, Ohio. 0 0 8 7 8 1 0 S E II RN 9’ mil; / I, I L” .” V” I” N” U” E” ” Tillis I S/illll ”9 ”/2 fl [/1 Ila I ”