THE COPPER-MANGANESE RELATIONSHIP IN THE GROWTH OP OATS, SPRING WHEAT, AND ALFALFA BY LLOYD LESTER SPARKS A THESIS Submitted to the School of Graduate Studies of Michigan State College of Agriculture and Applied Science in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Department of Soil Science 1947 ProQuest Number: 10008732 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest. ProQuest 10008732 Published by ProQuest LLC (2016). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 4 8 1 0 6 - 1346 ACKNOWLEDGMENT The author expresses his sincere appreciation to Dr. R. L. Cook for his guidance and helpful suggestions, and to Dr, Kirk Lawton for suggestions in relation to chemical analysis. TABLE OP CONTENTS Page Introduct ion........................................... 1 Review of Literature................................... 2 Experimental........................................... 4 Results................................................ 6 Plants during growth................. 6 Plainfield............. 6 Pox......................................... . 7 Alfalfa...................... 7 Pox....................... 7 Plainfield................................... 8 Discussion..... 8 Conclusions............... 10 Literature Cited....................................... 11 THE COPPER-MANGANESE RELATIONSHIP IN THE GROWTH OP OATS, SPRING WHEAT, AND ALFALFA INTRODUCTION There has been considerable work done In late years on manganese and its relationship with the growth of plants. The Interest in trace elements Is growing and we are now at­ tempting to find a reason or reasons why deficiencies or tox­ icity occurs as plants are growing. Most of the work done with copper has been done on organic soils. Our problem, therefore, is to see if copper and manganese have a definite relationship in the mineral bal­ ance of plants. In this investigation there were two soils used and the growth of Oats, Spring Wheat, and Alfalfa were observed after applying varying amounts of lime, manganese, and copper. Sommer (16) suggests that the function of Copper in plant metabolism Is that of chlorophyll formation. The usual method of administration is by the use of bordeaux mixture in the form of spray. The observance In this Investigation was with copper sulphate administered to the soil. In this manner it Is believed to serve as a catalyst. In other investigations with manganese deficiencies it was found that these conditions were mainly overcome by the addition of manganese sulphate. 1. With copper sulphate added to Figures in parentheses refer to "Literature Cited," P. - 2 soils it was found that some crops were least responsive on acid soils when varying amounts of lime were added. REVIEW OP LITERATURE Willis (18) reports on his work carried on in 1936 with the relationship of copper to manganese and iron. He found that copper serves as a catalyst, and it serves as a soil amendment, decreasing the availability of iron and pos­ sibly manganese. It may be favorable or not, depending on the oxidation intensity and the manganese content of the soil. Although no conclusive evidence has been found it is assumed that the maintenance of manganese in field soils is dependent on the presence of a catalyst such as calcium. Copper is most beneficial on well-aerated soils. McHargue (10), in experimenting with acid soils which contained approximately one-tenth of one per cent of manganese, found that only small amounts of the total man­ ganese were soluable in water. By adding manganese in the form of the sulphate to the acid soil he caused a decrease in the yields of the crops. An excess of manganese sulphate in a soil renders it sterile with respect to the growth of plants. Calcium Carbonate in the soil causes a diminution in the toxic effects produced by an excess of manganese sulphate. Experimenting with the relation of copper on dif­ ferent soil types in Florida, Hill (6 ) found that he obtained stimulation by using copper on soils of lowest productivity. 3 This indicated that copper has a nutritive value and may be associated with the formation of plant hormones, possibly Vitamins, or related compounds. Arnon (l) investigated nutrition of barley plants grown at different seasons by controlling the variables of reaction, aeration, and concentration of manganese and cop­ per. He found that the plants were affected extensively and favorably by either forced aeration of the culture'solution or by the addition of manganese, copper, or certain other metals, without forced aeration. Piper (12-13) in experimenting with manganese, found deficiency is overcome most successfully by applying manganese sulphate or by water-logging prior to seeding. He also found in an extensive investigation on copper defi­ ciencies, that oats grown in a copper-free nutrient solution until the development of acute deficiency symptoms occurred, recovered, and completed their normal life cycle on the ad­ dition of sufficient copper to the solution. He observed that rye has a greater absorbing power than oats and can grow to maturity on a soil on which oats fail from copper deficiency. Lipman (8 ), in 1 9 3 1 * discovered that barley plants were unable to produce seed without the presence of a small quantity of copper in the root medium. This was given ano­ ther conclusion, namely, that copper is essential in every phase of plant growth. The amount needed was very minute, one-sixteenth to one-eighth of a part per million of copper 4 in the root medium is sufficient. In experiments at Michigan State College* Lucas (9 ) found that by the addition of copper sulphate the copper content was increased as much as three times, but the recov­ ery amounted to a small fraction of the fertilizer applica­ tion. The copper sulphate did not alter the manganese content of plants growing in adequate amounts of copper. The copper was least responsive to oats around a pH of 5*5 when grown in acid muck soils receiving varying amounts of limestone. EXPERIMENTAL In this experiment two Michigan soils were used. It was the intention to obtain sandy soils as acid as possi­ ble. The soils selected were a Pox sandy loam, and a Plainfield sandy loam. Plainfield a pH of 5-2. The Pox had a pH of 5-^ and the The soils were obtained from an area of Michigan containing vast amounts of these two soil types. Care was taken to find soils that had never been limed. The soils were screened and air-dried before potting. Three-gallon jars were used for the alfalfa and one-gallon jars for oats and spring wheat respectively. A uniform application of 3 -1 2 -1 2 fertilizer was used in the jars and was applied in bands about three inches below the surface. There were twelve treatments on each of two soils, and all treatments were on the basis of pounds per acre. jars. The lime was mixed thoroughly with the soil In the 5 The treatments were as follows: 1. No lime 2. Three tons lime 3* Six tons lime 4. Nine tons lime 5* No lime-/-200# MnSOij. 6. 3tons lime-/-200# M11SO4 7. 6 tons lime-/-200# MnSOjj. 8. 9tons lime-/-200# M11SO4 9. No lime-/-200# M11SO4 -/-2 5 # CUSO4 10. 3tons lime-/-200# MnS04»/-25# CUSO4 11. 6 tons lime-/-200# M 11SO4 -/-25 # CUSO4 12. 9tons lime-/-20 0 # M11SO4 -/-25 # CUSO4 The seeds selected were Marion oats, Henry spring wheat, and Hardigan alfalfa. 26. They were all planted on June They were planted thickly and thinned after germination to twelve plants. On July seventh the manganese sulphate and copper sulphate treatments were added in solution. The oats and spring wheat were harvested about a week after heading, August 15. They were placed in paper sacks and weighed after allowing them to air-dry. The plants were observed during growth to see if copper and manganese affect­ ed their manner of growth. Pictures were taken to show pos­ sible differences in height and growth tendencies. The soil was tested for the availability of manga­ nese. Samples were obtained for these tests by mixing the 6 contents of the Jars and screening. Since there were three Jars for each treatment* the soil from them was thoroughly mixed before the samples were taken. The amount of manganese in the soil was determined by the Peech method as follows: To ten grams of air-dry soil, add a quarter teaspoonfull of Darco Carbon G-60, and 40 cc. of 0.13n HC1. for 1 minute and filter. Shake vigorously Place 5 cc. of the clear filtrate in a 15 ml. centrifuge tube. To this add 0.5 ml. of concen­ trated H 2 SO4 and mix thoroughly. Cool this mixture and add and excess of sodium bismuthate and stir. Centrifuge for five minutes and carefully pipette 3 ml. of the liquid into absorption tubes and read in a colorimeter. The alfalfa was observed during growth in the same manner as the oats and spring wheat. RESULTS Plants During Growth Germination was rapid and good in both soils and all crops. The growth was normal and quite uniform until after the application of manganese sulphate and copper sul­ phate . Plainfield: After thirty days of growth the oats and spring wheat were slightly behind the same crops grown on Pox sandy loam. Twelve days after the addition of manga­ nese sulphate and copper sulphate the new leaves on both crops became brown and in some cases dried up completely. The leaves on the plants which received the three-ton lime 7 application did not show the effects as badly as did those on the plants which received the six and nine-ton applica­ tions. The plants treated with copper sulphate had a slight difference in appearance later in growth. shorter stem and seemed to stool more. The grain had a See plate (III). After heading the grain did not fill out well. This was general on all treatments so It could have been due to the soil not being high in plant nutrients. Fox: After thirty days of growth the oats and spring wheat reacted much In the same manner as they did on Plainfield sand. The new leaves became brown* first at the tips* then gradually over the entire leaf. ALFALFA Fox: Germination was good and growth was rapid on this soil for thirty days. Within fifteen days of treat­ ment with manganese sulphate and copper sulphate there was a difference in growth. The untreated plants with lime had a slightly greener color and were taller. In the jars treated with copper sulphate* the buds and leaves around the buds died on some stems. In some jars entire plants died. As shown by the results In Table 1* lime alone caused an increase in alfalfa yields but decreased yields resulted from additions of manganese and/or copper. Soil analyses showed the soil treated with manganese to contain more manganese than did the untreated soil. The manganese and copper treatments decreased the height of the plants. 8 In observing root development* the plants without manganese sulphate or copper sulphate added* had a very good nodule development. Those with treatment had very poor nodule development and in some cases nodules were completely lacking. Plainfield: On this soil germination and growth was also rapid during the first 30 days. The plants on this soil reacted in the same manner to treatment as the plants in the Pox sandy loam. In general the foliage was a lighter green and was somewhat yellow. This condition was found to be a nitrogen deficiency which was not exper­ ienced on the Pox sandy loam. The weights - see Table 2 - in general reacted in the same manner as the Pox. of manganese in the soil had a wider margin. The ppm The nodule condition was the same. DISCUSSION In this investigation three crops were used on two acid sandy soils. It was the intention to observe the growth of these crops after varying amounts of calcium carbonate was added and see If the addition of manganese sulphate and copper sulphate materially increased or decreased plant growth. Since calcium ties up available manganese* the addition of calcium carbonate would tend to make the plants deficient In manganese. There seemed to be little success In attaining deficiency symptoms in the plants. This was perhaps due to the presence of available manganese In excess 9 amounts by the addition of manganese sulphate. The copper sulphate had little affect on the growth of the plants. Sommer (16) suggests that copper functions in chlorophyll formation. It takes so very little copper to satisfy the requirements of plants that some investigators say plants may receive enough from the air. Willis (18), in his work with the relationship of copper to manganese, found copper to act as a catalyst, and it serves as a soil amendment, possibly decreasing the availability of manganese. The oats and spring wheat seemed to show the effect of the addition of copper sulphate late in growth in the formation of grain and appearance of plants. The alfalfa during growth seemed to show the effects of treat­ ment mainly in color. There was some difference in vege­ tative growth and in root formation. This may support the investigations stating the catalytic effects of copper. The root weights went down with treatment as did average heights. In the root observance it was noted that nodule formation was very lacking on the treated Jars. had very good nodule formation. The untreated Jars In general the foliage was a lighter green on the Plainfield soil than on the Pox soil. This was due to a nitrogen deficiency. 10 CONCLUSIONS From observing growth and from data collected these conclusions may be drawn: 1. There seemed to be sufficient available manganese in the soil on both Plainfield and Fox, 2. The copper did not materially affect the availability of manganese but slightly affected vegetative growth and root development. 3* Treatment with manganese sulphate and copper sulphate decreased nodule develop­ ment of alfalfa on both soils. 11 LITERATURE CITED (1) Arnon, D. I. 1937 Ammonium and Nitrate Nitrogen Nutrition of Barley at Different Seasons in Relation to Hydrogen-Ion Concentration, Manganese, Cop­ per, and Oxygen Supply, Soil Science 44: 91-121 (2) Conner,. S. D. 1932 Factors Affecting Manganese Availability in Soils. Jour. Amer. Soc. Agron. 24: 726-733 (3) 1518" Soil Acidity as Affected by Moisture Condi­ tions of the Soil. Jour. Agr. Res. 15* 321-329 (4) Cook, R. L. and Millar, C. E. 1941 Manganese for Oats and White Beans in Michigan. Soil Sci. Soe. of America. 6: 224-227 (5) Fujimoto, C. K. and Sherman, G. D. The Effect of Drying, Heating, and Wetting 1945 on the Level of Exchangeable Manganese in Hawaiian Soils. Soil Sci. Soc. of America. 10: 269-274 (6) Hill, M. F. and Bryan, 0. C. 1937 The Nutritive Relation of Copper on Different Soil Types in Florida. Jour, of Amer. Soc. of Agron. 29J 8 0 9 -8 1 3 (7 ) Harmer, P. M. and Sherman, G. D. 1943 The Influence of Manganese Deficiency on the Synthesis of Ascorbic Acid in the Foliage of Plants. Soil Sci. Soc. of America. 8: 346-350 (8) Lipman 1931 Proof of the Essential nature of Copper for Higher Green Plants. Plant Physiology. 6: 593-599 (9) Lucas, R. E. The Effect of Addition of Sulphate of Copper, 1945 Zinc, and Manganese on the Absorption of these Elements by Plants. Soil Sci. Soc. of America, 10: 269-273 12 (10) McHargue, J. S. 1925 The Occurrence of Copper, Manganese, Zinc, Nickel, and Cobalt in Soils, Plants, and Animals and Their Function as Vital Factors, Jour, of Agr. Res. 30: 193-196 (11) McHargue, J. S. 1923 The Effect of Different Concentrations of Manganese Sulphate on the Growth of Plants in Acid and Neutral Soils and the Necessity of Manganese as a Plant Nutrient. (12) Piper, C. S. 1931 Availability of Manganese in the Soil. Agr. Sci. 21: 762-779 Jour. (13) Piper, C. S. 1942 Investigations on Copper Deficiency in Plants. Jour, of Agr. Sci. 32: 143-179 (14) Remington, R. E. and Shiver, H. E. Iron, Copper, and Manganese Content of Certain Common Vegetable Foods. Jour. Assoc. Off. Agrie. Chem. 13: 129-131 (15) Schollenberger, C. J. 1928 Manganese as an Active Base Sci. 25: 357 (1 6 ) Sommer, Anna L. 1940 Copper and Plant Growth. in the Soil. Soil Soil Sci. Vol. 60: 71-81 (17) Sullivan, N. X., and Robinson, W. 0. 1913 Manganese as a Fertilizer. U. S. Dept, of Agr. Bur. Soils Circ. 75* 3-5 (18) Willis, L. G. 1928 The Response of Oats and Soybeans to Manganese on Some Coastal Plain Soils. N. Car. Agr. Exp. Sta. Bull., 257 Table 1. The Effect of Lime, Manganese, and Copper on the Yield and Height of Alfalfa Grown on Pox Sandy Loam Soil and the Effect of Treatment on the Manganese Content of the Soil. 13 p 0 bO P P 0 cd U O p Q 0 G 0 rH P 0 cd > QU bO 'P G CD rH 0 cd P CM H iH rH rH(fJ ON O 00 oo ON rH S-i <3 ,£j fcj O 0 > «M S 3 <3 O P 10 •H rH 10 o O CM oo CM M LfN CO JC5j - -=t LfN Sri in 0 U ro > • P P <3+5 » bO £U cd S 3 •O U tH P I 0 O S h ^ • OP <3 P P3 <3 CM ■ = 3- o & GO £ 0 bQ bO cd ci WOn CoO 0 2 • • • tP rH ■=J- LfN • CO -=i" • • VO • CM • O • m v o v o o N i n v o b - b - • o • « T•=3" T ~ T O -=3* O 'f -=J~ o CO -p *3 0 £ 0 £ P -p GQ cd 0 Jm Eh 0 £ P tH O & S3 O P m S 3 O 0 P Ju CJ M P 0 EH CO CM CO 0 £ rH GQ S3 o p O CM P $ n o cm CM 0 "L 0o £ P £ 03 p p rH O 0 S3 CO o *0 O CO in vo VO CO o o o CM o o CM CO CO 0 £ P 0 £ P £ P P rH ■=}• rH -=t” CO CO GO CO CO CO OO 00 op VO CM O S3 3 ON a CM CO CM 00 ON o I —1 O 44 $ o S3 3 44$ ON CM CM Table 2. The Effect of Lime, Manganese, and Copper on the Yield and Height of Alfalfa Grown on Plainfield Soil and the Effect of Treatment on the Manganese Content of the Soil 14 p Cl 0 U O bQ*H •H 0 Cd Cm -P 0 to & 0 rH 0 bfl«P CQ JL, id H 0 cd OJ CO I—I o OJ CM i—1 o rH I—I rH O i —I on ON .oa W > a • O •*&rltCH < P < EH £ CO rH CO CO CM CM CM OJ 6 tons lime-/-MnSOi|.; No. 4 , 9 tons lime " /' MnSOij. • 23 f Plate 9 . Treatment of alfalfa on Plainfield sand. No. 1 , no lime-/-MnS0i|.-7^“CuS0^; No. 2 , 3 tons lime-T^MnSO^-V-CuSOij.; No. 3 , 6 tons lime-/-MnSOi|.-/“ CuSOij.; No. 4 , 9 tons lime-/-MnSOi|.-/-CuSOi|..