THE YIELD AND MANGANESE CONTENT OF SEVERAL CROPS GROWN ON SOILS TREATED WITH DIFFERENT FORMS OF MANGANESE CARRIERS Thai: for the Degree of Ph. D. MICHIGAN STATE UNIVERSITY Columbus Burgess Rick: 1955 This is to certify that the thesis entitled The Yield and. Manganese Content of Several Crops Grown on Soils Treated with Different Forms of Manganese Carriers presented by Columbus Burgess Ricks has been accepted towards fulfillment of the requirements for DOC'ISOIdS degree in PhilOSODhy Oklaelve‘i? Major 'professor Date December 9. 1955 0-169 THE YIELD AND MANGANESE CONTENT OF SEVERAL CROPS GROWN ON SOILS TREATED WITH DIFFERENT FORMS OF MANGANESE CARRIERS "" IMJ".V". Ifl'. efqfifi-I' - rum.» .‘o \ w tvarmdwv :- BY \7 ‘ 3c. . -_ “-1) ”I Columbus Burgess Ricks AN ABSTR ACT Submitted to the School of Advanced Graduate Studies of Michigan State University of Agriculture and Applied Science in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Soil Science Year 1955 Approved 0‘; L. .efi-rfi% LIBRARY Michigan State University Columbus Burgess Ricks ABSTRACT The occurrence of manganese deficiency in plants is pri- marily due to adverse soil conditions which render the element un- available to the plant. Recently workers have been studying the possibility of supplying manganese to crops by soil applications of slowly available carriers or metal-organic complexes. Experiments were conducted in the laboratory, greenhouse, and field to determine the feasibility of applying manganese to cr0ps using (1) readily soluble manganese salt, (2) a soluble chelate, (3) slightly soluble glassy frits, (4) slightly soluble oxides, and (5) a moderately soluble sulfate-carbonate compound. The main factor under consideration was the influence of source of manganese on the dry weight yield and manganese content of several cr0ps as affected by (1) soil type, (2) rate of carrier, (3) rate of liming, and (4) method of application of carrier. The data from laboratory studies showed that the solubility of glassy frit in salt solution was a function of pH. The more acid the extracting solution, the more manganese was removed from the frit in a given length of time. Thus it is believed that soil reaction affects the solubility of frit applied to soil. ii Columbus Burgess Ricks The addition of manganese, regardless of carrier, significantly increased the dry-weight yield and manganese content of all crops studied over the control. The relative effectiveness of the several carriers applied in Experiment 1, in which no attempt was made to use equivalent amounts of manganese, was (1) frit, (2.) sulfate, and (3) chelate. In general, as the rate of each manganese carrier was in- creased, the dry-weight yield and manganese content of each cr0p was increased. However, the two-tons-per-acre application of frit did not produce any more dry matter than did the one—ton rate. Liming had a marked influence on the amount of manganese cr0ps were able to obtain from a glassy frit. As the soil reaction increased from strongly acid to alkaline condition in three soils, the amount of manganese in oat and field bean plants decreased. Regardless of rate of frit applied to these soils, this same relation- ship held. In Experiment 4 the method of application of manganese car- rier for onions in the field was found to be important. Whether the carrier was applied to the soil or sprayed on the foliage the yield results from addition of manganese were very significant over the check. greater yields of onions were found when manganese carriers were applied to the soil than when they were used as a foliage spray. iii Columbus Burgess Ricks The carriers manganese sulfate and NuM applied to the soil gave the highest yields; and mangansoil gave the highest manganese con- tent. Yields of spinach from pots receiving all rates of manganese sulfate and the highest rates of frit FN-239B were significantly higher than those of the control. Soil application of all carriers increased the manganese content of this crop when compared with the check. The amount of easily reducible manganese in soils of Experi- ment 1 after treatment and cropping was highest in soil treated with frit and least in soils receiving the chelate. These values can be related to the quantity of manganese applied. After varying rates of lime were applied and crops grown in Experiment 2, this manga-- nese fraction increased as the rate of lime and frit increased. It is believed that the greater residual quantity of easily reducible manganese present under alkaline conditions is due to less manganese being absorbed at higher rates of lime. iv THE YIELD AND MANGANESE CONTENT OF SEVERAL CROPS GROWN ON SOILS TREATED WITH DIFFERENT FORMS OF MANGANESE CARRIERS BY COLUMBUS BURGESS R ICKS A THESIS Submitted to the School of Advanced Graduate Studies of Michigan State University of Agriculture and Applied I Science in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Soil Science 1955 /¢ 7~5‘ f tgiii ABSTRACT The occurrence of manganese deficiency in plants is pri- marily due to adverse soil conditions which render the element un- available to the plant. Recently workers have been studying the possibility of supplying manganese to crops by soil applications of slowly available carriers or metal-organic complexes. Experiments were conducted in the laboratory, greenhouse, and field to determine the feasibility of applying manganese to cr0ps using (1) readily soluble manganese salt, (2) a soluble chelate, (3) slightly soluble glassy frits, (4) slightly soluble oxides, and (5) a moderately soluble sulfate-carbonate compound. The main’factor under consideration was the influence of source of manganese on the dry weight yield and manganese content of several cr0ps as affected by. (1) soil type, (2) rate of carrier, (3) rate of liming, and (4) method of application of carrier. The data from laboratory studies showed that the solubility of glassy frit in salt solution was a function of pH. The more acid the extracting solution, the more manganese was removed from the frit in a given length of time. Thus it is believed that soil reaction affects the solubility of frit applied to soil. ii The addition of manganese, regardless of carrier, significantly increased the dry-weight yield and manganese content of all crops studied over the control. The relative effectiveness of the several carriers applied in Experiment 1, in which no attempt was made to use equivalent amounts of manganese, was (I) frit, (2) sulfate, and (3) chelate. In general, as the rate of each manganese carrier was in- creased, the dry-weight yield and manganese content of each crop was increased. However, the two—tons-per-acre application of frit did not produce any more dry matter than did the one-ton rate. Liming had a marked influence on the amount of manganese cr0ps were able to obtain from a glassy frit. As the soil reaction increased from strongly acid to alkaline condition in three soils, the amount of manganese in oat and field bean plants decreased. Regardless of rate of frit applied to these soils, this same relation- ship held. In Experiment 4 the method of application of manganese car- rier for onions in the field was found to be important. Whether the carrier was applied to the soil or sprayed on the foliage the yield results from addition of manganese were very significant over the check. Greater yields of onions were found when manganese carriers were applied to the soil than when they were used as a foliage spray. iii The carriers manganese sulfate and NuM applied to the soil gave the highest yields; and mangansoil gave the highest manganese con- tent. Yields of spinach from pots receiving all rates of manganese sulfate and the highest rates of frit FN-Z39B were significantly higher than those of the control. Soil application of all carriers increased the manganese content of this crop when compared with the check. The amount of easily reducible manganese in soils of Experi- ment 1 after treatment and cr0pping was highest in soil treated with frit and least in soils receiving the chelate. These values can be related to the quantity of manganese applied. After varying rates of lime were applied and crops grown in Experiment 2, this manga- nese fraction increased as the rate of lime and frit increased. It is believed that the greater residual quantity of easily reducible manganese present under alkaline conditions is due to less manganese being absorbed at higher rates of lime. iv ACKNOWLEDGMENTS The author is very grateful to Dr. Kirk Lawton, his major professor, for the sympathetic and unselfish guidance of his course of study and for the constructive criticisms rendered during the period of this investigation. He is particularly indebted to Drs. L. M. Turk and R. L. Cook, Director, Michigan State Agricultural Experiment Station, and Head, Soil Science Department, respectively, for interceding, in his behalf, with the governments of Liberia and the United States for permission for him to remain in this country to continue his advanced graduate studies at Michigan State Univer- sity. He also wishes to register his acknowledgment of the consid- erations shown him by the members of his guidance committee. Special appreciation is directed to Dr. J. F. Davis, Research Professor, Soil Science Department, for the assistance given in Ex- periments 3 and 4, the taking of the pictures used in this thesis, and the reading of the manuscript. The invaluable help of Dr. E. .I. Benne of the Agricultural Chemistry Department in the chemical analysis, and Professor H. Brown of the Farm CrOps Department in the statistical analysis of this study is sincerely appreciated. The author wishes to thank his country through Hon. E. J. Yancy, Secretary of Public Instruction, and His Excellency William V. S. Tubman, President of the Republic of Liberia, for the grant- in—aid given him during part of his period of study in the United States. All of the individuals, organizations, and companies who have given the author the privilege of working for them will always be remembered. Without such employment he would not have been able to obtain the necessary funds to sustain him while undertaking his study in this country. To his clear wife he tenders his appreciation for her faith and confidence. She has been very thoughtful and kind. Ere he closes, permit him to express his gratitude to the sainted memories of his departed sister, Angie F. Uso, for the material help given during the early days of his education in Liberia. In the words of my deceased brother, Henry R. W. Ricks: "Your praise will always be mine to ring while life lasts! H, vi TABLE OF CON TENTS G reenhouse Expe riments ....................... Experiment 1: The Effect of Kind and Rate of Manganese Carrier on the Dry-Weight Yield and Manganese Content of Spinach, Cats, and Field Beans .................................. Experiment 2: The Effect of Varying Rates of Lime and Frit on the Dry-Weight Yield and Manganese Content of Oats and Field Beans ....... Experiment 3: The Effect of the Type of Frit and Rate of Application of Frit and Manganese Sulfate on the Dry-Weight Yield and Manganese Content of Spinach ......................... Field Experiment ............................ vii LABORATORY ................................ Method of Soil Analysis ....................... Moisture Equivalent ........................ Soil Reaction ............................. Cation Exchange Capacity Determination .......... Easily Reducible Manganese Dioxide ............. Determination of Total Manganese in Plant Material ................................ Statistical Analysis ........................... Solubility Studies of F rit ....................... RESULTS AND DISCUSSION .............. I ......... General ................................... Experiment 1 . . . '. ........................... Spinach Crop ............................. Oat Crop ................................ Bean Crop ............................... Experiment 2 ............................... Oat Crop ................................ Bean Crop ............................... Experiment 3 ............................... Expe rim ent 4 ............................... viii 31 31 31 32 33 34 34 36 36 40 40 45 49 55 55 59 63 66 ix Table LIST OF TABLES Page Three carriers of manganese and their rates of application on Oshtemo, Thomas, and Houghton soils in the greenhouse in experiment 1 ......... 20 Rate of application of lime, fertilizer, and minor elements to three soils used in greenhouse ex- periment 2 ............................. 26 The rate of application of four carriers of man- ganese together with the amounts of boron, copper, and zinc applied to Houghton muck soil in the greenhouse in experiment 3 .................. 28 The rate of application of various manganese carriers applied to Houghton muck plots in experiment 4 at the Muck Experiment Farm ...... 30 The reaction of soil receiving various manganese treatments in greenhouse experiment 1 .......... 37 Solubility studies of manganese in frit (FN-l86) as affected by extraction with acetic acid and ammonium hydroxide solutions of varying pH ..... 38 The dry-weight yield of spinach as influenced by the kind and rate of application of manganese carrier to three soils in greenhouse experiment 1 . . 41 The effect of kind and rate of application of manganese carrier on the manganese content of Spinach grown on three soils in greenhouse ex- periment 1 .............. i ............... 43 The dry-weight yield of oat plants as influenced by the kind and rate of application of manganese carrier to three soils in greenhouse experiment 1' . . 46 Table Page 10. The effect of kind and rate of application of manganese carrieron the manganese content of oat plants grown on three soils in green- house experiment 1 ....................... 48 11. The dry-weight yield of bean plants as influenced by the kind and rate of application of manganese carrier to three soils in greenhouse experiment 1 . . 50 12. The effect of kind and rate of application of manganese carrier on the manganese content of bean plants grown on three soils in green- house experiment 1 ....................... 52 13. The effect of kind and rate of application of manganese carrier on the easily reducible manganese content of soils following the har- vest of craps in greenhouse experiment 1 ........ 56 14. The effect of varying rates of lime and frit on the dry-weight yield of oat plants grown on three soils in greenhouse experiment 2 ......... 57 15. The effect of varying rates of lime and frit on the manganese content of oat plants grown on three soils in greenhouse experiment 2 ....... 59 16. The effect of varying rates of lime and frit on dry-weight yield of bean plants grown on three soils in greenhouse experiment 2 ......... 61 17. The effect of varying rates of lime and frit on the manganese content of bean plants grown on three soils in greenhouse experi- ment 2 ................................ 62 18. The effect of rate of application of lime and frit on the easily reducible manganese content of soils following the harvest of cr0ps in experiment 2 ............................ 64 xi Table 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. The effect of the type of frit and rate of frit and manganese sulfate on the yield and manganese content of spinach grown on Houghton muck in greenhouse experiment 3 ...... The effect of type of manganese carrier and its method of application on the yield and manganese content of onions grown on Houghton muck in field experiment ........... Analysis of variance for the yield of spinach in greenhouse experiment 1 ................. Analysis of variance for the manganese content of spinach in greenhouse experiment 1 ......... Analysis of variance for dry weight of oat plants in greenhouse experiment 1 ............ Analysis of variance for the manganese content of oat plants in greenhouse experiment 1 ....... Analysis of variance for the dry weight of bean plants in greenhouse experiment 1 ........ Analysis of variance for the manganese content of bean plants in greenhouse experiment 1 ...... Analysis of variance for the dry weight of oat plants in greenhouse experiment 2 ......... Analysis of variance for the manganese content of oat plants in greenhouse experiment 2 ....... Analysis of variance for the dry weight of bean plants in greenhouse experiment 2 ........ Analysis of variance for the manganese content of bean plants in greenhouse experiment 2 ...... xii Page 65 6'7 84 85 86 87 88 89 90 91 92 93 Table 31. 32. 33. 34. 35. 36. 37. 38. 39. Analysis of variance for the yield of spinach in greenhouse experiment 3 ................ Analysis of variance for the yield of onions in the field experiment ................... The effect of kind and rate of application of manganese carrier on the dry-weight yield of Spinach grown on three soils in greenhouse expe riment 1 .......................... The effect of kind and rate of application of manganese carrier on the manganese content of spinach grown on three soils in greenhouse experiment I . ......................... The effect of kind and rate of application of manganese carrier on the dry-weight yield of oat plants grown on three soils in greenhouse experiment 1 .......................... The effect of kind and rate of application of manganese carrier on the manganese content of oat plants grown on three soils in green- house experiment 1 ..................... The effect of kind and rate of application of manganese carrier on the yield of beans grown on three soils in greenhouse experi- ment 1 .............................. The effect of kind and rate of application of manganese carrier on the manganese content of beans grown on three soils in greenhouse experiment 1 .......................... The effect of varying rates of lime and frit on the dry-weight yield of oat plants grown on three soils in greenhouse experiment 2 ..... xiii Page 94 100 102 104 106 108 Table 40. 41. 42. Page The effect of varying rates of lime and frit on the manganese content of oat plants grown on three soils in greenhouse experiment 2 ....... 109 The effect of varying rates of lime and frit on the dry‘weight yield of bean plants grown on three soils in greenhouse experiment 2 ....... 110 The effect of varying rates of lime and frit on the manganese content of bean plants grown on three soils in greenhouse experi- ment 2 ................................ 111 xiv Figure 1. LIST OF FIGURES Effect of solutions of different pH on the solubility of manganese from frit (FN-186) ..... The effect of three manganese carriers on the manganese content of spinach grown on Oshtemo soil in greenhouse experiment 1 ...... The visual appearance of field bean plants grown .on three alkaline surface soils without added mang ane s e ....................... The effect of manganese from frit on the appearance of field bean plants grown on a limed Houghton muck surface soil . . . .- ....... The effect of rate and kind of various man- ganese carriers on the growth of onions in field experiment on Houghton muck soil ....... The effect of method and rate of application of several manganese carriers on the growth of onions in field experiment on Houghton muck soil ............................ XV Page 39 44 53 54 70 72 INTRODUCTION The results of many experiments have demonstrated the im- portance of minor elements in plant nutrition. One of these ele- ments, manganese, haS‘ been given much consideration because in many instances it has been found to be a limiting factor in crop production. Small amounts of this element are found in almost every soil, and since it is needed by plants in only minute quantities, it is usually present in the soil in adequate amounts for plant growth. The reason for the occurrence of deficiencies of this element is to be found in chemical and physiological processes which render it unavailable to the plants or make it inactive in its physiological functions within the plant. The availability and fate of manganese contained in the soil, returned in plant residues, or added as fer- tilizer are governed by soil release and retention mechanics. Minor elements until recently were applied in the form of soluble salts, either alone or in mixed fertilizers. The use of sol- uble salts is not always wholly satisfactory because certain elements, when applied in concentration sufficient to support growth over an entire season, may be toxic, retard growth, and actually reduce yield. To overcome this disadvantage, repeated small applications may be necessary. In addition, small amounts of minor elements in soluble salts may be quickly rendered unavailable to plants under certain conditions. There is, therefore, a growing need for mate- rials which will furnish adequate amounts of the minor elements in one application which is safe, will not leach from the soil, will not ”tie-up" and become unavailable, and which will cause no physical difficulties when incorporated in mixed fertilizers. Several materials have been deve10ped to fulfill these condi- tions. One of these carriers is frit, which is a special type of glass, in which the selected ingredients, including the trace ele- ments, are smelted under controlled conditions, quenched (fritted) in water, dried, and ground. The trace elements thus actually are an integral part of the glass itself. The prOportion in which each trace element is released from the frit corresponds roughly to its proportion of the total trace element content. The availability of the minor elements in the frit may be varied by altering the per— centage composition of the minor element or elements concerned, the matrix (the amount and pr0portion among themselves of the remaining ingredients of the glass), the melting and cooling process, and the particle size. In general, they are slowly soluble com- pounds which will supply the minor elements to plants without any danger of toxicity. The total amount available for release depends, of course, upon the total amount present in the frit. The rate of release, on the other hand, is largely a function of the composition of the frit. From the technical point of view, sufficient amount of the trace elements should be present to support a season's growth, and the release rate should be adequate butrnot excessive. Another material containing trace elements is the chelate, a cyclic organic compound, in which a metal is joined to two or more donor groups of a single molecule or ion (22); these are par- ticularly important since they have exceptionally high stability. The most commonly used chelating complex is that of ethylenediamine- tetraacetate acid (EDTA). The most interesting and valuable property of EDTA. is its ability to form stable complexes with the alkaline earths and heavy metals. This compound is water-soluble and slightly alkaline. The higher the constant (K2), the less the metal- EDTA will dissociate as the pH is lowered. The Log K ranges 2 from 8.69 (Mg) to 25.0 (Fe). Manganese is 13.47 (35). Several commercial compounds of EDTA. are available which contain man- ganese, iron, or other metals. The trade name of the product used in this study was ”Sequestrene." The purpose of this study was to explore the value of glassy frits, manganese oxide, manganese sulfate-carbonate compound, and a chelate as sources of manganese for various crops grown under a variety of soil conditions, and to compare their efficiency in sup- plying manganese with that of the commonly used carrier, manganese sulfate. REVIEW OF LITERATURE Manganese deficiency of various cr0ps has been reported in many areas of the world. The most prominent case of manganese deficiency in crops is perhaps the so-called ”gray speck" disease of oats, which is common in parts of EurOpe, Australia, and the United States. In Australia, Samuel and Piper (27) first proved that the disease was identical with manganese deficiency. Symp- toms of manganese deficiency on oats have also been reported by Willis (45) and Alberts (1) in soils of the eastern coastal plains in the United States and by Sherman and Harmer (30) in alkaline or- ganic soils in Michigan. Manganese deficiency of oats and field beans has also been reported by Cook and Miller (6) to occur in alkaline or neutral soils in several areas in Michigan. The yield of field beans has been substantially increased in many instances in these areas by the application of manganese sulfate. In the past decade, Leeper (18, 19) and Piper (26) have stressed the importance of the role that oxidation- reduction reac- tions in the soil plays in determining the availability of manganese to plants. According to Leeper (18), reducing conditions are impor- tant in supplying available manganese if adequate quantities of easily reducible manganic manganese are present in the soil. He suggested a new hypothesis in which the soil manganese would exist in an equilibrium which can be fundamentally expressed in the fol- lowing equation: manganous manganese : colloidal hydrated MnOZ : inert MnOZ This theory is substantially identical with that prOposed by early French workers, quoted by Mellor (25), based on experiments in which they showed that hydrated manganous oxide is precipitated in a very fine state of subdivision when a manganous salt is added to neutral or alkaline solutions. This hydrated oxide is readily changed to the hydrated dioxide when the media, is neutral to alkaline. This hydrated dioxide is easily reduced by such reducing agents as hydroquinone . According to Leeper, plant roots are able to reduce colloidal manganese dioxide. He has shown that soils which contain one hun- dred parts per million of easily reducible manganese will grow normal plants. Soils containing less than fifteen parts per million would be definitely deficient in respect to plant growth. He has proposed an empirical method for the determination of easily re- ducible manganese dioxide present in the soil as a means of esti- mating the adequacy of the manganese in the soil for plant growth. Leeper's method was successfully used to identify certain manganese— deficient alkaline organic soils in Michigan by Sherman (29), but was unsatisfactory on acid soils, which have been heavily limed. It is now generally accepted that manganese deficiencies of crOps may occur when soils are naturally neutral or alkaline or when soils are heavily limed. On some well-drained mineral and organic soils, evidence of manganese deficiency in some susceptible crOps has been noted at soil reaction values as low as pH 5.8. McGeorge (24), Johnson (16), Shive (31), and Somers (34) have shown that a high manganese level in soils or in nutrient solutions will induce chlorosis in plants and that this chlorosis can be over- come by increasing the iron concentration in the nutrient solution or by sprays of iron salts. The interrelationship between manganese and iron is of considerable importance on certain soils, such as those rich in manganese in the Hawaiian Islands. In growing cer- tain cr0ps on these soils a continuous application of iron to the plants is necessary in order to avoid chlorosis. Some reports in the liter- ature indicated that the elements iron and manganese are functionally interrelated in their physiological effect on plants. Tottingham and Beck (36) studied this interrelationship in nutrient cultures of wheat. Their data indicated that the best growth of the plants was obtained when the ratio of iron to manganese in nutrient solution was 1:1. The occurrence of manganese deficiency is, as pointed out by Connor (5) and Willis (46), mainly due to oxidation and precipitation of the man- ganese in the soil, the highly oxidized forms being unavailable to plants. An example of a disturbance in the manganese and iron nu- trition of plants is the so-called lime-induced chlorosis which is the limiting factor in the production of certain tree fruits in several parts of the world. Bennett (2) and Wallace (41) have demonstrated that this type of chlorosis can be eliminated by sprays or by injec- tions of iron salts. Lime-induced chlorosis is believed to be due to a high calcium carbonate content of the soil which increases the pH value of the soil to such an extent that iron or manganese is precipitated and made unavailable to plants. The importance of iron and manganese deficiencies lies in the difficulty with which they are controlled. Treating soils with soluble salts containing these elements, or with sulfur to make them more acid, is often unsatisfactory, since the conditions in the soil causing the original deficiencies still exist. Skinner and Ruprecht (32) concluded from their experiments with truck cr0ps on calcareous soil that much of the manganese added to the soil became insoluble within three months. Gilbert (9) found that it was necessary to apply manganese before each crop gr0wn under alkaline soil conditions. Wallace and Ogelvie (40) reported that manganese sulfate and manganese chloride used as fertilizers at a rate equivalent to 100 pounds of manganese sulfate per acre, were effective in combating manganese deficiency in Globe beets only during the early stages of their growth. Harmer (11), working with organic soils, stated that the total content of manganese in an alkaline organic soil-is generally several times that in an acid soil but that in the alkaline soil is relatively unavailable. He sug— gested that the Optimum rate of application of manganese sulfate required for satisfactory growth depends on the degree of alkalinity, the depth of the alkaline layer, the reaction of the underlying soil, the drainage conditions, and the kind of cr0p grown. The quantities which can be used safely on organic soils are much larger than can be used on mineral soils. Wain, Silk, and Willis (37) treated soils in the laboratory and in the field with solutions of manganese sulfate and then examined at intervals the amounts of manganese which could be extracted with neutral 1 N ammonium acetate. They found in an experiment with a highly calcareous soil that the extractable manganese down to a depth of 12 inches fell to its original level seven days after treatment. To avoid the influence of the disturbing soil factors, some workers have resorted to spraying and injection of irOn and man- ganese salts. The latter of these two alternatives can only be 10 applied to trees, and, although effective on some trees, Wallace (38, 39) has shown it may give rise to gumming of stone fruits. Sprays require considerable labor unless they are a part of an insecticide or disease control program, and sometimes are unsatisfactory since they may be damaging at effective concentrations. In case of lime— induced chlorosis several‘applications must be made during a single season to keep the plants sufficiently well supplied with manganese or iron, because these elements in such instances are relatively immobile. McCall and Davis (23))reported that the most effective means of applying manganese for onions, in terms of yield reSponse per pound of manganese applied, was as a spray. However, dust and soil applications were both effective in increasing the yield of onions. In lieu of the difficulties thus encountered in maintaining a sufficient supply of available iron and manganese, the possibility of supplying the elements. by adding (I) slowly available inorganic compounds, or as (2) organic metal complexes to the soil, presents an intriguing approach to the problem. Materials containing slowly available nutrients should ideally have the following pr0perties: (l) The solubility in water should be relatively small in order to prevent the elements from leaching, and also to prevent them from being rendered unavailable to the plants 11 through chemical reactions in the soil. The absorption by the plant root would, therefore, necessarily have to take place directly by contact between the plant root and the material. (2) The material should be nontoxic to plants in high concentrations so that large amounts can be applied at once to furnish an ample supply of the nutrient over a long period. (3) The rate of release of the nu- trients from the material should be adequate for plant growth, but must not attain a toxic magnitude. The implication of a contact absorption does not present any serious objection to the deve10pment of such a material. An active role played by the absorbing root surfaces in releasing nu— trient elements from the solid phase of the soil has already been suggested by Jenny (15). According to this worker, colloidally adsorbed nutrients may be absorbed directly by the plant roots without the intervention of water solubility when there is a contact between the colloidal particles and the absorbing surface of the plant root. The reaction taking place is described as being merely an exchange of adsorbed ions. This mechanism will, of course, not explain a possible re- lease to the plant roots of nutrient elements held in a crystalline or amorphous matrix. There exists, however, good evidence that 12 plant roots have the ability to break down such structures to a lim- ited extent and to obtain nutrients during the process. Jones and Leeper (17) prepared a number of oxides of man- ganese and their crystalline structures were identified by X rays. These oxides were added to several soils on which plants suffered from manganese deficiency. Oxides of the structures manganite, manganous manganite, and pyrolusite cured manganese deficiency on oats and peas. All the successful oxides consisted of very small particles, as shown by electron micrographs. Oxides containing up to 68 percent manganese are now commercially available for allevi- ation of manganese deficiency. Eaton (7) claims that 0.1 percent of magnetite mixed with quartz sand makes unnecessary the use of soluble iron in the culture solutions maintained on the acid side of neutrality, and that a number of cr0p plants obtain sufficient amounts of iron from magnetite even when the pH value is as high as 8. Chapman (4) reported that citrus seedlings grew successfully in quartz gravel containing 0.1 gram of magnetite per 100 grams of gravel flooded with a nutrient solution at pH value from 5.8 to 7.0. He found that the addition of calcium carbonate to the gravel resulted in chlorosis unless the amount of magnetite was correspondingly increased. This experiment indicates 13 that there must be sufficient area of contact between the magnetite and the plant roots in order to prevent chlorosis. Guest (10) used bentonite and magnetite incorporated into quartz sand as a solid-phase source of certain nutrients in hydrophic cultures. He found that even at alkaline reactions of nutrient solu- tion, chlorosis did not appear in citrus seedlings as long as the magnetite was finely ground in order to present a large surface area. Incorporation of finely ground dolomite in the sand induced chlorosis, which he assumed was due to interference of solid dolomite particles with the contact between the roots and the magnetite par- ticles. The development of frits, finely ground silicate glasses which are capable of releasing iron, manganese, and other micronutrients to plant roots so far has been basedlmainly upon greenhouse stud- ies. Only a few experiments have been reported in which the frit has been applied to soil under field conditions. Wynd and Stromme (48) applied finely ground iron- and manganese-containing frit to a calcareous soil in the greenhouse, and found an increase in the yield and the manganese content of seeds and stems of bean plants, while the iron content of the same fractions was appreciably decreased. This result suggested that the ratio of iron to manganese in the frit must be carefully adjusted in order to avoid unfavorable ratios of 14 available iron to manganese in the soil. Wynd and Bowden (4?) ap- plied a finely ground iron-containing frit to a fertile greenhouse soil and found increased growth of snapdragons, which indicated that iron was a limiting factor in plant growth even though no deficiency symptoms were visible. A. chelating agent has been described by Foy (8) as any com- pound which will inactivate a metallic ion with the formation of an inner ring structure in the molecule, the metallic ion becoming a member of the ring. Natural chelation plays a very important role in the metabolism of both plants and animals. The synthesis of chlor0phyll, hemoglobin, metallo-enzymes, and (metallo-proteins all involve chelation. The synthetic chelating agent, ethylenediamine tetraacetic acid, frequently called EDTA., has the following structure: 9 9 Ho-c-CH2-\ /CH2- -OH / N-CHZfCHZ-N \ HO—C-CH - CH -C-OH ("3 2 2 ("3 Since this compound is not water-soluble, it is commonly prepared and sold as a water-soluble sodium salt. The tetra Sodium salt reacts with metallic ions such as manganese to form a chelate (Mn-EDTA.) which is represented by the following struc- ture: 15 Heck and Bailey (12) and Jacobson (14) first reported the use of an iron chelate as a satisfactory source of iron for plants grow- ing in solution cultures. Leonard and Stewart (21), Leonard (20), and Wallace 23:1. (42) have corrected an iron deficiency chlorosis in plants grown on soils by adding iron chelate to the soil. Wallace and North (41) extracted labeled nitrogen from corn seedlings sup- plied with Fe-EDTA isotopically labeled with nitrogen. Also, in a Split-root experiment, Weinstein (43) reported that the EDTA. absorbed by a sunflower plant chelated inactivated iron and transported it to a site of enzyme synthesis. Holmes and Brown (13) applied chelates at the same rate to a number of different soils. The (chelates reduced chlorosis in the plants on some soils, completely alleviated chlorisis in other soils, and produced toxicity symptoms in a third group. This showed the variable effect of the soil on chelate efficiency, which is also influ- enced by the iron requirement of the plants. A recent report by 1 Wallace and Lunt indicated that type of clay and other soil factors Paper presented at the annual meeting of the American Society of Agronomy, Davis, California, August, 1955. 16 influence the fixation of ethylenediaminetetraacetic acid. The iron concentration required in the growth medium for normal growth of chlorosis-susceptible soybean plants was greater than that for the nonsusceptible soybeans. Fishel and Mourkides1 compared the availability of equivalent amounts of manganese from four carriers to a tomato crOp grown on peaty muck, marl, and a sand soil. These workers found that MnSO4 (32.5 percent Mn) was slightly more available than MnO (68 percent Mn), which, in turn, was more available than gamma man— ganese dioxide (56 percent Mn) or Mn-EDTA (15.8 percent Mn). In addition to the EDTA. chelate, there are many others (13, 35) being investigated such as diethylenetriaminepentaacetic acid (DPTA), hydroxyethylethylenediaminetriacetic acid (EDTA.-OH), dihydryethylenediaminediacetic acid (EDDA), N-hydroxyethylethylene- diaminetriacetic acid (HEEDTA), cyclohexanediaminetetraacetic acid (CDTA), and aromatic polyaminocarboxylic acid (APCA). 1 J. G. A. Fishel and G. A. Mourkides. A. comparison of manganese sources using tomato plants grown on marl, peat and sand soils. Plant and Soils 6:313-331, 1955. EXPERIMENTAL METHODS G re enhouse Experiments These experiments were designed to study the effects of the application of different forms and rates of manganese materials to several soils upon the dry weight yield and manganese content of spinach, oats, and field beans. These three crops were chosen be- cause they represent different classes of crops known to exhibit manganese deficiency symptoms under certain soil conditions in Michigan. Experiment 1 Soil 5 Two mineral surface soils (Oshtemo loamylrsand and Thomas loam) and one organic (Houghton muck) surface soil were used for this study, and to each soil thirteen treatments were applied. There were four replications per treatment, thus requiring a total of 156 two-gallon glazed pots. The soils were screened through a 4 milli- meter sieve, and 10, 8, and 2 kilograms of air-dry soil for the Oshtemo, Thomas, and Houghton soils, respectively, were placed in 17 18 clean jars. A. basic application of nitrogen, phosphorus, and potas- sium equivalent to 1000 pounds per acre of 4-16-16 fertilizer was applied to each pot and thoroughly mixed with the soil. The Oshtemo sand soil was obtained from the Rose Lake Wildlife Experiment Station and had an original pH of 5.0. Calcium carbonate was applied to this soil at the rate of three tons per acre, and micronutrients were added at the rate of 10 pounds of cepper sulphate, 10 pounds of borax, and 2.5 pounds of zinc sul- phate per acre to each of fifty-two plots. The chemicals used were of C.P. grade and were thoroughly mixed with the soil. The Thomas loam soil was secured from a marsh near Bay City, and had an original pH of 7.6. In the greenhouse the Thomas soil was not limed, but did receive an application of 40 pounds of c0pper sulphate, 40 pounds of borax, and 10 pounds of zinc sulphate per acre. The Houghton muck soil was obtained from the Michigan Muck Experimental Farm near East Lansing. The reaction of this soil was pH 5.2; thus, calcium carbonate was applied at a rate of 12 tons per acre. In addition, copper sulphate, borax, and zinc sulphate were mixed with the soil at rates equivalent to 100, 100, and 25 pounds per acre, respectively. 19 The soils in all pots were thoroughly moistened with distilled water and incubated for six weeks to allow the lime, fertilizer, and micronutrients to react with the soil constituents. Mangane s e mate rials Three manganese-containing materials--frit, chelate, and manganese sulfate-~were thoroughly mixed with each soil after the moist incubation period. The frit used was FN-186, containing 16.5 percent manganese, obtained from the Ferro Corporation, Cleveland, Ohio. This material was applied at the rate of 500, 1000, 2000, and. 4000 pounds per acre (see Table 1), and thoroughly mixed with the soil in each jar. The chelate used was disodium manganous-ethylenedeamine- tetraacetic dehydrate, containing 12 percent manganese as metallic. This material, more commonly referred to as Sequestrene-NaZMn or Mn-EDTA, was furnished through the courtesy of the Geigy Chem- ical Corporation, Bayonne, New Jersey. Based on preliminary re- ports, the rates of application selected were 50, 100, 200, and 400 pounds per acre. Manganous sulphate, monohydrate, was used as the source of a soluble manganese salt. This compound, containing 32.5 percent 20 Table 1. Three carriers of manganese and their rates of applica- tion on Oshtemo, Thomas, and Houghton soils in the green- house in experiment 1. Mangane se M . . . anganese Content Rate of Application of Carrier Carrier (lbs./a.) (pct) Frit (FN 186) .......... 16.5 500 1000 2000 4000 Chelate (Sequestrene or Mn-EDTA) ............ 12 50 100 200 400 Manganese sulfate . . . . . . . 32.5 25 50 100 200 Each treatment application was replicated four times. 21 manganese, was applied at the rate of 25, 50, 100, and 200 pounds per acre and thoroughly mixed with the soil. Crops Spinach. On January 12, 1954, after the different manganese materials had been thoroughly mixed with each soil, the soils were rewet and allowed to [dry to approximately the moisture equivalent. Twelve spinach seeds per pot were placed in a 6 inch diameter ring in the soil surface made by pressing an inverted flower pot about one-half inch into the soil. The seeds were lightly packed. Immediately after being seeded, the pots were covered with wrapping paper to reduce water evaporation from the soil surface. The paper was removed after emergence of the seedlings. With this and succeeding cr0ps, it was noted that the control of soil moisture was critical at this stage. Sufficient moisture and air had to be maintained in the surface inch or two of soil for almost a week until the seedlings emerged and began developing their first true leaves. By this time, the root system was usually well enough developed to remove moisture from greater depths, so surface evaporation losses became less important, and the formation of a crust over the soil as a result of watering was less detrimental. In order to maintain an adequate oxygen supply for the germinating 22 seeds, the surface soil could not be too moist. Therefore there was only a narrow range around the Optimum moisture in which the moisture of the soils could vary without seriously retarding germination. Difficulties arose when one attempted to add water to the surface of the soil before the seedlings emerged be- cause of pronounced tendency of the soil to cake over and form a crust through which the seedlings emerged with difficulty. Therefore, it was found from experience that germination was greatly improved if enough water was added several days prior to planting to bring the entire body of soil in the pot well above Optimum moisture. Since the surface dried the fastest, in a few days it was down to Optimum moisture while the soil below still held excess water. By planting the seeds when the surface soil was down to optimum mois- ture, they were able to emerge without difficulty because the air above the soil was partially saturated due to the pots being covered with paper. The pots were arranged in a completely random manner on the greenhouse bench within each of the four replications. Nine medium rolling tables were used. Thus, the tables could be turned around and moved at weekly intervals to lessen any bias that could be introduced through a favored location on the table (as closer to heating pipes, stronger lights, etc.). During the winter, daylight was 23 supplemented with artificial overhead fluorescent lighting so that the plants received 14 to 16 hours of light daily. About two or three weeks after planting, when the seedlings were well established, they were thinned to four plants per pot. The discarded plants were left on the surface of the pot, as were all weeds that were removed in order not to remove any nutrients from the pot. An attempt was made to keep the moisture content of the soils in the pots close to the moisture equivalent by weighing and adding distilled water when necessary. Close Observations were made for deficiency symptoms. The entire above-ground portions of the, spinach plants were harvested March 15, 1954, dried in an electric oven at 65°-75°C., weighed, and ground in a Wiley mill. The plant material from each replicate treatment was stored in a glass bottle and analyzed at a later date. After the harvest of spinach crop, the soils in pots were allowed to dry. The soil of each pot was thoroughly mixed and composite sample of the four replicates of each treatment was taken to the laboratory for pH determination. Ammonium nitrate was then applied to each pot at the rate of 50 pounds of nitrogen per acre, prior to seeding oats. 24 Oats. Oats (Clinton variety) were seeded on April 3, 1954, in a manner similar to that described above for the spinach. About two weeks after germination the plants in each pot were thinned to twenty. The plants were observed very carefully during their entire growth period. The plants were harvested in the dough stage on May 25, 1954. As with the spinach, the plants were dried, weighed, ground, and samples stored for manganese analyses. Field beans. Essentially the same procedure was followed firfi for the bean cr0p. After NH4NO3 was applied to each pot at the rate of 50 pounds of nitrogen per acre, the pots were seeded to beans on June 1, 1954, and were thinned to eight plants per pot when the seedlings were established. Observations were made and color pictures were taken of some of the plants showing characteristic dif- ferences due to manganese deficiency and soil type. The plants were harvested in bloom stage on July 10, 1954, were dried, weighed, ground, and samples stored for manganese analyses. After the above three crops were harvested six samples of soil from each of the four replicates of each treatment were taken and thoroughly mixed. A representative sample of the composite was taken to the laboratory for easily reducible manganese to run on them. The results are given in Table 7. 25 Experiment 2 This experiment was designed to study the effect of soil re- action on the uptake of manganese from a manganese-containing frit applied to several soils. Three soils were used, namely Oshtemo sand, Hillsdale sandy loam, and Houghton muck. Each soil re— ceived six different lime treatments, and each treatment was repli- cated three times, requiring. a total of 108 one-half gallon glazed pots. The rates of lime and major and minor elements applied to each of the three soils are given in Table 2. Two frit rates of 500 and 2000 pounds per acre were applied to each lime treatment. The basic fertilizer for the Oshtemo soil was 500 pounds of 4-16-8 per acre, for the Hillsdale soil 750 pounds of 4-16-8 per acre, and for the muck soil 2000 pounds per acre. The minor elements were the same as applied in Experiment 1. The Hillsdale soil received the same amounts of minor elements as the Thomas soil. The oats were planted March 13, 1954, and harvested May 7, 1954. The beans were planted May 14, 1954, and harvested June 23, 1954. Oats and field beans were planted, grown, harvested, and an- alyzed exactly as in Experiment 1. Because of the smaller-sized pots the oats were thinned to six plants and the beans to four plants 26 Table 2. Rate of application of lime, fertilizer, and minor elements to three soils used in greenhouse experiment 2. Rate of Rate of Appli- Rate of Application of Appli- cation - Minor Elements Soil Type cation of Fer- (lbs./a.) of Lime tilize r (t./a.) (fig-513;? CuCl2 ZnSO4 Na2B4O7 NquMoO7 Oshtemo sand 0 500 20 - - - 1/4 500 20 - .. .. 1/2 500 20 - .. _ 1 500 20 - - _ 2 500 20 - - - 3 500 20 - - - Hillsdale sandy 0 750 - 5 - - loam 1 750 - 5 - - 2 750 - 5 - - 3 750 - 5 - - 4 750 - 5 - - 5 750 - 5 .. - Houghton muck 0 1000 50 10 20 10 3 1000 50 10 20 10 6 1000 50 10 20 10 9 1000 50 10 20 10 12 1000 50 10 20 10 15 1000 50 10 20 10 Rates of frit: 500 pounds and 2000 pounds per acre were applied to each lime treatment. 27 per pot. After the last of the two crops grown in Experiment 2 was harvested the soils of three replicates of each treatment were thor- oughly mixed and representative samples were taken to determine their content of easily reducible manganese. The results are given in Table 8. Experiment 3 The crops for Experiments 3 and 4 were grown under the supervision of Dr. J. F. Davis, Research Professor, Soil Science Department. The purpose of this experiment was to compare the effectiveness of four different manganese carriers in supplying man- ganese to spinach grown on Houghton muck. There were fourteen treatments, each replicated three times, giving a total of 42 two- gallon glazed pots. Detailed fertilizer treatments are listed in Table 3. The spinach was planted January 11, 1955, and harvested February 23, 1955. The crop was planted, grown, harvested, and analyzed as in Experiment 1. There were eight spinach plants per pot. Field Experiment The ObjeCt of this experiment was to determine the effect of several manganese carriers (1) placed in contact with the seed and 28 Table 3. The rate of application of four carriers of manganese to— gether with the amounts of boron, c0pper, and zinc applied to Houghton muck soil in the greenhouse in experiment 3. Rate of Application of Manganese Carrier and Treat- Minor Element Compound in Pounds per Acre ment A MnSO4 FN239B FN501 FN502 H3BO3 CuO ZnSO4 1 o ‘ o 50 25 2 100 60 50 25 3 200 60 50 25 4 400 60 50 25 5 400 0 so 25 6 50 60 so 25 7 100 60 50 25 8 200 60 so 25 9 50 o o o 10 100 o o o 11 200 No 0 o 12 5o 0 o o 13 100 o o o 14 200 o o o Lime and fertilizer common to all treatments were 10 tons CaCO3 per acre and 3000 pounds 10—10-30 per acre. Analyses of frits used: FN239B: This is a single-element manganese frit containing 40 percent manganese as MnOz, which is equivalent to 25.3 percent elemental manganese. ' FN501: This is a multiple trace element frit with the follow- ing guranteed analysis: 17.5 percent Fe203, equal to 12.3 percent iron; 7.8 percent MnOz, equal to 4.9 percent manganese; 5.0 percent ZnO, equal to 4.0 percent zinc; 2.5 percent CuO, equal to 2.0 per- cent copper; 6.5 percent B203, equal to 2.0 percent boron; 0.2 per- cent M003, equal to 0.13 percent molybdenum. FN502: This frit has the following guaranteed analysis: 9.0 percent B203, equal to 2.8 percent boron; 15.4 percent MnOz, equal to 9.7 percent manganese; 5.0 percent ZnO, equal to 4.0 percent zinc; 2.5 percent CuO, equal to 2.0 percent copper; 0.2 percent M003, equal to 0.13 percent molybdenum; 5.6 percent FezO3, equal to 3.9 percent iron. 29 (2) sprayed on the plants, on the yield and manganese content of onions. One check, three soil, and three spray treatments were included in the experiment. Included as soil and spray applications were manganese sulfate, NuM (manganese sulfate-carbonate com- pound), and mangansoil (finely divided MnO). Each treatment was replicated three times, giving a total of twenty—one plots. Data on the rate of each manganese carrier, its manganese content, and the method of application used are given in Table 4. Downing Yellow variety of onions was grown. The plots which were sprayed received five applications of four pounds each of elemental manganese per acre. The onions were planted May 7, 1954, and harvested Sep- tember 17, 1954. The onion bulbs were harvested and weighed, oven-dried, ground, and analyzed for manganese. 30 Table 4. The rate of application of various manganese carriers ap- plied to Houghton muck plots in experiment 4 at the Muck Experiment Farm. Treat- Manganese Method Manganese Manganese ment , Content of Ap— a Carrier (lbs./a.) , , No - (pct. ) plication 1 1 Check - - - 2 NuM 41 50 Soil 3 MnSO4 25 50 Soil 4 Mangansoil 68 50 Soil . b 5 Mangansofl 68 20 Spray 6 NuM 41 20 Spray 7 MnSO4 25 20 Spray a All plots received 1000 pounds 5-10-20 per acre, banded 2 inches below the seed. Materials in spray form were applied at a rate equal to 4 pounds elemental manganese per acre per Spraying. All spray plots received five Sprayings during the growing season. LABOR ATOR Y Method of Soil Analjsis Moisture Equivalent The moisture equivalent was found by centrifuging the saturated soil for thirty minutes at a force of one thousand times that of grav— ity (Briggs and McLane, 3). Soil R eac tion Soil pH was determined potentiometrically with a Beckman alternating current pH meter with glass electrode, using a 1:1 soil- to-water suspension. Cation Exchange Capacity Determination The ammonium acetate procedure of Schollenberger and Simon (28) was used for the determination of the cation exchange capacity of the soil. Detailed procedure is given in the appendix. 31 32 Easily Reducible Manganese Dioxide The determination of easily reducible manganese in soil was carried out according to the procedure of Leeper (18) with slight modification. A soil sample of 25 to 50 grams was placed in a 500 milli- liter Erlenmeyer flask and 250 milliliters of neutral normal ammo- nium acetate solution containing 0.2 percent hydroquinone was added to the flask. The soil suspensions were agitated with a rotary me- chanical shaker for eight hours and then filtered through Buchner funnels into 1 liter Berzelius tall form Pyrex beakers. Ten milli- liters of a 1:1 H2504 to H20 solution and 10 to 20 milliliters of concentrated HNO3 were added to the filtrate and evaporated to dryness by boiling vigorously over gas burner. (Nitric acid must be in excess so that when the acetate solution approaches dryness, it will foam, due to the escaping nitric oxides. This technique will prevent spattering. It is essential that all hydroquinone be destroyed by the acid-heat treatment). The residue after evaporation should be a translucent mass. The residue was dissolved in 25 to 50 milliliters of a 1:4 H2504 to H20 solution. Finally 1 milliliter HNO3, 10 dr0ps of H3PO4, 3 drops of H2804 (helps the color to develop faster), and l milliliter of periodic acid solution (30 grams 33 be . . . . . 1‘ 100 milliliters distilled water) were added to the contents Of the Qalter. This solution was heated until the complete permanganate color developed and then transferred to a volumetric flask and brought up to volume (usually 100 milliliters) with distilled water. The percent transmission of the silica-free permanganate solution was ready in a Coleman, Jr. spectrophometer using a wave length of 530 millimicrons. Determination of Total Manganese in Plant Material The manganese content of various plant materials was de- termined by a‘wet ashing procedure followed by the deve10pment of color of the permanganate ion using the method of Willard and Greathouse (44). However, certain modifications were employed. To 3 grams of plant material in a 250 milliliter tall form Berzelius “beaker were added 15 milliliters of a mixture of two volumes 72 percent HClO4 and one volume concentrated H2504. The 25 milli- liters concentrated HN03 was added and the plant material digested slowly at moderate temperatures of 125 to 150 degrees centigrade on an electric hotplate. The temperature was gradually raised to 200 degrees centigrade and the excess HNO was completely volatil- 3 ized and fumes of perchloric acid appeared .at this point. After the traces of perchloric acid fumes were removed, sulfuric acid fumes 34 the . . . . . . . . Ve10ped indicating a completion of the digestion. The remaining % “lfuric acid was evaporated to dryness and the beakers allowed to C001. Fifty milliliters of distilled water was added to each, and the contents thoroughly loosened from the bottom and side of the beaker with a rubber policeman. The permanganate color was de— veloped as described under “Easily Reducible Manganese Dioxide." Statistical Analjsis Analyses of variance were made on the dry weight yields and manganese content of each of the cr0ps grown, except for the manganese content of spinach in Experiment 3 and the onions in Experiment 4. The significance of each calculated F value was de- termined from Snedecor's tables (33). Solubility Studies of Frit In order to obtain an insight into the solubility of manganese in the frit used in greenhouse experiments 1 and 2 as affected by variation in soil reaction, a laboratory study was undertaken. Several liters of 1N HAc and 1N NH4OH solutions were made up separately, from which solutions buffered to the following reaction values were obtained: pH 4.0, 5.0, 5.5, 6.0, 6.5, 7.0, and 8.0. 35 A. 1 gram sample of frit was weighed into a 500 milliliter Erlenmeyer flask, and 450 milliliters of the pH 4.0 buffered solution were added to the flask. The flask was securely stOpped, placed in a rotary mechanical shaker, and agitated continuously for two weeks. The flasks were removed from the shaker and allowed to stand for 48 hours to allow the frit to completely settle. A. 50 milliliter aliquot of the supernatant liquid was pipetted into a tall form 250 milliliter Berzelius beaker. The permanganate color was then developed and manganese determined as described under ”Easily Reducible Manganese'Dioxide.” This procedure was followed with the remaining buffered pH solutions. The manganese content of each pH solution was run in duplicate. RESULTS AND DISCUSSION General The pH of the three soils used in greenhouse experiment I remained very consistent during the period these cr0ps were grown, as indicated in Table 5. The manganese carriers had little effect on soil reaction. The pH of soils in Experiment 2, listed in Table 19, rose rather uniformly as lime rate was increased, although the last three increments of lime applied to Houghton muck produced only small changes in soil reaction. It is also evident that differ- ent rates of frit had no effect on soil reaction. According to Table 6, the solubility of the frit decreased as the pH of the extracting solution increased. At pH 4.0 almost 95 percent of the manganese contained in this frit was soluble, while at pH 8.0 only 55 percent became soluble over a two-week period. Thus, it can be assumed that soil reaction does play an important part in the solubility of the frit used in the experiments. More manganese will be released from the same amount of frit when the soil reaction is more acid, as indicated in Figure l. 36 37 Table 5. The reaction of soil receiving various manganese treat- ments in greenhouse experiment 1. Rate of , a Manganese Appli- 5011 pH Of Carrier cation Oshtemob Tho wa H ht (lbs./a.) m s Oug on Control ............ - 7.7C 7.8 7.6 7.6 7.7 7.5 MnSO4 ............. 25 7.6 7.8 7.6 7.7 7.7 7.5 50 7.7 7.9 7.7 7.7 7.6 7.5 100 7.7 7.9 7.7 7.6 7.7 7.5 200 7.7 7.9 7.6 7.6 7.7 7.5 Frit .............. 500 7.7 7.7 7.7 7.7 7.7 7.5 1000 7.7 7.9 7.7 7.7 7.7 7.5 2000 7.7 7.9. 7.6 7.6 7.6 7.4 4000 7.7 7.9 7.6 7.7 7.7 7.5 Chelate ............ 50 7.7 7.8 7.6 7.7 7.7 7.5 100 7.7 7.8 7.6 7.6 7.8 7.5 200 7.6 7.9 7.7 7.7 7.8 7.4 400 7.7 7.8 7.6 7.6 7.8 7.5 Values represent the mean of replicates. The cation exchange capacity of the Oshtemo, Thomas, and Houghton soils are 5.34, 9.87, and 84.36 milliequivalents per 100 grams of soil, respectively. C The first column for each soil represents pH after harvest of spinach. The second column represents soil pH at the end of the experiment after harvest of beans. 38 Table 6. Solubility studies of manganese in frit (FN-186) as affected by extraction with acetic acid and ammonium hydroxide so- lutions of varying pH. pH of Manganese Extracting in Solution Solution (PPm) 4.0 338 5.0 313 5.5 289 6.0 264 6.5 236 7.0 220 8.0 200 The above parts per million values were obtained after shak- ing 1 gram of frit in 450 milliliters of buffered ammonium acetate solution for two weeks and allowing frit particles to settle for 48 hours. pH of Extracting Solution Figure 1. 39 8.0 l" x 7 5.. \ 7.0 .. x. 6.5 .. x 6.0 «- x 5.5 «r- ' X 4.5 1b 4,0 : : 1 t .L X4 200 220 240 250 250 300 320 340 Parts per Million of Soluble Manganese in Frit (FN-186) Material Effect of solutions of different pH on the solubility of manganese from frit (FN-186). 40 Experiment 1 Spinach Crop The data presented in Table 7 show that the addition of man- ganese, regardless of the carrier, significantly increased the yield of spinach over the control on the three soils. When considering carriers in terms of rates of application on soils, it is evident that the dry weight of Spinach receiving the frit was significantly higher than the yields obtained when manganese sulfate or the che- late were applied. The yields obtained with Mn-EDTA treatments were significantly lower than those recorded when the sulfate was used. This difference between the latter two carriers was obtained not only for the average of the three soils, but also for dry plant weights from the Oshtemo and Houghton soils. Although the chelate did not depress growth when compared with no manganese treatment, there is some evidence in the literature that this complex. is injuri- ous to some plants within the range of application used in this ex- periment. AS the rate of each carrier was increased, spinach yields rose from a minimum of 60 percent increase for frit applied to Thomas soil to 167 percent increase for Mn—EDTA on Oshtemo sand. It should be noted that no additional increase in dry weight of spinach 41 Table 7. The dry weight yield of spinach as influenced by the kind and rate of application of manganese carrier to three soils in greenhouse experiment 1. Man- Rate of Dry Weight (gms./pot)a on APP“- ‘ Carrier ganese , Carrier cation Oshtemo Thomas Houghton Mean (lbs. /a .) Sand Loam Muck b Control - 3.3 5.8 4.4 4.1 Mnso4 25(8.3°) 4.0 7.2 8.2 50 4.8 9.1 9.1 100 7.3 11.1 11.4 200 9.0 13.7 13.8 Mean 6.3 10.0 10.5 8.9 Frit 500(82.5°) 7.1 10.4 9.5 1000 8.8 12.3 11.8 2000 11.2 16.6 17.5 4000 10.4 16.1 18.0 Mean 9.0 13.5 14.5 12.3 Chelate 50(6.0C) 3.4 7.0 7.4 100 4.3 8.3 8.4 200 5.6 10.3 11.3 400 7.8 12.5 13.6 Mean 5.2 9.8 10.2 . 8.4 Soil mean 6.5 10.7 11.2 a Dry weight of four plants per pot. Values represent the mean of four replicates. C Pounds per acre of manganese applied at lowest rate. Soils L.S.D. at 5% = 0.2; at 1% = 0.3. Carrier L.S.D. at 5% = 0.4; at 1% = 0.5. Rates within carrier L.S.D. at 5% = 0.6; at 1% = 0.8. 42 was recorded for any of the soils when the highest rate of frit was applied. These results suggest that under the conditions studied 2000 pounds per acre of frit may be the maximum amount from which increased growth can be expected. The addition of each manganese carrier to the soil signifi- cantly increased the manganese content of spinach on all soils, as shown in Table 8. The plants absorbed less manganese from Mn- EDTA. treatments than from soil to which sulfate or frit was added. The glassy frit was somewhat more effective than the sulfate as a source of manganese when the average contents of this element ap- plied at all rates are compared. Since the carriers were not ap- plied on the basis of equivalent amounts of manganese, it should be pointed out that the relative rate of elemental manganese used were chelate, 1.00; sulfate, 1.33; and frit, 16.67. As the amount of each carrier was increased, highly signifi- cant increases in the manganese content of Spinach were obtained at each successive higher rate. This trend is illustrated in Figure 2 for Oshtemo soil. Although no manganese deficiency symptoms were noted on spinach in this experiment, the percent of manganese was as low as 0.003 and 0.005 in plants from Oshtemo sand and Houghton muck soils , respectively. 43 Table 8. The effect of kind and rate of application of manganese carrier on the manganese content of spinach grown on three soils in greenhouse experiment 1. Parts per Million of Manganese Rate of . . Manganese Appli- 1n Dry Plant Tissue on Carrier Carrier cation Mean (lbs /a ) Oshtemo Thomas Houghton ' ' Sand Loam Muck a Control . . . . - 34 60 53 49 MnSO‘4 ..... 25 91 141 102 50 143 171 155 100 207 244 224 200 236 284 262 Mean 169 210 186 188 Frit ...... 500 101 136 125 1000 155 191 179 2000 224 255 247 4000 253 301 281 Mean 183 221 208 201 Chelate . . . . 50 69 103 85 100 126 150 134 200 184 204 187 400 211 269 256 Mean 148 182 166 165 Soil 157 1 3 176 Mean 9 a Parts per million are mean of four replicates. Soils L.S.D. at 5% = 3; at 1% = 5. Carrier L.S.D. at 5% = 3; at 1% = 4. Rates within carrier L.S.D. at 5% = 5; at 1% = 7. 44 manganese sulfate —— glassy frit - -— — chelate —- - ° —- 300. 280- 260- \x Q) U) 2 240- ‘30 2 g 200- ‘6' I" 180. *8 ‘53, a. 140. 2 g: 120- 1.. 845 100- m 80- 13 60 d I n. 404 20 0 V f l fl lbs. manganese sulfate: 25 50 100 200 lbs. frit: 500 1000 2000 4000 lbs. chelate: 50 100 200 400 Figure 2. The effect of three manganese carriers on the manganese content of spinach grown on Oshtemo soil in greenhouse experiment 1. 45 Observations during the growth period showed that the spinach grown on Thomas and Houghton was more vigorous than that on Osh- temo. As a whole, the spinach did not do as well as the succeeding crops and this could be attributed to boron toxicity during the early stage of growth. No symptoms of manganese deficiency were evident on any of the plants from the several treatments. Oat Crop The effect of the several forms and amounts of manganese carriers on the growth of oat plants is given in Table 9. Significant increases in dry weight of this crop were found for the average values of the three carriers as compared with the control and for each succeeding rate of manganese added within each carrier. The highest dry weight was obtained using the glassy frit, while the sul- fate and chelate treatments produced plants of lOwer weight. The latter two carriers were equally effective in improving growth when their average effect for all soils‘is considered. Similar yields were obtained on Houghton muck from acre applications of 200 pounds of sulfate, 1000 p0unds of frit, and 400 pounds of chelate. It should be noted as in the case of the previous spinach cr0p, increasing the rate of frit from 2000 to 4000 pounds per acre did not affect the growth of oats on the two mineral soils. On the muck soil the additional 46 Table 9. The dry weight yield of oat plants as influenced by the kind and rate of application of manganese carrier to three soils in greenhouse experiment 1. .1 Rate of Dry Weight (gms./pot)a on Man- , . anese Appll- w ~— Carrier (glarrier cation Oshtemo Thomas Houghton Mean (lbs./a.) Sand Loam Muck b Control - 29 30.6 29.3 29.7 Mnso4 25(8.3C) 29.4 31.9 32.9 50 30.9 34.5 35.0 100 33.1 36.2 36.5 200 34.2 38.4 39.3 Mean 31.7 35.3 35.8 34.3 Frit 500(82.5°) 31.3 34.7 35.1 1000 33.6 36.9 38.9 2000 35.6 41.1 44.3 4000 36.1 41.4 45.0 Mean 34.0 38.5 40.8 37.8 Chelate 50(6.0C) 29.4 31.5 32.5 100 30.4 33.4 34.7 200 32.3 35.0 ’ 36.0 400 33.9 37.7 39.0 Mean 31.3 34.3 35.5 33.7 Soil mean 32.1 35.6 36.8 a Dry weight of twenty plants per pot. Values represent the mean of four replicates. C Pounds per acre of manganese applied at lowest rate. Soils L.S.D. at 5% = 0.4; at 1% = 0.5. Carrier L.S.D. at 5% = 0.2; at 1% = 0.3. Rates within carrier L.S.D. at 5% = 0.6; at 1% = 0.8. 47 ton of frit produced a highly significant increase in dry weight yield. It is possible, Since the frit contained micronutrients other than manganese, that improved growth was due to boron, supplied by this material. This supposition is made with reservation, since all other treatments including the control received these micronutrients in the form of soluble salts. The yield response to added manganese applied to Oshtemo sand was significant when compared with the control, but definitely less than that found with the other soils. Since the organic matter content of the Thomas and Houghton soils is high, the difference in relative response to manganese may be due to (1) a lower original content of available manganese or to (2) more favorable conditions for 'growth, which would not limit response to this micronutrient. The effect of carrier on manganese content of oats was es- sentially the same as for spinach, except that the Spinach crop con- tained much less manganese. The data in Table 10 Show that Mn- EDTA. was the least effective and frit was most effective in supply- ing manganese to the harvested crop. Significant increases in man- ganese content of oat plants at the 1 percent level were found be- tween all increasing rates of each carrier with the exception of two highest rates of frit on the Thomas and Houghton soils and between the 100 and 200 pound rates of sulfate on the muck. The 48 Table 10. The effect of kind and rate of application of manganese carrier on the manganese content of oat plants grown on three soils in greenhouse experiment 1. Parts per Million of Manganese Rate of . . Manganese Appli- 1n Dry Plant Tissue on Carrier . t' Carrier (1:: 17: ) Oshtemo Thomas Houghton Mean ' ° Sand Loam Muck Control . . . . - 76"1 110 79 88 MnSO4 ..... 25 151 144 157 50 187 228 277 100 300 368 384 200 381 386 399 Mean 255 282 304 280 Frit ...... 500 163 167 184 1000 221 249 305 2000 383 400 V 392 4000 402 388 397 Mean 292 301 320 304 Chelate . . . . 50 121 135 109 100 190 202 215 200 310 309 366 400 342 365 396 Mean 241 253 272 255 5°11 248 266 282 Mean -—.— 1 Parts per million are mean of four replicates. Soils L.S.D. at 5% = 7; at 1% = 10. Carrier L.S.D. at 5% j: 5; at 1% = 8. Rates within carrier L.S.D. at 5% = 12; at 1% = 16. 49 Oshtemo sand gave the small percentage and Houghton the largest increase in manganese content as judged by soil averages. The low- est rates of carriers gave as much as 60 to 108 percent increase in manganese content over the control. Growth on all the soils was good, especially on the Houghton and the Thomas soils. There were no manganese deficiency symp- toms on the oat crop. Bean Crop The averages of dry weights of plants grown on soil treated with all manganese carriers were significantly higher in dry weight than the control. The yield averages of bean (plants grown on the Thomas and Houghton soils were essentially the same, while dry matter production on the Oshtemo soil was significantly less. As with the two preceding crOps the frit resulted in the highest yields and the chelate the lowest. Within each carrier there were signifi- cant increases in yields as the rates were increased. These data in Table 11 suggest a definite need for substantial amounts of man- ganese for field beans. This was evident throughout the experiment except the 2000 pound frit treatment which resulted in yields equal to the 4000 pound rate. The yield pattern of the three cr0ps grown in Experiment 1 was very similar. 50 Table 11. The dry weight yield of bean plants as influenced by the kind and rate of application of manganese carrier to three soils in greenhouse experiment 1. Rate of Dry Weight (gms./pot)a on Man- . . anese Appli- v Carrier Carrier cation Oshtemo Thomas Houghton Mean (lbs . la.) Sand Loam Muck b Control - 15.4 18.4 16.2 16.3 Mnso4 25(8.3°) 17.9 20.3 18.5 » 50 19.2 25.6 23.5 100 24.7 26.8 25.5 200 25.2 26.9 26.3 Mean 21.8 25.0 23.8 23.5 Frit 500 19.3 29.6 25.2 1000 21.9 28.3 29.5 2000 24.6 31.0 32.4 4000 24.8 31.2 34.0 Mean 22.8 30.0 30.3 27.7 Chelate 50(6.oc) 17.5 20.0 21.8 100 18.5 21.4 23.3 200 22.0 24.4 25.8 400 21.9 25.5 23.9 Mean 20.3 22.8 23.8 22.3 Soil mean 21.0 25.0 25.3 a Dry weight of eight plants per pot. Values represent the mean of four replicates. C Pounds per acre of manganese applied at lowest rate. Soils L.S.D. at 5% .-= 0.4; at 1% = 0.5. Carrier L.S.D. at 5% =2 0.5; at 1% = 0.8. Rates within carrier L.S.D. at 5% = 0.4; at 1% = 0.5. 51 The effect of the carrier on the manganese content of the bean crOp was essentially the same as with the two preceding crOps. The control was significantly lower on the average than for any of the manganese treatments. The addition of manganese in the several forms increased the amount of manganese in the bean plants as shown in Table 12. As the amount of each carrier was increased, highly signifi- cant increases of manganese content of beans were obtained at each successive higher rate. Beans grown on the Thomas soil were highest in manganese and those from the Oshtemo soil were the lowest. Within the control the Thomas gave the highest manganese content. Beans grown on Thomas soil receiving the 4000 pound rate of frit were not as high in manganese as those grown on the Osh- temo or Houghton soils. The plants were more vigorous, in general, on the Thomas soil than on the Houghton or the Oshtemo. There were no manganese deficiency symptoms on the Thomas soil. However, manganese de- ficiency symptoms developed in plants of the control and the first two rates of manganese sulfate and the chelate on the Houghton and Oshtemo soils. The visual appearance of the control treatments for each soil is given in Figure 3. In Figure 4 the effect of frit in alleviating manganese deficiency can be noted. 52 Table 12. The effect of kind and rate of application of manganese carrier on the manganese content of bean plants grown on three soils in greenhouse experiment 1. Parts per Million of Manganese ,Rate of . D . Manganese Appli- 1n ry Plant Tissue on Carrier Carrier cation Mean (lbs/a ) Oshtemo Thomas Houghton ' Sand Loam Muck Control . . . . - 82a 126 100 103 MnSO4 ..... 25 151 195 171 50 192 288 .235 100 269 448 390 200 370 365 423 Mean 246 349 307 301 Frit ...... 500 174 215 174 1000 239 277 259 2000 374 413 360 4000 407 428 404 Mean 299 333 299 310 Chelate . . . . 50 130 155 141 100 200 233 182 200 312‘ 348 267 400 354 414 354 Mean 249 288 236 258 5°11 250 308 267 Mean Parts per million represent mean of four replicates. Soils L.S.D. at 5% = 6; at 1% = 9. Carrier L.S.D. at 5% = 5; at 1% = 8. Rates within carrier L.S.D. at 5% = 12; at 1% = 16. Figure 3. 53 The visual appearance of field bean plants grown on three alkaline surface soils without added manganese (M = Houghton muck, O = Oshtemo sand, and T = Thomas sandy loam). . *uu —. Figure 4. 54 The effect of manganese from frit on the appearance of field bean plants grown on a limed Houghton muck surface soil (0 = no frit, It.“4 = 4000 pounds of frit per acre). 55 It is pointed out in Table 13 that Thomas soil contained more easily reducible manganese remaining in it after the three crops were harvested in Experiment 1 than did the other two soils. It is of particular interest to note the larger amounts which were residual from the frit treatments. Experiment 2 Oat Cr0p The dry weight yield of the oat plants grown on soil of dif- ferent reaction treated with two rates of frit is listed in Table 14. The data show that the dry weights obtained were significantly higher as the pH of the soils was increased. Increasing the amount of frit also resulted in significantly greater dry matter at every pH level. The highest yields were obtained on Houghton muck followed in or- der by those of Hillsdale and Oshtemo soils. These data suggest that as the organic matter in the soils increased a more favorable condition for the growth of the cat plants was created. According to solubility studies more manganese should have been released from frit under conditions of low soil pH but this did not influence the yield of the oats. When frit was applied but no 56 Table 13. The effect of kind and rate of application of manganese carrier on the easily reducible manganese content of soils following the harvest of crOps in greenhouse experiment 1. Rate of Parts per Million of Manganese Manganese Appli— in Soil on Carrier cation (lbs . /a.) Oshtemo Thomas Houghton Control ............ - 0a 3 2 f ’ Mnso4 ............. 25 2 5 4 ; 50 4 7 7 g p, 100 7 1 1 1 o 53.1" 200 9 14 13 Frit (FN 186) ........ 500 7 ~ 12 10 1000 10 15 13 2000 12 19 17 4000 14 25 20 Chelate (Mn-EDTA.) . . . . 50 1 3 2 100 3 5 4 200 5 8 7 400 7 11 9 Values represent mean of four replicates. 10.550»? Josue rs..- .) It.“ s . ft.» . k . 57 Table 14. The effect of varying rates of lime and frit on the dry- weight yield of oat plants grown on three soils in green- house experiment 2. Lime Dry Weight (gms./pot)a with Soil Treat-L Soil Soil Type ment pH 500 lbs. 2000 lbs. Lime Mean (t./a.) Frit/a. Frit/a. Mean b c Oshtemo sand 0 5.0 7.0 8.7 7.9 1/4 5.5d 8.8 11.1 9.9 1/2 5.6 9.9 12.7 11.3 1 6.1 12.4 16.0 14.2 2 6.7 15.7 18.5 17.1 3 7.2 16.3 17.8 17.0 Mean 11.6 14.1 12.8 Hillsdale 0 5.0 8.1 9.8 8.9 sandy loam 1 5.5 10.1 11.8 10.9 2 6.3 12.7 14.4 13.5 3 6.8 14.3 17.3 15.8 4 7.2 16.8 19.9 18.3 5 7.4 17.1 19.7 18.4 Mean 13.5 15.5 14.5 Houghton 0 5.2 9.7 13.3 11.5 muck 3 6.6 13.5 15.1 14.3 6 7.2 15.2 17.2 16.2 9 7.3 17.4 18.2 17.8 12 7.4 20.0 . 21.0 20.5 15 7.4 20.3 21.7 21.0 Mean 16.0 17.8 16.9 a Dry weight of Six plants per pot. Results represent the pH of composite soil samples from each lime treatment. The cation exchange capacity of the three soils are given in Table 19. C Values represent the mean of three replicates. A difference of 0.1 pH was found between the soils receiv- ing frit at the rate of 500 and 2000 pounds per acre. Soils L.S.D. at 5% = 0.2; at 1% = 0.4. Frit L.S.D. at 5% = 0.7; at 1% =' 1.6. Lime within soils L.S.D. at 5% = 0.5; at 1% = 0.7. Lime within frit within soils L.S.D. at 5% = 0.8; at 1% = 1.0. .. :1 .o» w. 1.1.5... is". Jam a.“ w 5%. . 58 lime the yields were lowest. This relationship suggests that the need for lime was appreciably greater than the need for manganese. However, since no treatment of lime without frit was included, no proof can be given for this statement. It should be noted that at the higher rates of lime, an additional increment of frit did not produce substantially greater yields than where the soil was strongly acid. In contrast highly significant decreases in manganese occurred as the lime rate was increased. This was true regardless of the rate of frit. These data indicate that the higher pH was favorable for the growth of oats, but unfavorable for the accumulation of manganese in the plants. Solubility studies presented in Table 8 support the latter conclusion. When over 12 tons of lime was added to the Houghton the manganese content dr0pped considerably. The results of the interaction between the rates of frit and lime as incorporated in the soil was consistent. The oats grOwn on the Hillsdale and the Oshtemo soils were significantly higher in man— .ganese content than those grown on the Houghton muck as shown in Table 15. Oat plants on the Houghton soil were by far more vigorous and thrifty in appearance than those on the Hillsdale soil, which in 59 Table 15. The effect of varying rates of lime and frit on the man- ganese content of oat plants grown on three soils in green- house experiment 2. Parts per Million Lime Manganese in Dry Lime , Treat- Plant Tissue with per Soil 8011 Type ment Acre Mean (t./a.) 500 lbs. 2000 lbs. Mean Frit/a. Frit/a. A Oshtemo sand ..... 0 4443‘ 705 575 1/4 414 661 538 , 1/2 354 577 466 § 1 315 535 425 2 184 577 381 ‘-, , 3 150 413 282 L j Mean 310 578 444 "W” Hillsdale sandy loam 0 502 683 593 1 459 653 556 2 423 562 493 3 296 525 411 4 232 401 317 5 159 392 276 Mean 345 536 441 Houghton muck . . . . 0 426 594 510 3 385 545 465 6 292 518 405 9 227 454 341 12 169 324 247 15 90 244 167 Mean 265 447 356 a Parts per million represent mean of three replicates. Soils L.S.D. at 5% = 9; at 1% = 15. Frit L.S.D. at 5% = 1; at 1% = 1. Lime within soils L.S.D.. at 5% = 11; at 1% = 15. Lime within frit within soils L.S.D. at 5% = 16; at 1% = 21. 60 turn were more healthy than plants grown on the Oshtemo soil. No manganese deficiency was observed on plants grown on any soil. Bean Crop The dry-weight yield of the bean plants as influenced by lime and frit are given in Table 16. Plants from the Houghton muck pro- duced the most dry matter, with those grown on the Hillsdale soil next. As with the oat cr0p, it appears that the organic matter con- tent of the soils was beneficial to the growth of bean plants. As the rate of frit increased, dry weights also increased. The dry weight of plants from the no-lime treatment was significantly lower than where the lime was added to soils receiving the same amount of frit. As the lime was increased the yield on all three soils was increased up to the fifth rate, after which the yield remained the same or decreased slightly. The yield pattern of the bean was essentially similar to that of the oats. The data in Table 17 of the manganese content of field beans are similar to that of the oats. The lowest manganese content was found in plants grown on Houghton muck, while beans on the two min- eral soils contained about the same amount of this element. A con- sistent and highly significant increase resulted when 2000 pound rate of frit was compared with the 500 pound per acre application. As the lime rate was increased the manganese content decreased 61 Table 16. The effect of varying rates of lime and frit on dry-weight yield of bean plants grown on three soils in greenhouse experiment 2. Dry Weight in lee Grams per Pota with lee _ , Treat- per 5011 8011 Type ment Acre Mean (t./a.) 500 lbs. 2000 lbs. Mean Frit/a. Frit/a. b __ f’“ Oshtemo sand . . . . 0 5.4 6.9 6.1 f 1/4 7.7 9.3 8.5 5 1/2 8.8 10.4 9.6 f, 1 10.6 15.0 12.8 , 2 12.8 16.2 14.5 ‘ 3 11.9 16.3 14.0 i Mean 9.6 12.1 10.8 ,3, 3,; Hillsdale sandy loam 0 6.4 9.1 7.7 1 8.2 12.5 10.3 2 11.1 13.7 12.4 3 12.1 16.1 14.1 4 13.1 17.2 15.1 5 12.3 16.6 14.4 Mean 10.5 14.2 12.3 Houghton muck . . . . 0 8.4 10.9 9.6 3 10.7 13.6 12.1 6 11.9 14.3 13.1 9 13.6 18.4 16.0 12 15.9 19.6 17.7 15 _ 14.8 19.4 17.1 Mean 12.5 15.8 14.1 a Dry weight of four plants per pot. Values represent the mean of three replicates. Soils L.S.D. at 5% = 0.5; at 1% = 0.8. Frit L.S.D. at 5% = 0.4; at 1% = 0.9. Lime within soils L.S.D. at 5% = 0.6; at 1% = 0.7. Lime within frit within soils L.S.D. at 5% = 0.8; at 1% = 1.0. 62 Table 17. The effect of varying rates of lime and frit on the man- ganese content of bean plants grown on three soils in greenhouse experiment 2. Parts pe r Million Lime Manganese in Dry Lime Soil Type Treat- Plant Tissue with per Soil ment ~+ Acre Mean (t./a.) 500 lbs. 2000 lbs. Mean Frit/a. Frit/a. ,9 Oshtemo sand ..... 0 522a 712 617 . 1/4 482 677 580 g 1/2 434 588 511 ' 1 371 553 462 “ 2 282 491 387 ,, . 3 180 414 297 ;~ 3 Mean 379 573 476 ”— Hillsdale sandy loam 0 536 684 610 1 514 661 588 2 463 568 516 3 343 544 444 4 244 450 347 5 177 400 289 Mean 380 551 466 Houghton muck . . . . 0 415 571 493 3 384 553 469 6 320 502 411 9 244 444 344 12 183 311 247 15 100 227 164 hdean 274 435 355 a Parts per million are mean of three replicates. Soils L.S.D. at 5% = 2.75; at 1% = 4.57. Frit L.S.D. at 5% = 6.74; at 1% = 15.55. Lime within soils L.S.D. at 5% = 10.50; at 1% = 13.97. Lime within frit within soils L.S.D. at 5% = 14.85; at 1% = 19.75. 63 regardless of the amount of frit applied. The effect of lime and frit on the manganese content of field beans was essentially the same as found for the oat crop. There were manganese deficiency symptoms evident on beans grown on the Houghton muck when the highest rate of lime was ap- plied With 500 pounds 0f frit. In ganeral, the Houghton muck Produced f 7 the best-appearing plants. : The Oshtemo and Hillsdale soils in Experiment 2 gave the I higher readings of easily reducible manganese, followed by Houghton 5. :w muck. Table 18 shows that as the rate of the frit was increased, on all soils, the readings of the easily reducible manganese were increased. Experiment 3 The data in Table 19 Show that the yield of Spinach was sig- nificantly lower on the check pots than on treatments 2, 3, 4, 5, 7, and 8, which include manganese sulfate and frit FN-239B. Yields comparable to the check were obtained using frit FN-501 at the lowest rates. Since the amount of elemental manganese is not comparable, discretion must be used in a comparison of yield and chemical com— position. 64 Table 18. The effect of rate of application of lime and frit on the easily reducible manganese content of soils following the harvest of crOps in experiment 2. Parts per Million Lime Manganese in Soil Type Treat— Soil Soil with ment pH fl .. (t./a.) 500 lbs. ‘ 2000 lbs. Frit/a. Frit/a. read; a b Oshtemo sand ........... 0 5.0 5 29 1/4 5.5 6 32 1/2 5.6C 7 36 1 6.1 9 38 2 6.7 11 42 3 7.2 12 43 Hillsdale sandy loam ...... 0 5.0‘ 6 30 1 5.5 7 32 2 6.3 7 34 3 6.8 8 36 4 7.2 10 37 5 7.4 11 39 Houghton muck .......... 0 5.2 5 25 3 6.6 6 27 6 7.2 7 27 9 7.3 8 29 12 7.4 8 29 15 7.4 9 30 a Results represent the pH of composite soil samples from each lime treatment. The cation exchange capacity of the Oshtemo, Hillsdale, and Houghton soils are 5.34, 6.83, and 84.36 milliequiv— alents per 100 grams of soil, reSpectively. Values represent the mean of replicates. C A difference of 0.1 pH was found between the soils receiv- ing frit at the rate of 500 and 2000 pounds per acre. 65 Table 19. The effect of the type of frit and rate of frit and manga- nese sulfate on the yield and manganese content of spinach grown on Houghton muck in greenhouse experiment 3. Dry Weight Yield E1 - e in Grams per Potb Mn Treat- mental , (ppm) Manganese W Yield , ment , Mn Ap- , , , in Dry a Carrier , Repli- Repli- Repli- Mean No. plied , , Plant cation cation cation , (lbs./a.) Tissue 1 2 3 -r .-_ 1 Control - 1.3 1.8 2.0 1.7 79C 2 MnSO4 25 3.5 3.8 3.0 3.4 110 3 MnSO4 50 2.0 4.0 5.4 3.8 140 _ 4 MnSO 100 2.3 5.0 6.2 4.5 180 3- d 4 15.—.3" 5 MnSO4 100 5.4 4.2 5.8 5.1 180 6 FN-239B 12-1/2 2.0 4.0 3.5 3.1 108 7 FN-239B 25 3.8 4.2 4.8 4.2 109 8 FN-239B 50 5.8 4.6 4.4 4.9 140 9 FN-501 2-1/2 1.4 1.8 3.2 1.8 110 10 FN-501 5 0.8 2.0 1.5 1.4 108 11 FN-501 10 2.6 2.0 3.4 2.6 360 12 FN-502 5 0.8 2.4 3.0 2.0 100 13 FN—502 10 2.6 2.4 2.0 2.3 106 14 FN-502 20 1.8 3.4 1.4 2.2 108 L.S.D. at 1% level 1.5 a Description of treatments given in Table 3. b . . Dry weight eight plants per pot. C Replicates were composited for chemical analysis. d No boron applied. 66 Manganese sulfate applied at a rate of 400 pounds per acre, including copper and zinc, gave the highest mean dry weight. It is of interest to note that when boron was added to the same treatment the yield of the Spinach was depressed. In general, the manganese sulfate gave the highest yields and followed in decreasing order by frits FN—239B, FN-502, and FN—501. - ...._ The addition of manganese to Houghton muck resulted in a substantial increase in the manganese content of Spinach when com- pared'to the control. Spinach growing in pots receiving FN-501 at 200 pound per acre rate was the highest in manganese of plants from any treatment. The manganese sulfate treatments of 400 pounds per acre resulted in the second highest content of manganese fol- lowed by manganese sulfate and FN-239B at the 200 pounds per acre rate. Manganese deficiency was observed on the check. In general, the higher the yield the less chlorotic were the spinach plants. Experiment 4 The effect of type of manganese carrier and its method of application on yield of field-grown onions is presented in Table 20. Regardless of the manganese carrier or its method of application significantly greater dry-weight yields of onions were obtained than 67 Table 20. The effect of type of manganese carrier and its method of application on the yield and manganese content of onions grown on Houghton muck in field experiment. giaeld in 5:10 Mn gs per cre - th Tmr::: Manganese 1‘04: Agd Yield 1:132; No. Carrier plication Repli- Repli— Repll- Mean Bulb cation cation cation Tissue 1 2 3 b 1 Check - 468 443 328 413 88 2 NuM Soil 835 824 788 816 109 3 MnSO4 Soil 900 817 792 837 100 4 Mangansoil Soil 792 781 738 770 300 5 Mangansoil Spray 637 724 720 694 179 6 NuM Spray 742 724 684 717 120 7 MnSO4 Spray 689 752 752 734 101 L.S.D. at 5% level 76 a See Table 4 for manganese content of carrier and rate of applicatio b Replicates were composited for chemical analysis. 11. 68 when no manganese was applied. When NuM and manganese sulfate were applied to the soil, yields obtained were almost double that of the check. Mangansoil, NuM, and manganese sulfate applied as Sprays resulted in yields significantly lOwer than those Obtained with soil applications. The manganese content of the onion bulbs was greater when manganese was added to the soil. The highest manganese content was found in bulbs of plantS'receiving manganese applied to the soil. Plants from the mangansoil spray were next highest in manganese, followed in order of decrease by the NuM spray plottreatment and the NuM added to the soil. Of all the treatments, the lowest man- ganese content was found in bulbs where manganese sulfate was added to the soil or as a foliage spray. Manganese deficiency symptoms were observed on the check plots. The comparative growth and size of the onions grown in this experiment can be seen in Figures 5 and 6. 6 9 Figure 5. The effect of rate and kind of various manganese carriers on the growth of onions in field experiment on Houghton muck soil (0 = check, 1 = 50 pounds elemental manganese as NuM, 2 = 50 pounds elemental manganese as manganese sulfate, and 3 = 50 pounds elemental manganese as man- gansoil). All of the manganese was applied to the soil. 70 Figure 6. The effect of method and rate of application of several manganese carriers on the growth of onions in field ex- periment on Houghton muck soil (3 = 50 pounds elemental manganese as mangansoil, 4 = 20 pounds elemental man- ganese as mangansoil, 5 = 20 pounds elemental manganese as NuM, and 6 = 20 pounds elemental manganese as man- ganese sulfate). Number 3 was applied to the soil and numbers 4, 5, and 6 were applied as spray. 72 SUMMARY The occurrence of manganese deficiency in plants is primarily due to adverse soil conditions which render the element unavailable to the plants. The use of a plant spray or injection of salts of this element in order to avoid the disturbing soil factors is not always applicable and does not always give satisfactory results. The possibility of supplying the element by adding slowly available forms or artificially prepared physical complexes to the soil has been discussed and the ideal properties of such materials have been defined. It has been pointed out that partial absorption of the element will take place through contact between the material and the plant roots. Cases in which such contact absorption is as- sumed to take place have been cited. This study was designed to investigate what effects three dif- ferent types of manganese carriers have upon the growth 'and man- ganese content of different cr0p plants when applied to three mineral soils and one organic soil. The types of manganese carriers studied were (1) readily soluble manganese sulfate; (2) a soluble chelate, called Mn-EDTA or Sequestrene; and (3) very slightly soluble glassy frits. 73 74 Experiments were conducted in the greenhouse, field, and laboratory. The greenhouse experiments were undertaken to deter- mine the effect of varying applications of lime and of five manganese carriers upon the yield and manganese content of spinach, oats, and field beans. The field experiment was undertaken to ascertain the effect of kind of manganese carrier and methods of application upon — the yield and manganese content of onions. The laboratory study of the solubility of glassy frit in buffered pH solutions was carried out to help explain the behavior of frit in soils of widely different re- action. 1. The solubility studies in the laboratory on frit showed that as the pH of the extracting solution increased the manganese released from the frit decreased appreciably. Thus it seems very probable that soil reaction affects the solubility of manganese from frit applied to soils. 2. The addition of manganese, regardless of carrier, signifi- cantly increased the yield and manganese content in all of the crops studied compared with that of the control. 3. When considering carriers, in Experiments 1 and 2, frit gave the highest, manganese sulfate the next, and Sequestrene (the chelate) the lowest. In general, as the rate of each of the manganese carriers was increased the yield and manganese content of the 75 harvested plants were increased. However, 2000 pounds of frit per acre produced essentially the same amount of dry matter as did 4000 pounds. 4. As the rates of lime in Experiment 2 were increased, regardless of the rate of glassy frit, the manganese content of two cr0p plants was decreased. This is believed to be related to the solubility of frit in media of varying reaction. 5. In Experiment 4 the method of application of manganese carrier for onions in the field was found to be important. Whether the carrier was applied to the soil or sprayed on the foliage the yield increases from addition of manganese were very significant compared to that of the control. Greater yields of onions were found when manganese carriers were applied to the soil than when' they were used as a foliage spray. 6. The data for dry weight and manganese absorption by the several crOps indicated a relatively large release of manganese by the different manganese carriers used. No symptoms of manganese deficiency appeared when more than 50 pounds per acre of any of the manganese carriers were applied. In general, the higher the yield the more vigorous were the crops grown. 7. Yields obtained from all rates of manganese sulfate and the two higher rates of frit FN-239B, in Experiment 3, were highly 76 significant over those of the check. Plants grown on soil treated with the highest rate of frit FN-SOl absorbed the largest amount of manganese. 8. The residual manganese in the soils in Experiment 2 in- creased as the rates of lime and frit were increased, thus estab- lishing a relationship between soil reaction and amount of frit ap- plied. LITERATURE CITED Alberts, W. B. Further observations on manganese deficiency in oats at Florence, South Carolina. South Carolina Agr. Exp. Sta. 47th Ann. Rep., p. 45, 1934. Bennett, J. P. The treatment of lime-induced chlorosis in fruit trees. PhytopathOIOgy 17:745-748, 1927. («e Briggs, L. J., and J. W. McLane. The moisture equivalent of f soils. USDA. Bur. Soils Bull. 45, 1907. 5 Chapman, H. D. Absorption of iron from finely ground magne- J -t1te by citrus seedlings. Soil Sci. 48:309-317, 1931. 1 Connor, S. D. Factors affecting manganese availability in soils. J. Am. Soc. Agron. 24:726-733. 1932. Cook, R. L., and C. E. Millar. Manganese for oats and white beans in Michigan. Soil Sci. Soc. Amer. Proc. 6:224- 227, 1941. Eaton, F. M. Automatically Operated sand-culture equipment. J. Agr. Research 53:433-444, 1936. Foy, C. L. Effects of 2,2-dichloropr0pionic acid (dalapon) on cotton and annual weeds. West. Weed Control Conf. Research Prog. Report 14:90-92, 1954. Gilbert, B. E. Normal Cr0ps and the supply of available soil manganese. Rhode Island Agr. Exp. Sta. Bull. 246, 1934. Guest, P. L. Root contact phenomena in relation to iron nutri- tion and growth of citrus. Proc. A.m..Soc. Hort. Sci. 44:43-48, 1944. Harmer, P. M. The occurrence and correction of unproductive alkaline organic soils. S. S. S. Am. Proc. 72378—386, 1942. 77 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 78 Heck, W. W., and L. F. Bailey. Chelation of trace metals in nutrient solution. Plant Physiol. 25:573, 1950. Holmes, R. S., and J. C. Brown. Chelates as correctives for chlorosis. Soil Sci. 80:167-179, 1950. Jacobson, L. Maintenance of iron supply in nutrient solution by a single addition of ferric potassium ethlenediamine tetraacetate. Plant Physiol. 26:411-413, 1951. Jenny, H., and R. Overstreet. Contact effects between plant roots and soil colloids. Proc. Nat. Acad. Sci. U. S. 24:384-392, 1938. Johnson, M. O. Manganese as a cause of the depression of assimilation of iron by pineapple plants. J. Ind. Eng. Chem. 9:47-49, 1917. Jones, L. H. P., and C. W. Leeper. The availability of various manganese oxides to plants. Plant and.Soi1 3:141-153, 1951. Leeper, G. W. Manganese deficiency of cereals. Plot experi- ments and a new hypothesis. Proc. Roy. Soc. Victoria 47:225-261, 1935. Experiments on manganese deficiency disease (grey speck) of cereals. Proc. Roy. Soc. Victoria 52:138- 152, 1940. Leonard, C. D. Correction of iron chlorosis in citrus with chelated iron. Proc. Florida State Hort. Soc. 66:49-54, 1953. Leonard, C. D., and 1. Stewart. Chelated iron as a corrective for lime-induced chlorosis in citrus. Proc. Florida State Hort. Soc. 65:20-24, 1952. Martell, A. E., and C. Melvin. Chemistry of the metal chelate compounds. Prentice-Hall, Inc., New York, pp. 1-15, 1952. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 79 McCall, Wade, and J. F. Davis. Foliar applications of plant nutrients to crops grown on organic soils. Quarterly Bulletin, Mich. Agr. Expt. Sta., V01. 35, No. 3, pp. 373- 383, 1953. McGeorge, W. T. The chlorosis of pineapple plants grown on manganiferous soils. Soil Sci., 16:269-274, 1923. Mellor, J. W. A. comprehensive treatise on inorganic and theo- retical chemistry. New York: Longmans, Green and Co., 1932, Vol. 12. Piper, C. S. The availability of manganese in the soil. J. Agr. Sci. 21:762-779. 1931. Samuel, (3., and C. S. Piper. Grey Speck (manganese deficiency) disease in oats. J. Dept. Agr. 5. Australia, 31:699- 705, cont. 789-799, 1928. Schollenberger, C. J., and R. H. Simon. Determination of ex- change capacity and exchangeable bases in soil-ammonium acetate method. Soil Sci. 59:13-24, 1945. Sherman, G. Donald. The activation of iron in plants by man- ganese and other chemicals in a lime-induced chlorosis. Thesis, Michigan State College, 1940. Sherman, G. Donald, and P. M. Harmer. Manganese deficiency of oats on alkaline organic soils. J. Am. Soc. Agron. 33:1080-1092, 1941. Shive, J. W. A three-salt, solution for plants. Am. J. Botany 21 157-160, 1915. Skinner, J. J., and R. W. Ruprecht. Fertilizer experiments with truck cr0ps. 111. Truck cr0ps in manganese on calcare- ous soil. Florida Agr. Exp. Sta. Bull. 218, pp. 37-65, 1930. Snedecor, G. W. Statistical methods. Ed. 4. The Collegiate Press, Ames, Iowa, 1946. :- ._ .h... . . _ , ' . I.. a. . 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 80 Somers, I. 1., and J. W. Shive. The iron manganese relation in plant metabolism. Plant Physiol. 17:582-603, 1942. Stewart, 1., and C. D. Leonard. What chelates are. National Fertilizer Review, pp. 9-11, 4th Quarter, 1954. Tottingham, W. E., and A. J. Beck. Antagonism between man- ganese and iron in the growth of wheat. Plant World 19:359-470, 1916. Wain, R. L., B. J. Silk, and C. B. Wills. The fate of manganese f “M sulfate in alkaline soils. J. Agr. Sci. 33:18-22, 1943. -‘ Wallace, T. Investigations on chlorosis of fruit trees. 11. The l composition of leaves, bark, and wood of current season’s t: Shoots in cases of lime-induced chlorosis. J. Pomol. ‘ Hort. Sci. 7:172-183, 1928. -» a...) Investigations on chlorosis of fruit trees. IV. The control of lime-induced chlorosis in the field. J. Pomol. Hort. Sci. 7:251-269, 1929. Wallace, T., and L. Ogilvie. Manganese deficiency of Agricul- tural and Horticular cr0ps. Summary of investigations, season 1941. Ann. Rep. Agr. and Hort. Research Sta., Long Ashton, Bristol, 1941, pp. 45-48, 1941. Wallace, A., and C. P. North. Lime-induced chlorosis. Calif. Agr. 728-10, 1953. Wallace, A., et a1. Chlorosis in ornamentals. Calif. Agr. 7: 13-14, 1953. Weinstein, L. H., et a1. Chelates, absorption and translocation of ethylene-diaminetetraacetic acid by sunflower plants. Agr. and Food Chem. 2:421-425, 1954. Willard, H. H., and L. H. Greathouse. The colorimetric deter- mination of manganese by oxidation with periodate. J. Am. Chem. Soc. 39:2366-2377, 1917. Willis, L. G. Response of oats and soybeans to manganese on some coastal plain soils. North Carolina Agr. Exp. Sta. Bull. 257, 1928. 46. 47. 48. 81 The effect of liming soils on the availability of man- ganese and iron. J. Am. Soc. Agron. 24:716-726, 1932. Wynd, F. L., and R. A. Bowden. Responses of snapdragons to very insoluble iron-containing frit. Lloydia 14:No. 1, 1951. Wynd, F. L., and E. R. Stromme. Absorption of manganese and iron by Navy bean plants grown in a calcareous soil fertilized with a manganese-containing glassy frit. Lloydia 14:No. 1, 1951. APPENDIX Cation Exchange Capacity Determination (28) A 5 gram sample of air-dry soil was placed in a 300 milli- liter Erlenmeyer flask, and 100 milliliters of neutral normal ammo- . nium acetate were added to it. This was shaken for several minutes and allowed to stand overnight. The contents were then transferred to a Buchner funnel, fitted with moistened 5.5 centimeters Whatman No. 42 filter paper and gentle suction applied. The soil was then leached with an additional 400 milliliters of the extracting solution adding small portions at a time and using gentle suction, so that the leaching process would not require less than one hour. (The filtrate was saved.) The excess ammonium acetate was washed out with excess (200 milliliters or more) of 95 percent ethyl alcohol using small portions and draining well each time. (Note: To de- termine if all the occluded ammonia was removed by leaching with ethyl alcohol, one drop of Nessler's reagent was added to three drops of the leachate on a spot plate. The color obtained was com- pared to standard color chart for ammonia. A, very pale yellow color indicates approximately 1 part per million of ammonia present.) The alcohol leachate was discarded. The soil was next leached with 82 83 450 milliliters of 10 percent NaCl and this extract distilled from a Kjeldahl flask to which had been added 20 milliliters of 2N NaOH. The distillate was then taken up to 50 milliliters of 4 percent boric acid solution and titrated with standard 0.1N HCl using bromocresol green as the indicator. 84 Table 21. Analysis of variance for the yield of spinach in green- house experiment 1. Source D.F. SS MS F Total ............. 155 2308.1 Replication ......... 3 2.0 0.7 Soils ............. 2 635.4 317.7 2118** by E1 Controlzothers ...... 1 331.1 331.7 1440*"? by E2 Carrier (Mn) . . . . . . . 2 471.9 236.4 481** by E3 Rates within carrier . . 9 752.9 84.3 171*" by E4 Soils X controlrothers . 2 24.5 12.3 37** by ES Soils X carrier ...... 4 1.5 0.4 l n.s. by E5 Soils X rates within carrier ........... 18 47.4 3.1 8** by ES Replication X soil (El). 6 0.9 0.2 Replication X control: others (E2) ........ 3 0.7 0.2 Replication X carrier (E3) ............. 6 2 9 0 5 Replication X rates within carrier (E4) . . . 27 13.1 0.5 Remainder-error (E5) . 72 23.7 0.3 I— ‘ f V‘ Soils L.S.D. at 5% = 0.19; at 1% 0.28. Carrier L.S.D. at 5% = 0.35; at 1% = 0.53. Rates within carrier L.S.D. at 5% = 0.59; at 1% = 0.79. 85 Table 22. Analysis of variance for the manganese content of spinach in greenhouse experiment 1. Source D.F. SS MS F Total .......... 115 827930 Replication ...... 3 105 35 Soils .......... 2 34934 17467 437** by El Control: others . . . 1 207713 207713 8775** by E2 Carrier (Mn) . . . . 2 37394 18697 745** by E3 Rates within carrier . . . . . . . . 9 510505 56723 1343** by E4 Soils X control: others ......... 2 295 148 0.4 n.s. by ES Soils X carrier . . . 4 676 169 0.4 n.s. by ES Soils X rates within carrier . . . 18 4003 222 0.5 n.s. by ES Replication X soils (E1) ...... 6 240 40 Replication X controlzothers (E2). 3 71 24 Replication X carrier (E3) ..... 6 151 25 Replication X rates within carrier (E4) ..... 27 1140 42 Remainder-error (E5) .......... 72 30704 426 Soils L.S.D. at 5% = 3.03; at 1% = 4.60. Carrier L.S.D. at 5% Rates within carrier L.S.D. at 5% 2.50; at 1% = 3.79. = 5.44; at 1% = 7.35. 86 Table 23. Analysis of variance for dry weight of oat plants in green— house experiment 1. Source D.F. SS MS F Total ............... 155 2409.7 R eplication ........... , 3 1.8 0.6 Soils ............... 2 577.9 289.0 525** by El Controlzothers ........ 1 361.8 361.8 804** by E2 Carrier (Mn) ......... 2 456.3 228.1 1342** by E3 Rates within carrier . . . . 9 845.1 93.9 177** by E4 Soils X control:others . . . 2 40.5 20.3 72** by 1335 Soils X carrier ........ 4 38.8 9.7 35** by ES Soils X rates within carrier ............. 18 79.3 4.4 16** by ES Replication X soil (E1) . . 6 0.3 0.6 Replication X control: others (E2) .......... 3 1.3 0.5 Replication X carrier (E3) 6 1.0 0.2 Replication X rates within carrier (E4) ..... 27 14.4 0.5 Remainder-error (E5) . . . 72 20.5 0.3 I: L A J L: r _J_ Soils L.S.D. at 5%: 0.36; at 1% = 0.54. Carrier L.S.D. at 5% = 0.21; at 1% = 0.31. Rates within carrier L.S.D. at 5% = 0.61; at 1% = 0.82. 87 Table 24. Analysis of variance for the manganese content of oat plants in greenhouse experiment 1. Source D.F. 55 MS F Total .............. 155 1878489 R eplication .......... 3 181 6 0 Soils .............. 2 28988 14494 8040:: by El Control:others ....... 1 404862 404862 3542””? by E2 Carrier (Mn) ........ 2 58126 29063 259** by E3 Rates within carrier . . . 9 1321894 146877 730** by E4 Soils X control:others . . 2 4961 2481 11** by E5 Soils X carrier ....... 4 2527 632 3* by ES Soils X rates within Carrier ............ 18 33563 18646 85** by ES Replication X soil (El) . 6 1091 182 Replication X control: others (E2) ......... 3 343 114 Replication X carrier (E3) .............. 6 674 112 Replication X rates within carrier (E4) . . . . 27 5435 201 Remainder-error (E5) . . 72 15844 220 Soils L.S.D. at 5% = 6.5; at 1% = 9.8. Carrier L.S.D. at 5% = 5.3; at 1% = 8.0. Rates within carrier L.S.D. at 5% = 11.9; at 1% = 16.1. 88 Table 25. Analysis of variance for the dry weight of bean plants in greenhouse experiment 1. Source D .F . SS MS F Total ............... 155 3080.0 R eplication ........... 3 0 .4 0.1 Soils . . . . . . . . . . . . . .. 2 606.5 303.2 3032*”? by E1 Control:others ........ 1 644.3 644.3 1841** by E2 Carrier (Mn) ......... 2 621.0 310.5 2823** by E3 Rates within carrier . . . . 9 960.4 106.7 593** by E4 Soils X control:others . . . 2 28.6 14.3 72** by ES Soils X carrier ........ 4 150.9 37.7 189** by ES Soils X rates within carrier ............. 18 46.7 2.6 13*" by ES Replication X soil (E1) . . 6 0.3 0.1 Replication X control: others (E2) .......... 3 1.0 0.4 Replication X carrier (E3) ............... 6 0.6 0.1 Replication X rates within carrier (E4) ..... 27 4.9 0.2 Remainder-error (E5) . . . 72 14.3 0.2 Soils L.S.D. at 5% = 0.36; at 1% = 0.54. Carrier L.S.D. at 5% = 0.52; at 1% = 0.79. Rates within carrier L.S.D. at 5% = 0.36; at 1% = 0.48. 89 Table 26. Analysis of variance for the manganese content of bean plants in greenhouse experiment 1. Source D.F. SS MS F Total ............ 155 1887584 Replication ........ 3 392 131 Soils . ........... 2 90982 45491 304** by E1 Control:others ..... 1 387407 387407 5884** by E2 Carrier (Mn) ...... 2 77178 38589 340** by E3 Rates within carrier . 9 1251380 139042 708** by E4 Soils X control:others. 2 530 265 2 n.s. by E5 Soils X carrier ..... 4 34367 8592 67** by ES Soils X rates within carrier .......... 18 29019 1612 13** by ES Replication X soil (E1) ............ 6 898 ‘ 150 Replication X control: others (E2) 3 198 66 Replication X carrier (E3) ............ 6 680 113 Replication X rates within carrier (E4) . . 27 5300 196 72 9256 129 R emainder- error (E5) fl bu: ‘1; Soils L.S.D. at 5% = 5.87; at 1% = 8.90. Carrier L.S.D. at 5% Rates within carrier L.S.D. at 5% 5.32; at 1% — — = 8.10. 11.74; at 1% = 15.85. 90 Table 27. Analysis of variance for the dry weight of oat plants in greenhouse experiment 2. 7 Source DiF. SS MS Total ............... 107 1750.6 Replication ........... 2 1.2 0.6 Soils ............... 2 290.5 145.2 1037** by E1 Frit ............... 1 127.0 127.0 192** by E2 Soil X frit ........... 2 2.5 1.3 6** by 1533 Lime within soils . . . . . . 15 1297.2 864.8 4118** by E3 Lime within frit within soils ............... 15 16.8 1.1 5** by E3 Replication X soil (El) . . 4 0.6 0.1 Replication X frit (E2) . . . 2 1.3 0.7 Remainder-error (E3) . . . 64 13.6 0.2 t: W In: T L Soils L.S.D. at 5% = 0.24; at 1% =3 0.41. Frit L.S.D. at 5% = 0.67; at 1% = 1.55. Lime within soils L.S.D. at 5% = 0.53; at 1% = 0.70. Lime within frit within soils L.S.D. at 5% = 0.75; at 1% = 0.99. 91 Table 28. Analysis of variance for the manganese content of oat plants in greenhouse experiment 2. Source D.F. SS MS F Total ....... 107 2792725.2 Replication . . . 2 1.1 0.6 Soils ....... 2 164050.5 82025.3 430** by E1 Frit ....... 1 1167712.0 1167712.0 5838560103 by E2 Soil x frit .. . 2 25627.9 12814.0 137** by E3 Lime within soils . ...... 15 1403951.3 93596.8 997** by E3 Lime within frit within soils ....... 15 24608.8 16410-6 18*”: by E3 Replication X soil (E1) . . . . 4 763.4 190.9 Replication X frit (E2) ' . . . . 2 0.4 0.2 Remainder- error (E3) . . . 64 6009.8 93.9 Soils L.S.D. at 5% = 9.04; at 1% = 14.99. Frit L.S.D. at 5% = 0.37; at 1% = 0.85. Lime within soils L.S.D. at 5% = 11.19; at 1% = 14.88. Lime within frit within soils L.S.D. at 5% I 15.82; at 1% 2 21.05. 92 Table 29. Analysis of variance for the dry weight of bean plants in greenhouse exPeriment 2. L Source D.F. SS MS F Total .............. 107 1445.1 Replication .......... 2 3.9 2.0 Soils .............. 2 207.3 103.7 207*" by El Frit ...... I ........ 1 301.7 301.7 1509*" by E2 Soil X frit . ......... 2 3.5 1.8 8 n.s. by E3 Lime within soils . . . . . 15 884.2 59.0 256"" by E3 Lime within frit within soils ......... 15 27.3 1.8 8*" by E3 Replication X soil (El) . 4 2.0 0.5 Replication X frit (E2) . . 2 0.4 0.2 Remainder-error (E3) . . . 64 14.8 0.2 J- A r A - -Iri . - i 5611s L.S.D. at 5% =' 0.46; at 1% = 0.77. Frit L.S.D. at 5% = 0.37; at 1% = 0.85. Lime within soils L.S.D. at 5% = 0.55; at 1% = 0.74. Lime within frit within soils L.S.D. at 5% = 0.78; at 1% = 1.04. 93 Table 30. Analysis of variance for the manganese content of bean plants in greenhouse experiment 2. Source D.F. SS MS F Total ............. 107 2628499 Replication ......... 2 46 23 Soils ............. 2 324382 162191 916340: by El Frit ............. 1 828801 828801 12501403 by E2 5611 x frit ......... 2 5320 2660 32* by E3 Lime within soils . . . . 15 1437041 95803 1159** by E3 Lime within frit ..... 15 27415 1828 2243* by E3 1 V J Replication X soil . . . . 4 71 18 Replication X frit . . . . 2 133 66 Remainder-error . . . . 64 5292 83 w fir Soils L.S.D. at 5% =- 2.75; at 1% = 4.57. Frit L.S.D. at 5% = 6.74; at 1% = 15.55. Lime within soils L.S.D. at 5% 3 10.50; at 1% 8 13.97. Lime within frit within soils L.S.D. at 5% = 14.85; at 1% : 19.75. 94 Table 31. Analysis of variance for the yield of spinach in greenhouse experiment 3. Source D.F. SS MS F Total ..................... 41 87.34 Replication ................. 2 6.87 Treatments ................ 13 59.21 4.55 5.55"" Remainder-error . ........... 26 21.25 0.82 it "C ‘ L.S.D. at 1% = 1.52. 95 Table 32. Analysis of variance for the yield of onions in the field experiment. “— Source D.F. SS MS F Total ................... 20 388457 19432 Replication ............... 2 6767 3383 Treatments .............. 6 259545 43257 42.96" Remainder-error . ......... 12 22145 1895 L.S.D. at 5% = 76. 96 Table 33. The effect of kind and rate of application of manganese carrier on the dry-weight yield of spinach grown on three soils in greenhouse experiment 1 (dry weight in grams). Rate of h . . Manganese Appli- Os temo $011, Replication Carrier cation 1 2 4 . (1bs./a.) 3 Avg Control ........... 0 2.9 3 0 3 6 3 8 3 3 MnSO4 ............ 25 4.0 3.8 4.6 3.4 3.7 50 5.6 4.0 4.5 5.0 4.7 100 7.1 6.4 8.4 7.2 7.2 200 8.9 9.0 8.6 9.4 8.9 Frit ............. 500 6.9 7.1 6.7 7.8 7.1 1000 8.0 9.1 9.3 8.9 8.0 2000 10.0 11.1 12.1 11.9 11.2 4000 10.1 11.5 9.8 10.3 10.4 Sequestrene ........ 50 3.5 3.1 2.9 3.9 3.3 100 4.0 5.1 4.5 3.6 4.3 200 6.0 5.9 5.5 4.9 5.8 400 7.9 8.1 6.9 8.2 7.7 Table 3 3 (Continued) 97 Thomas Soil, Replication Muck Soil, R eplic ation 1 2 3 4 Avg. 1 2 3 4 Avg. 6.0 5 6 5.4 6.1 5. 5.1 4.0 3.9 4.5 4.3 7 1 7.4 6.9 7.3 7. 8.0 7.9 8.6 8.1 8.1 9 1 8.9 8.8 9.4 9. 9.6 9.4 8.9 8.6 9.1 10.4 11.0 10.9 12.2 11. 11.3 10.4 11.6 12.1 11.3 13.0 14.1 13.4 14.4 13. 14.0 13.6 13.4 14.3 13.8 9.6 10.1 11.4 10.4 10. 10.1 9.4 8.9 9.6 9.5 12.1 13.0 11.8 12.4 12. 10.9 12.4 12.1 11.8 11.8 16.1 15.2 17.0 18.0 16. 16.6 17.1 18.4 17.9 17.5 15.1 16.3 17.1 16.0 16. 19.0 18.1 17.1 17.8 18.0 6.9 7 4 7.1 6.6 7. 7.1 6.9 8.4 7.3 7.4 8 9 9.0 8.4 8.7 8. 8.1 8.4 7.9 9.1 8.6 10.1 10.1 9.9 11.0 10. 10.3 12.0 11.4 11.3 11.2 13.1 11.9 12.6 12.4 12. 14.1 13.4 13.8 13.1 13.6 98 Table 34. The effect of kind and rate of application of manganese carrier on the manganese content of spinach grown on three soils in greenhouse experiment 1 (parts per million). Rate of , Manganese Appli- Oshtemo Soil, Replication Carrier cation 5 W T m 2 . . (lbs./a.) 1 3 4 Avg Control ........... 0 30 29 41 34 33.5 MnSO4 ............ 25 89 96 87 90 91 50 137 143 150 141 143 100 201 212 207 205 207 200 234 243 238 229 236 Frit ............. 500 94 103 99 109 101 1000 152 163 149 157 155 2000 220 226 230 219 224 4000 247 261 250 219 253 Sequestrene ........ 50 73 64 70 67 69 100 126 127 120 132 126 200 187 193 174 182 184 400 212 209 206 215 211 99 Table 3 4 (Continued) Thomas Soil, Replication Muck Soil, Replication 1 2 3 4 Avg. 1 2 3 4 Avg. 64 56 60 . 59 59.8 54 50 49 58 52.8 139 143 134 145 140 103 99 97 107 102 164 172 169 177 171 147 158 161 154 155 250 239 245 241 244 219 223 234 220 224 289 283 278 287 284 271 263 253 259 262 140 135 130 139 136 121 118 133 129 125 187 193 196 189 191 173 184 179 181 179 256 249 253 261 255 243 239 249 255 247 I 297 301 299 308 301 283 249 287 274 281 103 98 109 101 103 82 88 79 91 85 151 154 149 147 150 131 129 140 136 134 201 211 199 205 204 189 194 176 190 187 274 263 270 268 269 254 249 263 258 256 100 Table 35. The effect of kind and rate of application of manganese carrier on the dry weight yield of oat plants grown on three soils in greenhouse experiment 1 (dry weight in grams). Rate ,°f Oshtemo Soil, Replication Manganese Appli- fl Carrier cation 1 2 3 4 A . (lbs./a.) Vg Control ........... 0 28.0 29.1 30.1 28.9 29.0 MnSO4 ............ 25 29.1. 28.9 30.1 29.4 29.0 50 30.1 31.4 30.4 31.7 30.9 100 33.6 32.9 33.0 32.8 33.0 200 34.6 34.1 33.8 34.3 34.2 Frit ............. 500 30.1 31.3 31.9 32.0 31.3 1000 33.0 34.1 33.6 33.6 33.3 2000 35.4 35.9 36.0 34.9 35.5 4000 36.0 35.9 36.1 36.3 36.0 Sequestrene ........ 50 30.1 29.6 28.4 29.6 29.4 100 30.4 31.0 30.4 29.9 30.4 200 32.4 31.9 32.0 32.8 32.2 400 33.9 34.0 34.0 33.7 33.9 Table 35 (Continued) 101 Thomas Soil, R eplication Muck Soil, Replication 1 2 3 4 Avg. 1 2 3 4 Avg 30.1 31.1 30.4 30.6 30.5 28.9 30.1 28.4 29.6 29.2 32.1 31.8 32.3 31.4 31.9 33.1 32.6 33.4 32.5 32.9 34.1 35.4 34.6 34.0 34.5 35.1 34.9 34.8 35.3 35.0 36.1 35.9 36.4 36.5 36.2 35.9 36.4 36.7 36.8 36.4 37.9 38.1 38.4 39.1 38.3 39.1 38.9 39.4 39.6 39.2 34.1 33.9 35.1 35.8 34.7 33.9 34.6 36.0 35.9 35.1 37.1 36.8 36.4 37.3 36.9 38.0 39.1 38.9 39.6 . 38.9 41.1 41.5 40.9 40.7 41.0 44.0 45.0 43.9 44.2 44.2 42.0 41.3 40.8 41.4 41.3 46.1 44.3 44.1 45.3 44.9 31.9 32.0 31.8 30.4 31.2 32.1 33.0 32.9 31.8 32.4 33.6 33.1 32.9 34.0 33.4 34.0 34.3 35.0 35.3 34.5 35.0 34.9 35.2 34.8 34.9 36.0 35.8 36.7 35.4 35.7 37.0 36.9 38.1 38.9 37.9 38.9 39.1 39.5 38.3 38.9 102 Table 36. The effect of kind and rate of application of manganese carrier on the manganese content of oat plants grown on three soils in greenhouse experiment 1 (parts per million). Rate ,Of Oshtemo Soil, Replication Manganese Appli- f - f Carrier ~cation . 2 . . (lbs./a.) 1 3 4 Avg Control ........... 0 69 86 74 76 76 MnSO4 ............ 25 151 141 149 164 151 50 198 171 193 184 187 100 279 325 293 304 300 200 369 388 374 391 381 Frit ............. 500 160 164 170 156 163 1000 211 230 224 218 221 2000 379 398 364 398 383 4000 401 398 388 420 402 Sequestrene ........ 50 101 121 123 139 121 100 198 174 186 200 190 200 289 341 317 293 310 400 359 354 319 324 342 Table 36 (Continued) 103 Thomas Soil, Replication Muck Soil, Replication 1 2 3 4 Avg. 1 2 3 4 Avg. 115 105 121 99 110 88 79 80 69 79 156 145 139 139 144 139 156 160 172 157 225 229 238 219 228 269 243 259 338 277 369 345 371 386 368 398 376 384 377 384 396 379 400 367 386 401 396 411 388 399 170 160 159 179 167 174 200 184 179 184 244 252 260 239 249 291 301 310 319 305 390 399 401 410 400 401 397 389 379 392 401 384 389 376 388 410 396 401 378 397 141 123 140 135 135 110 99 107 120 109 199 201 189 219 202 234 198 225 201 215 291 319 297 329 309 352 364 379 369 366 354 364 371 369 365 398 406 388 391 396 104 Table 37. The effect of kind and rate of application of manganese carrier on the yield of beans grown on three soils in greenhouse experiment 1 (dry weight in grams). Rate ,Of Oshtemo Soil, Replication Mang ane s e Appll - v m Carrier cation 2 4 . (1bs./a.) 3 Avg Control ........... 0 15. 14.9 16.0 15.5 15.3 MnSO4 ............ 25 18. 17.8 18.3 17.5 17.9 50 19. 19.0 19.9 18.7 19.2 100 24. 24.6 25.1 24.9 24.7 200 25. 25.3 24.9 25.6 25.2 Frit ............. 500 19. 19.7 18.9 19.5 19.3 1000 21. 22.3 21.6 22.1 21.9 2000 24. 24.8 25.0 24.5 24.6 4000 25. 24.7 24.4 25.1 24.8 Sequestrene ........ 50 18. 17.2 17.6 17.1 17.5 100 19. 18.1 18.5 18.7 18.5 200 21. 22.4 21.9 22.1 22.0 400 21. 22.6 21.4 21.7 21.9 105 Table 37 (Continued) Thomas Soil, Replication Muck Soil, Replication 1 2 3 4 Avg. 1 2 3 4 Avg. 18.5 18.3 19.1 18.7 18.4 16.1 15.8 16.4 16.7 16.2 20.3 20.6 21.1 19.4 20.3 18.4 19.0 18.1 18.7 18.5 25.0 25.5 26.1 25.8 25.6 23.4 23.8 22.9 24.1 23.5 26.9 26.3 26.7 27.1 26.8 25.1 26.2 25.7 25.3 25.5 27.4 26.9 27.1 26.5 26.9 26.9 27.1 26.3 26.0 26.3 24.4 24.1 24.8 25.2 29.6 25.1 24.8 25.3 25.7 25.2 28.1 28.7 27.9 28.5 28.3 29.6 29.3 30.1 29.0 29.5 30.9 31.3 31.6 30.5 31.0 32.4 31.9 32.9 32.6 '32.4 31.7 31.2 30.9 31.0 31.2 33.9 34.1 33.7 34.5 34.0 20.1 19.8 19.6 20.7 20.0 21.5 21.7 22.0 22.1 21.8 21.9 21.3 22.2 21.5 21.4 23.0 23.7 24.1 23.5 23.3 24.2 24.8 24.5 25.1 24.4 25.8 25.3 26.1 26.3 25.8 25.9 25.2 24.8 26.1 25.5 26.4 26.6 27.0 25.9 26.4 106 Table 38. The effect of kind and rate of application of manganese carrier on the manganese content of beans grown on three soils in greenhouse experiment 1 (parts per million). Rate of h . . . Manganese Appli- O:temo Sail, Replication Carrier cation 1 2 4 . (1bs./a.) 3 Avg Control ........... 0 75 84 90 79 82 MnSO4 ............ 25 152 151 160 142 151 50 187 201 192 189 192 100 256 287 271 262 269 200 381 369 359 371 370 Frit ............. 500 184 171 164 176 174 1000 231 250 245 229 238 2000 371 365 382 379 374 4000 421 399 400 409 407 Sequestrene ........ 50 133 120 129 136 130 100 209 198 202 189 200 200 302 316 319 312 312 400 352 344 362 359 354 107 Table 38 (Continued) J Thomas Soil, Replication Muck Soil, Replication 1 2 3 4 Avg. 1 2 3 4 Avg. 125 129 130 121 126 99 109 101 89 99 196 204 187 193 195 164 172 178 169 171 301 289 274 286 288 251 249 259 253 235 437 456 447 450 448 296 399 384 379 390 464 469 456 470 465 426 431 420 416 423 211 198 231 220 215 176 169 180 171 174 284 276 280 269 277 230 344 227 235 259 411 412 408 420 413 366 351 364 359 360 431 429 433 419 428 408 411 401 397 404 163 159 146 150 155 142 139 136 147 141 226 233 243 229 233 179 186 172 190 182 347 334 353 358 348 268 274 256 269 267 414 409 411 420 414 356 349 350 360 354 108 Table 39. The effect of varying rates of lime and frit on the dry— weight yield of oat plants grown on three soils in green- house experiment 2 (in grams). Lime Frit (lbs./a.) Frit (1bs./a.) Soil .Type 15:: - “/a.) 500 500 500 Avg. 2000 2000 2000 Avg. Oshtemo 0 6.5 7.3 7.1 7.0 8.9 8.3 9.0 8.7 sand 1/4 9.3 8.8 8.3 8.8 10.4 11.6 11.2 11.1 1/2 10.0 9.3 10.5 9.9 12.3 13.0 12.7 12.7 1 11.9 12.4 12.8 12.4 15.7 16.3 16.0 16.0 2 15.9 15.3 16.4 15.7 18.1 18.9 18.5 18.5 3 16.2 15.6 17.1 16.3 17.9 18.1 17.4 17.8 Hillsdale 0 8.3 7.9 8.1 8.1 10.3 9.6 9.5 9.8 and” ham 1 10.4 9.9 10.1 1071 11.4 12.1 11.9 11.8 2 13.0 12.4 12.8 12.7 14.3 15.4 14.7 14.4 3 14.3 13.9 14.7 14.3 16.4 17.9 17.6 17.3 4 16.8 17.4 11.3 16.8 19.4 20.3 19.9 19.9 5 17.1 16.8 17.3 17.1 19.3 20.1 19.6 19.7 Houghton 0 9.3 10.1 9.7 9.7 13.4 12.9 13.6 13.3 mud‘ 3 13.4 12.9 14.1 13.5 15.1 14.9 15.4 13.5 6 15.3 14.7 15.6 15.2 17.1 16.9 17.5 17.2 9 17.4 18.0 16.9 17.4 18.0 17.9 18.6 18.2 12 19.0 20.4 20.7 20.0 21.4 21.0 20.7 21.0 13 20.2 19.0 21.0 20.3 21.8 22.1 21.3 21.7 109 Table 40. The effect of varying rates of lime and frit on the man- ganese content of oat plants grown on three soils in green- house experiment 2 (parts per million). Lime Soil Treat- Frit (lbs./a.) Frit (1bs./a.) Type :3th 500 500 500 Avg. 2000 2000 2000 Avg. Oshtemo 0 456 432 445 444 694 709 711 7,05 sand 1/4 422 406 414 414 656 666 661 661 1/2 368 350 344 354 571 580 581 577 1 290 300 354 315 535 529 541 535 2 198 180 174 184 481 471 479 577 3 145 160 144 150 411 408 420 413 Hillsdale 0 501 494 511 502 689 679 680 683 3:11" 1 453 464 460 459 647 651 661 653 2 418 430 421 423 551 571 564 562 3 291 310 287 296 520 532 523 525 4 222 234 240 232 410 401 392 401 5 159 166 152 159 386 391 400 392 Houghton 0 431 421 426 426 599 588 594 594 mud‘ 3 391 384 379 385 555 543 537 545 6 283 301 291 292 521 518 515 518 9 221 232 229 - 227 463 449 451 454 12 174 163 169 169 333 323 315 324 15 97 89 83 90 241 253 239 244 110 14.8 18.8 Table 41. The effect of varying rates of lime and frit on the dry- weight yield of bean plants grown on three soils in green- house experiment 2 (in grams). Lime Frit (lbs./a.) Frit (1bs./a.) Soil Type 2:; e W - (t./a.) 500 500 500 Avg. 2000 2000 2000 Avg. Oshtemo 0 5.2 5.6 5.4 5.4 6.7 7.0 6.9 6.9 sand 1/4 7.1 8.0 7.9 7.7 8.4 9.6 10.0 9.3 1/2 8.9 9.0 8.4 8.8 10.3 9.9 11.0 10.4 1 11.1 10.6 10.1 10.6 15.3 14.9 14.7 15.0 2 13.4 12.9 12.0 12.8 16.3 15.9 16.4 16.2 3 12.4 11.1 12.1 11.9 16.8 16.2 15.9 16.3 Hillsdale 0 6.3 7.0 5.9 6.4 9.5 8.8 9.0 9.1 sandy ham 1 8.4 8.6 7.6 8.2 12.1 13.4 11.9 12.5 2 11.7 11.1 10.6 11.1 13.6 13.1 14.3 13.7 3 12.4 12.9 10.9 12.1 16.3 15.9 16.0 16.1 4 13.0 13.5 12.9 13.1 17.4 17.8 16.5 17.2 5 12.3 12.9 11.8 12.3 16.8 17.3 15.7 16.6 Houghton 0 8.2 8.6 8.4 8.4 10.9 11.3 10.4 10.9 "“1““ 3 10.1 11.0 10.9 10.7 13.7 14.0 13.1 13.6 6 11.9 12.0 11.8 11.9 14.6 15.0 14.3 14.3 9 14.1 13.6 13.1 13.6 18.9 17.8 18.5 18.4 12 16.4 15.9 15.3 15.9 19.6 20.1 19.1 19.6 15 15.4 14.9 14.0 20.1 19.3 19.4 111 Table 42. The effect of varying rates of lime and frit on the man- ganese content of bean plants grown on three soils in greenhouse experiment 2 (parts per million). Soil T111251:- Frit (lbs./a.) Frit (1bs./a.) Type $32“; 500 500 500 Avg. 2000 2000 2000 Avg. Oshtemo 0 525 530 510 522‘ 699 718 720 712 sand 1/4 486 470 470 482 671 682 679 677 1/2 451 421 430 434 589 590 584 588 1 381 370 364 372 551 545 563 553 2 280 276 291 282 491 499 483 491 3 190 164 186 180 399 424 419 414 Hillsdale 0 540 530 537 536 679 690 683 684 13:1? 1 513 520 509 514 653 658 671 661 2 461 470 459 463 571 563 569 568 3 341 352 337 343 544 538 551 544 4 234 251 247 244 459 441 449 450 5 178 169 184 177 409 401 ' 390 400 Houghton 0 409 421 416 415 579 564 569 571 “we" 3 381 397 374 384 563 541 554 553 6 309 331 321 320 501 493 512 502 9 254 235 242 244 453 441 438 444 12 186 174 189 183 311 314 309 311 15 106 101 94 100 231 223 227 227 Date Due , E“ WW Demco-293