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This is to certify that the thesis entitled Effect of Copper on Two Organic Soils Study- ing sources, Rates and Methods of application presented by K. Eustace E. Johnson has been accepted towards fulfillment of the requirements for , I'Iaslz"??? CP scienCfiegl-ce “1501]. Science i. MM Major professor Date F“ ) m m: 01' DETEODS AID ”HS 01' APPLICATION 01' W0 COPPER CARRIERS 0H m YIELD AID COPPER Gm 01' SPIIAGH LED SUDAN GRASS GROW! I] THE GRIIIHOUSI ON TWO ORGANIC SOILS By I. Bueteee I. Jehneon Al LBW! Subllttel. to the School of Wte Studiee of 11101115“ Stete College of Agriculture end Applied Science in pertiel fulfillment of the require-elite for the degree of MASTER 01' 8011110]: Depertnent of Soil Science 1952 # Approved. THESTS I. hetece 1B. Johneon ABSTRACT The Effect of Methode end Retee of Application of Two Copper Cerriere on the Yield end Copper Content of Spinach and Sudan Greee Grown in the Greenhouse on two Organic Soile. The etud: wee inetitnted to inveetigete eourcee, retoe, end nethode of epplicetion of copper on the yield end copper content of epinech end enden greee grown in the greenhouse on two organic eoile. The eoile were of varying acidity pH 3.7 and pH 6.0 obtained tron the Andereon fern in Lepeei\Connty end the n.s.c. Mick Experimental ran reepoctively. Beeic fertilizer treetnente tron c.p. chenicele to'both coil-e wee et the following retee: 3-9-18 et 3000 lbe. per acre, end chlordane (wire-worn control) et 10 pennde per acre. To the Andereon «11 (pH 3.7) we nae-e precipitated «1cm carbonate at the rete of 10 tone per ecro (which brought the pH up to 5.7) and. liner elenente et the following retee: einc eelfete (nonehydreto) et 25 pounde per ecre, Ingenone enlfete (nonohydrete) 100 poude per acre. end eodiun borete (deoehydrete) et 100 pounde per core. Copper wee applied to the eoil at two retee. 5 end 25 pounds per acre, and nice to the leevee ee e duet Ind epray. The copper for each of theee treat-onto wee derived tron two eourcee: copper enlfete (pentlhydrete) and copper oxide (e 50 percent copper oerrier eold under the trade none of Cele-ct Brown Copper Oxide by the Celenet end Heckle, Inc.. of Gelnnet, Nichigen.) . The firet four crepe were grown during the period of lete an end winter, and the eecond four crepe tron lete winter to epring, with ertificiel lighting eupplied when neceeeltry. 51‘. 9739539 I. hetece I. Johneon Seaplee of the eoile were taken fron each of the treetnente before end efter cropping end mlyned for copper. The, crepe were herveeted. weehed where folicr treetnente were epplied, dried ct 60—80%. and eenploe of each of tho treetnente were Inelyced for copper. It wee obeerved that in dry eehing eenplee for copper ennlyeie e teqereture of 150% wee eeeqeete intent of e te-pereture of 650°C. the two croppinge fron oech of the treetnente did not renove enough copper to chenge the copper content of the eoile eppreciehly. On the coil fron the Heck hperinentel hrn there ie conclneive evidence tint copper ie beneficial to the growth of epinech end eudnn greee. On the coil fron the Andereon fern only epinech ehowod benefite of copper epplicetione. In noet ceeee. the coil epplicetione reeulted in higher yields then folicr applicetione. There wce little or no difference in the effectiveneee of copper epplied ee oxide or eulfete. to increeee yielde or influence the copper content of the plent if they ere both need et the eene rete of total copper. . The 25 pound per core reto of coil epplicetion wee nore effective than the 5 pound per core epplicetion in increeeing the copper content of the plat tieenee. Only in the eecond crepe did the forner rete give higher yielde then the letter. Duet end eprey treetnente need in adequate (non-toxic) concentre- tione ere equnlly efficient in correcting copper deficiency end increee- ing yielde without giving ehnor-l percentegee of copper in the tieeuee. On the whole they were not quite on effective on eoil epplicetione. THE EFFECT 0! METHODS AND RATES OF APPLICATION OF TWO COPPER CARRIERS ON THE YIELD.AND COPPER CONTENT OF SPINACH.KND SUDAN GRASS GROWN IN THE GREENHOUSE ON TWO ORGANIC SOILS By K. Eustace E. Johnson A.TEESIS submitted to the School of Graduate Studies of Michigan State College of Agriculture and.Applied Science in partial fulfillment of the requirement- for the degree of MASTER OF SCIENCE Department of Soil Science 1952 .ACKNOWLEDGEMENT It is with great sincerity that the author expresses his grate— fulness for the generous support and counseling in making this achievement-possible. Inestimable value is placed on the willing- ness and congeniality with which time and advice were given. Special mention is made of the following: Dr. J. E. Davis and Dr. L. M. Turk for guidance and cooperation throughout the project. Dr. I. Lawton, Dr. R. L. Cook, and Dr. R. E. Lucas for suggest- ions and.use of equipment. I Dr. E. J. Benne and associates of the Agricultural Chemistry Department for cooperation in helping to solve some of the difficul- ties‘encountered. Dr. H. H. Huggins and family for making possible the coming to the United States to study. The authoris fellow graduate students for timely criticisms and assistance. Calumet and Heckla, Inc., Calumet, Ffichigan for financial support in this work. 1 l ‘) ‘1 f) ) ; w-qu-re— A. '. ,~. ’.--O k“ "3 my: r.‘.'ik'.‘d *""'T‘."i*?"m‘rf‘-\V w 19' ‘3";va ." W s e e e e e e e e e e e e e e e e e e e e e e o e I vwwv w..- -- "'2‘. ~r"*'1:-7~ In..;'...:.e'| CF 1.I :-?‘ph.‘~ -‘_'l . . . . . . . . . . . . . . . . . . . . . q '1 . - v . r x . " - : .,,.~ "1_1]l('t1_l,11q (:f CI‘F"Pr ’ v! I‘Kt'n a '( tin; ”3'! ' g Q g . . . p . . . . o q T-\ 1 n A 'Vr' ".'~ 3 r 1“.» ' ‘r;* L: “ Japfilnng. “1 “HI..- kl ‘1 l 'rj"“ SQ " 0 9 e e e e e e e e e e e e - 1‘. - ° ~ . .- .. .h . . - ,‘_.-1 6 :antinna: as.eciu «f copra? in "!.Q , , , , , , , , , , . ‘f"‘";."’"" ‘5"“3'7‘5 "“‘“‘(‘“"‘\’T“ A .1" «‘2' -' kl‘ lb ‘ :- !vsk..r'.l.j.'. H.. ‘1‘ . . . . . . . . . . . . . . . . . ' . . 1] '7‘», .. ' . = - ' ' 1‘ . w A 4.11:, 3 (firm: Tu'itif‘fi (if. Cr‘fl‘OI‘ In. I‘j‘i-Lfs' e e e e e e e e e e e e e I) "‘ -'- ."w .. a. ' .2'., a! .91‘3..Lz‘25 3141.113?) (if Cfaisjieg} 3‘3 $1.041”:S . . . . . . . _ . . . . . . 1'; 7-“! T;u~1\~" -,-vp~ - v;.v '37,? ‘ ‘ V L“ “~‘ "nu“ rd“ 1T‘ -‘* e e e e e e e e e e e e e e e e e e e e e .15 0‘ ”Pen ‘fi‘C' I“? _._;!‘..\,T,.~..;I‘5'- e e e e e e e e e e e e e e e e e e e e e e e e e e 2') (Was. Mar .1: a“)! .314. . g . e e e e e e e e e o e e e e e e e e e e e e e e J, FIR] I~sctloPtY e e e e e e e e e e e e e e e e e e e e e e e e O “2'6 INTRODUCTION In many organic soils it is impossible to grow certain crops without the addition of copper. Many of these soils are copper deficient to such an extent that response to copper can be observed, not only in the pasture crop, but also in the grazing herd. .As early as 1817 it has been reported that (6) investigators have shown that copper is essential to plant growth, and.1ater, have shown its necessity to higher forms of life and to man himself. Investigations concerning its addition to the soil or plant as a nutrient were initiated in 1921 (6). Several fungicides containing copper have been.used -— such as Bordeaux mixtures - with resulting increases in crop yields that could not be ascribed to the control of the disease. At present the recommendations for the use of copper on organic soils are made on the basis of soil reaction (pH) and the crop itself. Several copperAbearing materials are known (17) to correct copper deficiency, but are not at present extensively recommended in Michi- gan. This work was designed to investigate under greenhouse conditions the comparative effectiveness of copper sulfate (CuSOu-5H20), and. copper oxide* in increasing crop yields. Investigations were made of two organic soils, with different rates of application and different * Copper oxide was obtained from Calumet and Heckla, Incorpora— ted, and contained 50 percent metallic copper. It is sold under the trade name of Calumet Brown Copper Oxide. methods of application of copper using spinach.and sudan grass as indicator crops. REVIEW’OF.LITERATURE Most of the current work on copper has been extensively reviewa ed by Harmer, Somer, Lucas, Brown, Ruby and others (l7,39,27,“é}37) dealing with various aspects of the use of copper. In an effort to bring out the importance of copper to all forms of life, this review concerns itself with pointing out the functional role of copper in the soil, plant, animal and man himself. ggpgtions of coppgr 1p man.and anigglg. Copper plays an impor- tant role in the metabolism of humans and animals. Nutritional deficiency of copper is rarely observed in man but it is frequently apparent in animals that feed on copper deficient diets, such as pastures established on copper deficient soils. It is known to be present in small quantity in animal tissue. Some invertebrates such as orthropods and mollusks, surpass plants and.vertebrates in the accumulation and concentration of copper in the tissue (13). There are several processes known to require copper, yet how it functions in these processes is still not entirely clear. Some of the functions in the animal body in which copper is thought to be essential are: (a) the process of myelinisation of the central nervous system (8); (b) in erythropoesis, blood formation, chiefly red cells and haemoglobin (16); (c) for keratiniaation in sheep (10); (d) for hardening fresh cuticle, and toughening organs of attachment of invertebrates (13); (e) as an oxygen carrier in respiration (l6): and (f) for maintenance of nutrient balance and prevention of disease (32). Functions of coppgr in plants. Copper is essential for higher plants although this need is satisfied by mall quantities of the ele- ment. Capper is related to metabolic activity as evidenced.by its presence in enzymes or enzyme systems, and.its effect on the absorp- tion and utilization of other elements. Some workers relate its function to the prevention of certain diseases, and regulation of the phasic deve10pment of the plant. Copper as a constituent of plants was recognized early in the nineteenth century, and the amount was determined quantitatively about fifteen years after this discovery. Increases in yields'by use of copper was shown by (3,6,15,17,2?,36.37) and several other workers. Investigation as to the way in which capper is found in.plants has shown that it is located chiefly in enzymes, and enzyme systems, and the greatest portion in the chloroplasts of the leaves. Some of the known copper enzymes in.plante are: ascorbic acid oxidase; lcuc¢:ase; polyphenol oxidase or tryosinase; catechol oxidase; cytochrome oxidase; peroxidase; and.an enzyme inactivating indole acetic acid, an auxin in plants (1.2.5.11,2326,28.29,38,41). As an example of the quantity of capper, Dawson (11) points out that ascor— bic acid oxidase is a specific capper protein having a molecular weight of about 150,000 and containing 6 copper atoms per molecule. The total copper in plants varies with the type of plant (27,35), its physical, topographical and chemical environment (’4), as well as within tissues of the plant itself (6). It has been found by most workers to vary fromtz to 15 ppm for most plants under normal condi- tions (27,36), yet quantities up to 100 ppm have also been observed ‘by others (19,36). Arron (3) reports Neish as having found that 7u.6 percent of the total capper ih clover leaves is localized in the chloroplasts, and most of it was in organic combination. The copper in organic combin- ations or complexes are sometimes held in what are called "chelate linkages” and these are bound so strongly that it takes most of the power of strong concentrated acids to break them down. Delf (12), reveals that copper is translocated in both phloem and xylem, but, largely in the sieve tubes of the phloem. Several possibilities have been proposed.as to the role of copper in plants yet these have not been entirely agreed upon by all workers. Capper is considered to function as an oxidizing agent and aids in respiration (3,11,21,35). Hoagland (19) suggests that it plays a role in photosynthesis. Arnon (2) believes also that it may play a part in photosynthesis due to his observation of oxidation! reduction enzymes found in the chloroplasts of leaves of plants such as spinach. Sommer (39) shows that copper is effective as a cure for ”reclamation‘disease”, premature dying of onions, and refers to evidence of its curing effects on "die—back" of citrus, rosette of pears, and other plant abnormalities. Lipman and McKinney (26) state that it is necessary for the phasic development, as evidenced.by the inability of barley and flax.to produce seed when capper was with. held. Other workers support this view in the case of sudan grass and oats (6,27). Winthrow (#4) indicates that copper participates in certain steps of chlorophyll synthesis. Picton (36) says, “It seems to be agreed that copper must be available before iron can be used ....' which is indicative of the role in nutrient balance and governing effect on food utilization. Steinberg (#0) points out that copper is essential to protein breakdown, yet the evidence was not conclusive enough to indicate with certainty that it participates in the synthesis of amino acids or proteins. Experimental evidence is now sufficient to Justify the accept- ance of copper as a nutrient element and its being essential for growth of higher plants. It has been found to increase yield.and quality of crops when used where deficiencies occur. There is no one concensus of opinion as to its function in the plant, but it no doubt does influence the metabolic processes, and forms part of the plant constitution. \ Functional aspgcts of gappgr in soils. Copper is thought to exist in mineral soils either primarily as a cation and follow much the same pattern.as calcium and potassium (#2), or "strongly and irreversibly absorbed by soils especially in the organic matter" (35). In organic soils copper is believed to exist in very strongly bound complexes. According to Corwin (9) copper exhibits chelation phenomenon, which is the formation of simultaneous links to the same organic molecule, and there is so much stability of this multiple linkage, that if, for instance, a single linkage were so weak that its half-life expectancy is only about a minute at room temperature, a double link of the same strength would have a half-life expect- ancy of nearly a quarter of a million years, provided temperature changes or any other effects are eliminated. The protein derived components, phenolic-OH groups, B-SH, NH“ and 3.0003 groups react with copper, even within the same molecule in acid or alkaline solution to form complexes. Some of the primary copper complexes contain three atoms of copper, two molecules of cystein and one aromatic amine (9). The availability of copper in soils has been depicted in several ways. Jamison (22) writes that much of the copper is held in three forms: nonpreplaceable, slowly replaceable, and slowly soluble. Truog (#2) in a collective grouping uses three categories also: the readily available, moderately available, and slowly available. Adsorbed copper is believed to depend on the cupric-ion concentra- tion, nature of the soil, exchangeable acidity and other adsorbed ions (22). It is generally agreed that copper is to be found chiefly in the upper layers of the soil (22), or more emphatically as Lucas (27) puts it, ”rigidly held in the zone of placement". Holmes (20) in his analysis of United States soils reports that the copper con. tent varied from 6 to 67 ppm.with variations following no definite geographical distribution, yet he believes that parent materials and conditions of weathering influence the availability of copper. 8 Vermeet and Van der Bis, as quoted by Brown (6) conclude that copper released by weathering is in the ionic form, yet in contact with organic matter, it would sequentially be fixed in the organic mole- cule. Brown and Steinberg (7) report that ascorbic acid oxidase activity in the plant was a good index of the available copper supply whether the plant did or did not show visual copper defi- ciency symptoms, and that other micronutrisnt deficiencies can also be determined by enzymatic activities since the enzyme will be aberrant if it required the element for function. Brown (6) reports that copper influences the uptake of iron, nitrogen, potassium, phosphorus, magnesium and silica. Picton (36) and Jacks and Sherbatoff (21) believe that copper is necessary before iron can be used, and further that organic soils containing toxic quantities of ferrous iron my be corrected by copper applica- tion. Willis and Piland (#3) show that excess absorption of iron as a result of lining can be controlled by adding copper without which. a lodgement of iron in the nodes and decrease in growth may occur. McMurtrey and Robinson (30) state that some of the beneficial effects derived from copper compounds may be due to the precipitation of the toxic sulfide ion found in organic soils. Lipman (25) reports antagonism of copper and zinc to sodium chloride, sodium sulfate, and sodium carbonate which was regarded as a significant observation for the use of copper in the reclamtien of alkali soils. The primary function of copper, in soils is that of a nutrient element. Another function is that of an oxidizing agent. According 9 to hasarrev (24) organic soils which contain reduced substances such as iron and manganese do not respond to copper treatment, if the soil is treated with hydrogen peroxide. Copper and zinc are some- times referred to as mutually coordinating catalysts for oxidation and reduction (6). Copper neutralizes harmful conditions in soils (33,”2), as evidenced by the production of characteristic changes in organic acid content when there is a serious deficiency. Much of the work‘with regards to copper and soil reaction has been reviewed by Ruby (3?). It was shown that for the most part acid organic soils will give better response to liming if copper is also used. Harmer (17) states that in general, most crops benefit from copper if the natural pH of the organic soils is 6.0 or less, with the more responsive crops showing a need as high as pH 6.5, but, in effect, the more acid the organic soil, the greater the relative response to copper. Lucas (27) reports that the‘bindp ing of capper in the soil is stronger at higher and at lower pH values, in the region of pH 3.0 and 7.2. On addition of copper acetate to saturated E—Humus, it was believed that copper was adsorbed as the divalent cation Cu“ and the monovalent cation com. plex (CuAcO)‘ which was prdbably precipitated when the suspension pH was increased above “.7. Truog (42) and Hoagland (19) report contrasting results as to the availability of copper at pH 5.5-6.5. Lucas (27) embraces both points of view by saying that either the relationship of availability of copper and pH are not important if the copper content is low, or that the need for copper is more 10 dependent on balance of nutrients within the plant. Microbial activity is considered one of the factors associated with reduced availability of copper in soils. Miulder (33) considers that the presence of 'peaty substances," 32$ bacteria, and other microbial activity assist in the formation of complex organic copper compounds. Hasler (18) shows that the affinity of humus rich soil for trivalent cations makes it possible not to influence the micro- organism content by large dosages of copper. The action of micro— organisms in organic soils is believed to be so complex that the biological test - "Aspergillus Niger" - estimated as the most reliable test for available copper in sandy soils, is regarded as unsatisfactory for organic soils (10). As previously indicated, copper is known to be essential for the normal growth and.development of microorganisms (13,25), and there will be three competitors for the available capper -— the plant, the micrObe and the organic com— plex. 11 EXPERIMENQAL PROCEDURE Two organic soils were obtained; one from the Muck.Experimental Farm.(pH 6.0) Soil 1, and.the other from the Anderson Farm, Lapeer County (pH 3.7) Soil 2. The soils were partially dried and were screened through a quarter inch square mesh screen. A.uniform weight of soil was placed in 108 previously weighed, four—gallon glazed Jars. {An application equivalent to 3000 pounds per acre of 3-9—18 fertilizer, prepared from chemically pure grades of ammonium nitrate, potassium monophosPhate, and potassium chloride, was supplied to each Jar. In addition to fertilizer, to the acid.Anderson muck, the equiv- alent of 10 tons per acre of precipitated calcium carbonate was added, which increased the pH from 3.7 to 5.7. The following minor elements were added to the lined soil at the rates listed: zinc sulfate (ZnSOu-HZO), 25 pounds per acre; manganese sulfate (Mnsonofizo), 100 pounds per acre; and sodium'borate (Nang07-10N20), 100 pounds per acre. Chlordane was added at the rate of 10 pounds per acre to cone trol wireworms. The following nine treatments were replicated six times on each soil: 1. Control —~ no copper added. 2. Copper sulfate - mixed with soil -— 5 pounds capper per acre . 3. Copper oxide - mixed with soil -— 5 pounds copper per acre. h. Copper sulfate - mixed with soil -— 25 pounds capper per acre. 12 5. Copper oxide —- mixed with soil - 25 pounds copper per acre. 6. Copper sulfate - Foliar application -— 0.25 and 0.005 per- cent copper sprays. 7. Copper oxide - Foliar application -« 0.25 and 0.005 per— cent copper sprays. 8. Copper sulfate —— Foliar application - 6.25 and 2.5 percent copper dusts. 9. Copper oxide - Foliar application -— 6.25 and 2.5 percent copper dusts. The compounds were thoroughly mixed with the soil and distributed as uniformly as possible. The spray was applied by use of a hand-sprayer and.the dust by use of a dusting tower. A small quantity of detergent (0.3 gm.per litre of Draft) was included with the spray as a wetting agent. During foliar applications the soil was covered with paper as close to the plant as possible to prevent any of the treatment from falling on the soil. The moisture equivalents of 165 for soil 1, and 179 for soil 2, were used to bring the soils up to optimum moisture. Spinach and sudan grass, the indicator craps, were planted one week after the soil was moistened and on germination were thinned to 8 and 12 plants per Jar respectively. The first craps were grown during the period from November 31, 1951 to February 7, 1952 and the second crops from February 12, 1952 to July 7, 1952. Greenhouse lighting extended the light period from 5:30 P.M. to 10:30 P.M. daily. Harvesting of craps was done in the early stages of maturity, based on the emergence of seed-heads. 13 rafter harvesting fresh weights and oven-dry (60-80°C) weights were obtained. Those plants that were dusted or sprayed were washed before drying to remove particles of capper from the surface of the leaves. The method of washing was as follows: First, the plant material was placed in about three litres of distilled water at room temperature for two or three minutes and moved upward and downward to insure the thorough wetting of the material. Next, it was similarly washed in three litres of luke warm (SO-35°C) distilled water containing about 2 gms.of detergent, followed by three successive washings in the same quantity of water without detergent, and a final rinse with running distilled water. The plants were then placed on large clean porcelain dishes and dried. It was found that the wetted plant material tends to stick to paper, enamel pans, or boxes. Determination of copper in plants, (3%) The samples were ground in a Wiley Mill, using a 20 mesh screen for large samples and a 60 mesh for samples less than 2 grams. The samples were then oven-dried at 105°C for four hours to drive off moisture absorbed during grind» ing. The samples were removed from the oven, cooled in a desiccator, and known weights in porcelain crucibles were placed in a muffle furnace at 050°C for 10 to 12 hours for ashing. If there were visi- ble particles of carbon left, after ashing, three or four drop; of nitric acid were added to the contents of the crucibles which were then dried and re-ashed. The ashed material was treated with 3-5 ml. of concentrated hydrochloric acid and boiled for one minute. (The acid 1h had.to be added gently and under the hood; rapid addition of acid caused spattering and subsequent loss of ash). The solution was next transferred to a 200 or 250 ml. volumetric flask with.boiling redistilled water, and after cooling brought up to volume with re- distilled water. 4A1iquots of 50 ml. of less brought up to 50 ml. were placed in separatory funnels, to which 5 ml. of 15 percent citric acid were added.and shaken. The solutions were made slightly alkaline (using a piece of neutral litmus paper in the funnel as an indicator) with 1:1 ammonium hydroxide. Next 10 ml. of 0.01 percent sodiuxhdiethyl-dithiocarbamate solution were added and shaken, after which.four extractions were made using about 4 ml. of carbon tetrachloride each time until no color appeared in the 0014 layer, and.then the extract was filtered through anhydrous sodium sulphate in no. 12% or No. he Watman filter paper and brought up to 25 ml. volume with carbon-tetrachloride. The quantity of copper was then evaluated photometrically using a Cenco—Sheard-Sanford photelometer equipped with a Corning lantern blue glass filter (#5510 with minim transmittancy at 450 mu. Determinatign gf coppe; in ggils. (34) The above procedure was used for determdning copper in the soils. The sample was ground in an agate or porcelain mortar, then ovenpdried, weighed, ashed, HCl-digested, filtered, washed with hot water and diluted to a volume, aliquots of which were then analysed for copper by the procedure described above. 15 mm MENTAL 11351,st In preliminary studies, the extreme differences Obtained in the copper content of soil and.p1ant samples with those previously reported (6,27,36) made it necessary to investigate the reason for this variation. The situation was further complicated by the fact that good agreement was obtained in the copper content of duplicate samples, provided the size of sample remained the same. The blank determinations were not affected by the techniques. The temperature at which the samples were ashed appeared to be responsible for the variation. If the sample was ashed at “50°C, very good agreement between results previously reported for the sample was obtained, whereas, if ashing took place at 650°C, unsat— isfactory data resulted. Values obtained were from two to five times greater when aching occurred at the higher temperature. In order to determine the percentage distribution after copper applications and also to find out if results from foliar applications were due to soil contamination from these treatments, samples of soil from each treatment were taken.before and after cropping, analyzed and the percent copper reported in Table I. The data in Table I show that there was essentially no change in the copper content of the soils after two cr0ppings at the various levels of copper application. The effect of these treatments of the two soils on the yield and copper content of the first crops of spinach is given in Table II. TABLE I 16 The Effect of Cropping on the Copper Content of the Soil at the Various Treatments Percent copper Treatmgnt (Soil 1) (Soil 2) Pounds Method copper of per appli- Before After Before A¥va Source acre cation croppipg cropping cpoppipg croppipg ... .-. 0.0011 0.0010 0.0010 0.0010 Copper Sulfate 5 soil 0.002“ 0.0023 0.0024 0.0024 Copper Oxide 5 soil o.oozu 0.0021» 0.0021» 0.0021» Copper Sulfate 25 soil 0.0075 0.007h 0.007# 0.0070 Copper Oxide 25 soil 0.0075 0.007h 0.0070 0.0070 Copper Sulfate spray 0.0011 0.0012 0.0010 0.0012 Copper Oxide spray 0.0011 0.0011 0.0010 0.0011 Copper Sulfate dust 0.0011 0.0011 0.0010 0.0010 Copper Oxide dust 0.0011 0.0011 0.0010 0.0010 M4 fl :1- “—‘J 17 TABLE II The Effect of Methods and Rates of Application of Two Copper Carriers on the Yield and Copper Content of the First Crops of Spinach Grown in the Greenhouse on Two Organic Soils T’T‘Wroa .nent wooil '1'?” "' " —§_g_'ii"::‘"‘” Pounds Method Mean Mean copper of yield** yieldi'”I per appli- (grams Percent (grams Percent Source acre cation pgr jar) copper per jar) copper Non. --' 2.0 .1... 9.0 0.0017 Copper Sulfate 5 soil 10.0 0.0010 ‘ 10.4 0.001n Copper Oxide 5 I011 11.3 0.0011 12.1 0.001“ Copper Sulfate 25 soil 11.5 0.0016 11.“ 0.0016 Copper Oxide 25 soil 11.2 0.0016 10.1 0.0016 Copper Sulfate .- 0.25% 2.0 0.0015 4.3 0.0015 spray Copper Oxide —. 0.25% 5.0 0.0011» 6.3 0.0014 spray Copper Sulfate - 6.25% 2.6 0.0017 6.5 0.0016 dust Copper Oxide .- 6.25% 0.5 0.0015 8.0 0.0015 dust , L.S.D.*** 1 percent firl.7 -- 2.0 mu:w 5 percent 1.2 -- 1,7 --- *.A uniform.application of 3000 pounds per acre of 3-9-18 fert— iliser applied to all jars. Spinach harvested on December 28, 1951 and February 29, 1952 from soils 1 and 2 respectively. ** Averages of three replications dried for 72 hours at 60-80°C. *** Difference required for significance between any two treat-, ment means. 18 The data show that with soil 1, the yields obtained from all treat- ments except the copper sulfate dust and spray are significantly higher than the yield of the control at the 1 percent level of sig- nificance, with the soil applications giving the best results. There was no difference in yield from the 5 pound per acre applica- tions of copper applied in the form of the oxide and the 25 pound per acre applications either as oxide or sulfate. Yields from.Jars treat- ed.with 5 pounds per acre of copper supplied.as sulfate were signifi- cantly less at the 5 percent level than the yields obtained from Jars of the three above mentioned treatments on soil 1. With soil 2, only three treatments of the soil applications gave significantly higher yields than the control. The yields from the Jars treated with 5 pounds per acre of copper as sulfate weee not significantly higher than the yields from the untreated Jars. Both sprays and the copper sulfate dust treatments resulted in yields sig- nificantly lower than yields of the control due to the high concentra— tion of these treatments, as was also observed on the yields of foliar application treatments on soil 1. The percentage of copper in the tissues was approximately the same for the 25 pounds per acre treatments and the foliar application treatments, and slightly lower in the tissues from Jars receiving the lower rate of soil application. The source of copper did not influence the copper content of the plant. It is interesting to note that the copper content of the control crop was comparable to that of the 25 pounds per acre soil applications on soil 2. The copper content 19 of the spinach control grown on soil 1 was undetermined because of insufficient plant material. The yields of the second crop of spinach on both soils were all significantly higher than yields of the controls as shown by the data in Table 111. Only one treatment, the copper oxide spray, resulted in yields significantly greater at the 5 percent level. All other yield responses were significantly greater at the l per- cent level than yields of control jars. High rates of soil applications in the second crop of spinach resulted in highest yields with no differences due to the source of the copper. (Figs. 1 and 2) On soil 1, the yields from.jars of the oxide foliar applications were significantly higher than the yields from Jars of comparable sulfate treatments. The yields and copper content of the second crops were compara- tively lower than those of the first creps of spinach on both soils. The data in Table IV show that there was no response in yield to any of the copper treatments by the first crop of sudan grass on soil 2, while only one treatment, the sulfate spray, failed to give re- sponse significant at the 1 percent level on soil 1. (Figs. 3 and h) The dust applications resulted in higher yields than the 25 pound per acre treatments and spray applications, with the oxide dust showing the most outstanding performance. There was no significant difference in yields between rate of application of copper carriers in the soil application treatments in 20 TABLE III The Effect of Methods and Rates of Application of Two Copper Carriers on the Yield and Copper Content of the Second Crops of Spinach Grown in the Greenhouse on Two Organic Soils . Treatment Soil 1 $0115; Peunds Method Meant Mean copper of yield** yield“I per appli—, (grams Percent (grams Percent Sourc acre cation peg 12;} coppe; pez Jag) copper None -—- 1.2 —- 1.8 0.0010 Copper Sulfate 5 soil 6.8 0.0009 6.3 0.0010 Capper Oxide 5 soil 7.1 0.0010 7.0 0.0009 Copper Sulfate 25 soil 9.2 0.0010 7.7 0.0016 Copper Oxide 25 soil 9.? 0.001h 6.0 0.0015 Copper Sulfate —- 0.005% 0.7 0.0010 0.7 0.0007 Spray Copper Oxide .- 0.005% 8.2 0.0011 0.0 0.0008 spray Copper Sulfate _. 2.5% 5.6 0.0009 8.0 0.0009 dust Copper Oxide .. 2.5% 9.0 0.0012 6.3 0.0000 dust ieSeDe*** 1 Percent 1:7— ..- 2e5 m 5 percent 1.2 -- 1.8 -- '.L uniform application of 1500 pounds per acre of 3-9-18 fert- ilizer applied to all Jars of soil 1. Spinach harvested on March 25, 1952 and April 30, 1952 from soils 1 and 2 respectively. we Averages of three replications dried for 72 hours at 60-80°C. *** Difference required for significance between any two treat- ment means. Towards as .3300 season mm a a Jeane as nuance season 3. u n .3de as neaaoo menace m s N .eeuo me Sacco apnoea m s a £238 on u 3 .H :om so Academe me 527% on» so 33.2.3 .333 85 mo seduceaaaae mo even we assume 05.. .H .wrn . .. .. “M s a r e .; s e. _. . a r ... Thane ennui; seamen. u o madame 353 9233 u m .33 enemas. seamen u w .936 edema nuance u n .noaaoo on u 3 .H 30m. do message no £395 on» so 95.7823 nomaoc 25 no 30303.39» .333 no assume e5. .N .ma _. ..J.w. a . «L’L‘. . . . . .0 _ , o .. ob . a..a....eom o. .1... _ ,Hv. .. ”Heft . . . b. .. . s. . . A. M 4. re. . ! O . 0.- . ‘0' .he .. V ._ e .a. The TABLE IV 23 'ffect of Methods and Rates of Application of Two Copper Carriers on the Yield and Copper Content of the First Crops of Sudan Grass Grown in the Greenhouse on Two Organic Soils —. Percent 00 er 0.0018 0.0015 0.0016 0.0018 0.0018 0.0015 0.0019 0.0016 0.0027 peatment* Soil 1 0 Pounds Method Mean Mean copper of yield** yield?‘ per appli- (grams Percent (grams Source ac e cation r ar 00 or a None -—- 0.5 -- 59.0 Copper Sulfate 5 soil 61.7 0.0021 58.0 Copper Oxide 5 soil 66.3 0.0018 62.? Copper Sulfate 25 soil 48.7 0.0020' 60.3 Capper Oxide 25 soil 45.0 0.0024 58.0 Copper Sulfate .. 0.25% 17.0 0.0020 60.0 spray Copper Oxide .- 0.25% 50.0 0.0024 61.0 spray Copper Sulfate .. 6.25% 72.0 0.0023 61.5 dust Copper Oxide .. 6.25% 102.0 0.0022 62.0 dust . E.S.D.*** 1 percent 31.? -— 8.1 5 percent 23.0 -—- 5.9 t A uniform.application of 3000 pounds per acre of 3-9—18 fert- ilizer applied to all Jars. 1952 and.April l, 1952 from soils 1 and 2 respectively. ** Averages of three replications dried for 72 hours at 60—800C. *** Difference required for significance between any two treat- ment m 68-118 . Sudan grass harvested on February 7, 133d; as 8.33 season mm I n .038 as 8.53 a I I encoa mm H n .3de .3 8.500 gnome m I N .038 as seamen apnoea m u H £233 on u 3 .H Sow so 3ch dance no no: em on» .3 33.280 «egos or» no 5333a? we can." we assume 2%... .n .w: . . .. . V . 7 . "‘lQm’“. . . . A O In” a 0 ‘ r 1 Then“: enemas. aoaaoo I m Senna e38 8.83 n a .35 3.93.3 usages s w .33 038 commons m .8233 62 u 8 .H 38 do 3th adds» mo Anson» on» no oneness peace 85 no 83.33%? .333 no sesame sea .: .ME . . I» I .. $5.1m... Ix..fi . O .. I v . .u .. .r. the first crop of sudan grass on soil 1. The copper content of the first crop of sudan grass on soil 2 was not affected by the various treatments. On soil 1, the percent- ages differed proportionately with the rates of soil application, and the foliar treatments gave as high a percent copper in the crop as the 25 pounds per acre soil applications. The data in Table V show that the yields of thg second crops of sudan grass on both soils were lower than the first crepe. The copper content was also lower, and was proportionate to rate of application with no difference due to the copper carrier. All treatments on soil 1 were significant at the 1 percent level, whereas there was no signi- ficant response in yield to copper treatments on soil 2. 27 TABLE v The Effect of methods and Rates of.Application of Two Copper Carriers on the Yield and Copper Content of the Second Crops of Sudan Grass Grown in the Greenhouse on Two Organic Soils ‘ v—v'-.~»w— gpgltment* GEBilrl __ Soil 2 Pounds Method Mean Iean capper of yield** yield** per appli- (grams Percent (grams Percent §oppcs acre cation per jar) copper pergfiar) copper None —- 0.9 —-— 9.1 0.0008 Copper Sulfate 5 soil 32.3 0.0008 15.1 0.0006 Copper Oxide 5 soil 34.3 0.0008 17.5 0.0007 Copper Sulfate 25 soil 35.3 0.0009 16.8 0.0011 Copper Oxide 25 soil 39.1 0.0009 17.0 0.0010 Copper Sulfate — 0.005% 16 .5 0.0009 12.7 0.0012 Spray 1 Copper Oxide -_ 0.005% 9.3 0.0011 15.5 0.0012 spray Copper Sulfate .— 2.5% 16.3 0.0007 10.0 0.0012 dust Copper Oxide _. 2.5% 13.6 0.0010 11.1 0.0013 dust L.S.D.*** 1 percent 7.1 -—- 11.5 --- 5 percent 5.2 ——. 8.4 ..- * A uniform.application of 1500 pounds per acre of 3—9—18 fert- ilizer applied to all jars of soil 1. Sudan grass harvested on April 30, 1952 and.July 27, 1952 from soils 1 and 2 respectively. ** Averages of three replications dried for 72 hours at 60-80°C. *‘* Difference required for significance between any two treat- ment means. 28 DISCUSSION The resultant increase in values obtained by ashing the sample at 650°C could not be accounted for by techniques or reagents and the direct cause was not determined. There was no appreciable change in the copper content of the soils after two croppings which shows the relatively small amounts of copper necessary for plant growth. In most cases with soil 1, which responded to capper treatment, yields from the dust and spray treatments were significantly higher at the 1 percent level than the control. These yields were not as high as those Obtained from soil applications. In evaluating this difference in yields between foliar and soil applications, some consideration must be given to the fact that on all first crops the concentration of copper in all foliar treatments was high enough to cause leaf damage, and in the case of the sulfate sprays some spinach plants were killed. For this reason on the second crops the concenp tration of fbliar treatment was reduced to a point where no visible deleterious effects of the treatments were observed. Observations on the effect of spray and dust treatments showed that if the plants were sprayed.when they were too young they were more suscepitble to injury than if treated after three or four leaves hare grown out. If spraying is done too late the benefit from the treatment will not be very great, and the growing period would.be lengthened provided this effect is not masked'by photoperiodism. . 71Lw‘,’ ‘efivr‘c 1": "‘"T1‘. {'1 '1 .i‘ H. "o: ‘ 4C ‘9 .11“ z' “:33 :3“! ,. “war in *.e case "p ‘;.139" 32‘ saute} tlw s e. ("3 3*;Qizs of *v‘ea 3109.311 1,?) Lna"1‘9'.".::e in wilt“, Ending grass emuazw‘“e f?lffi€h;t than afifirntfin :0 t?: ’dt3+a" C‘L”(nh. tratiuns 3F falter treatments. with 339 6.35 fiercent cepner awe; . . '- ~ l .'. , . go. —, ' ' ,.. r "-v- -4 a -. . trearrwwrs seiner“ snawrd visa 10 $5M‘fums vf la»a.. fswm {*9 ur’ie Q senses of copper, w evens tve sufian grass d?5 not - - ‘0 _ . -.‘ ,J‘ a 4. _.,._‘, afrected by {LES same concentrating sf can a? fTOu twe sulfate senses. sail aonlicatiens proved .3 be mast effective in the ne‘erity sf A .. ’ I - o r .. ‘ ..“ . J . o- .\ v" —. 7* - ‘~ - ~ ‘u . . e. . cases observel. Alt wart Lute so-ls Conta19ed equal {encen axes 91 _ .4 ' Q ‘ . ‘ n . .-. n-.--..- v‘. . v . q.-" "n! -( v cerawc. Os sozl 2. sunav {rues did ant .85”09u sIgHIIrcnrtt. to a». u . ‘ “ Q “ '0 -‘ ' ‘w— ‘ ' ‘ ' ‘ a " . HQ 1” I ‘F treatments .x'm. the ascend crrm sum-'62.} a L.’.‘t‘;u1 taw:a."..s a Lama? fru- a soil 3? lica?%nn. .‘ A l ’0 u The cofi“er content 5; Lye C'ants was not ianJegccfi tv it? Garth-"‘1' ”99.1, ‘fFY‘O‘Vidfli £2791”. We same-e ramvnmt «1" nerve? was QI‘Z’W‘hzq‘ I?! q :11 cases of soil apolicatinpg, the coreer centert of t?e p varied directly with the quantity present in the soil, Ilene nu cooper was 1n' isd and plants sn°fersd from copper defi.iuncv, the Q I percentase of capfer was as nigh as other plants that showed no tanner def Us :0 ,4- to 33 ’3 ‘ FVUT‘C‘tOTHR. In g‘ eneral the COFNWDV 020019.017. Of tsp first. crates were hi ”2...? than. the see-3nd ore-5‘s. white is h...*“.~ver‘:. tn - be due to retid tie up ef copper in ’3 ' f f' ‘ r.) O CO 9 bob -..J C 0 "a O: (I) ,I‘ J) .3 .‘Z‘. :0 1...: Siffereuce in crew response since the perceviase of copper is t?» sails fer bnth craps wfis as entiaj'y the safe, Conner deficiency of stinnoh plant; regnlfg‘ 1n stursi ,rqfits’ a. s j .. - \~ 7 7 - a ,. V . - infu'i'if'y {’7 "Y"“."c‘18 529.013., 3"" ‘fif'flt‘htt'rfit 1.2-frat ‘. 2 Yir-r""‘s'-1‘:-: 1, .0 IA ilissiratei 11 fii?nre S. In snflau era 3 1 I '4 v . . . ‘ 3 I‘, .. , ~ .' -.. . ~ « 1 71:31 ‘ 'i’iy ‘0 1'17“.) fi.]ntbj }‘ 3.,:.‘; C! ’ $1117" ‘l'fl'; 31.1.3. awn 33177 c - _ p ‘ t . I- N v . \ e ' ‘ . V. -\ .- 5? eaves, especia;.y younn seates, are an many cases C"er.svs . v".4v" ‘11.? 119‘“? “'83? 5*1'). .t-j'J. "',“l..._‘ death n? tin entire plant. Figure 6 shows are of the largest an: GePiCSent plants beside a mefiium sized non—deficient leaf. .:9 .v'1fnbfi . k,‘ eucling of tte tins, and apparent inability to ones can he observed. This curled portion cf the end of the leaf was never opened, awfi J t*9 ‘98? Cort awed to prev t‘is reruiwn startlnf at the tin lint color aradna;ly and dr‘ed up rapidly. Tt was not uncom.ne to nlserve a leaf tta? bad one ttird of it conmletelY dry tewarle f 1 tip, and the adjoining two tlirds pa=e green. (.38 ‘t‘! Fig. 5. Normal (left) and copper deficient (right) spinach leaves. (Note reduced size and marginal necrosis of deficient leaf.) Fig. 6. Norm]. leaf (1am. copper deficient plant (right). The deficient plant was one of the largest obtained. in the Jere on Soil 1 with no capper added. - ' )) "JJ SVT?AFY Thi? efuay wan 99+ or to investirfite snnraea, raiee, aha mgtknqg of &“h3icatinn of corner on the Vieid and tonne? content n¢ gfifinmch ‘- . 3n* “"33“ Erafis Fr“wn in .he ereen‘onae on fwe erranio Pefi‘s. fine nf the gniig vi?“ a b? of 6.0 was ”htaired from tna §.5.C. ?u0k Exeerinenta? Farm anfl tFe nfher with a r” of 3.? van ohta‘ned {ran the AnSereon Farm in Threat Canniy. ¢h9 80i18 were driel to an annarent 0r*imnm mnistnre content and each eoilxne sieved throat? a 1/b irnh acreen after whinh a conviart weight of each was pieced 4n 108 nrevionsiy we‘ghefl, fowr-sailon, gla?ed Jars. A Iasic freafvpnt of q—Q—IB fertiiiwer at the rate of ““03 nnrnig T“? acre ani the equivalent of 10 pennfis 79? acre if ch?erdnyo {wire-worn CGfifVfiT) Was 88691 fig 33‘ treaingn+s on knfh $6119, Tn aql=tinh to the Shove, n” the avid Anaerefin 90‘1 73 f°nfi 59" acre ,v a? rrnriritsfefl calcium carhanate was aided whirh hrndeht the Te no frnm 1.7 to <.7. In Conjunction wiih Wime certein miner e‘ererfa 1 e w o -\ *1 f‘” " "\ f‘ -\ ‘ -- - l‘ W??? anufifl; Zinc awnfafe (Lnnfiu'rzx, at a5 hfiufifis be? acre, nma13ncsu 1": su‘fate (VnS-b'figfl) at 1“? nonnaq “er acre, ani snfiinm hernia (Vampe“7°13”on\ at 100 rownds “er acre, ¢ u , a ' ‘ ~ Ochre? was arpiiei t3 the :fiii af fwo rnfee, S and 25 “n“n53 be? ore, and 3196 to the 7 even as a dunk find as a snrav. The conjpv for eac? n? thpqe trenfmsqfe Rae Revived from LNG genre s: cnpwer snifate, ani cowrnr 01156. ”he f‘ret four crane were grown durinr fhe feriofi fr.m late f8+1 thrflnch wirfer, and the seconi few” crops fer late winter thr0"@h 9731'? 31.? wi {h arfificji EU, 115.14" *1 5 HR S"1""‘2 19% W99?! name 3&7? . Snmjies of the so¥13 were raven from each a? the treafimenta hefore and after crnpyin; and anaiyved for coffier. The crepe were harvee+ed, fresh weights recordel: waePnd where {07iar treafmenie were aj¢1iei, eni driei at 6“-RW”S after which the dry Wei§Ffe were renwrflefl. Plant aamjies of each of the treatments and cropringz were aWeh anQIyzed for cfiyffir. The fbiinwieg ohservafiene were mzde: 1. It is necessary to 89% safirles for any??? ana‘ys‘e at A 'I o - . I o w bSG C to ohtnin rerronucxhie reengus egreezng Wlffl those rercrfed rrevinnsiv hv other workers. I - O 2. The copper canfant of the 80315 IS not cha fed ernrec— iahiv after fww cronrinpe at the varieus ieveis of Geffen armiica+inn. 3. Cn soil 1, there is connEHSiv. evidence that CAfffiv is 7 hene?ic%ei to {he grnwth of srinch and swdan frees. 0n sci] 2, on’y S“iwanh «Fayed benefifs nf corner afpiieaiiwps. 3‘ h, 803? arhiicatjore in most cages gave ? tier resnite than fn1§ar afpiicafiwna, 5, There was 1itt?e or no ”Efferevcb in the effectiveness 9f either coprer oxide or carver sn’?ate to increase yieT£s or influence the center content of t R_f?ant if tppy are bofh uggd at f?e samn rate a? total cnyrer. 6. The 25 pound per acre rate a? 3911 afip1ica inn was wore effective than tVe 5 “ounce her acre ajw‘icatinn in ancraruing the ‘2“; CAHASP ennfen+ n? tie mWnnfi tiseue, “n7y in 3%? 9H9””3 0P7“? 33d t2» fnwmpr raie five ?‘€%er (15733 than the Ffltiér. 7. Dnsée and S?”8Y treafmenie need i“ 3390”8*9 (“‘““f“x;6; cunnantvaiiars are eanaJWF Efficient in Cfirrpr’i”€ carver 59f<¢=eney and increasinfi ?ie1de but not an effective 89 9011 3T$3103t3““3' ‘0 in. 12. FIFLIGGQAPPY ficimev, T., ani Pawnee, C. F. 0n the reaction inactivatjnn nf trvocirflse flnrfrr the aerflhic “xidaiion 1f rainchm1. Jn1r. Amer. Chem. Soc. 72:833. 1910, Arnnn, D. I. C11 er enzymoe in i111 Awi c}iorn“‘a¢fs and nn1vn p?en11 arifiaae in Pefa vv7wzrifi. PTant vaninl. 2h:7-74. VQiLQ. FunctionHT aenecfe of Cn““er in “Ennis. C“““P* —I- ”I -—-. ~ ~" mm Fetahniien Svmn,, John PofiV3rs Freya Paitimnre Yd w 33 “or-- W.— *.~ 1 ~ . . _ ’ . ’ - . . 1 ffi « D Peesnn F Coo anfl ”3*?”“9. G. mhe nn*ri°rt confent of nafive ‘3 forage in re!8tinn ‘0 and fermg ar1 RWE] fV"CS in ‘an h Carniiqa. 22:131.:ZLEZMLLII 2:32.. 3“?“ F“P"“9 Free“: FFL" t1 figure , Rd . . 1!: :‘y . :4?1;..:-L?9 . igfif: . Fodine, J. F., anfl Alien, T. V. Tryosinase and nr'nnie. ”rec. Sac. Yfrpti. FHI1F. hExi. 5°.Cfb1. 1935, Frown, J, C. Infjuenue of Conner comrowrde arfiiei to muvk soii an the yie7d, growth jaifern, anfi compesitieu of certain crops. Thesis for PhD., Nichigun State CAIIexe, E. lensing, Hich. -1QLQ. , ani Steinherg, R. A. Tree and confer enzymes in ieaf Iawina of fohance when deficient in micronutrienis or grown on chicareone anfi organic 80‘19. In Preeq. Cartw rirnf. G. E. Cnpfer metSRWnli m in nman SNPJGCtR. 0”“‘9? h.p ;+:.=!niigm_§322., Jehn ankins presg, .a‘timnre, Ffi., If, 22%- 287, i950. CnTWil'l, A. g. The formcm‘,‘ V Of CO :‘Y‘Qr Can1€I€~gCr~nwgr Vetahoitgp Svmn. Tenn” “0 kins Press, P3) timnre, Nd,, pr. ]—:!.5, 39‘4“. Cunninrham, I. J. COPTfiF deficiency in cait‘e anfi sheep on beat lands. ficw Peaiani Jonr. Sci. Tech. 23 {3):242—915. 1ou1. Eswsou, C. R. Correr firmiefin aecerbic acid oxidase. Conner Hefahn‘igm Svnn, John Packing Prepe, Pa1iim2re, Yd. W. ‘0. __--_.--.. 9 DeTf, E, N, Tr; fins7oc1tion 0f corner inns in plants, Nature, land. 15?: 6)& 608. laké. ha 3\ 99"‘9? V G Cnrrfir mefahwiiam 51 1%» 1“" tfenrates. chsupr P‘f3'1‘..f-; f)"l.5 1,7] lb“ . 9 ITOZ‘n E':.’!“1f‘-'i ’l S f}.€. sag ’ r1“: ti ’0‘er ’ a, .i . ’ "fl...“ . 1CQ-7 2 1: anffir tn haemHETOhin :vntLegig in tag cLick, 390?. pfo7. C}nm. Pb:13}-iL;. 13:: FeEFx, E. I. Currentinn of nunrnéuc‘1vp muck by adiitimn 1? Corner. Phytnpath. 17;hQ-;U. :37. 7333, F. P., and IanVF, J. r. some physiological ashects of COY‘HHY‘ '1?! t}?! OI‘r'un‘Sri. JO‘II‘, "30.1. Chem. 824:1(31—11'1‘. 1Q290 ?arrex, P. M. T?a Hu4k 9131! OF Vichigau. Mich. Ag. Exit, Sta. "asier, A. Fefentinn 1? cnpjer in $131. Abstract. Fibl. of Hinnr Riements. Chl1ean Vifrate Fur. Inc.. N. Y. V31. 1: 68 n O 1 gj';‘9 . Foag1and, D. R. lectures an tve Ennrganic nutritiun of plants. Ckrnnica Fatauica C0,, 3. Y., JQhL, Vnimc-, R. S. Gunner and zinc TTnited St.at q. SQEI Sci es and piant Janka. G, V,, and Sherhatnff, A. S.i1 deficierci “ 7 11. 1931;. disaases. Imh. ?nr. 3113 Sci. in some sa1fiy Jamisan, V. C. AdS‘Thiifin and f . ”P; r ° 3:287-297. 19L2. ix SM118 of central FTurjda. uni. Fallin, 3., and Nana, T. T3003$ e, a ane copper profein frnm Iatex of P“Ls SuC.€4"i;2 ature. 111d. 72bf:22 1039, Tazareva A0 Mo C" {muaaiirm Ea"C58-7593-ic Aé’l’. (TI.S.S.R.) T711. 71 éfl-éfi. Abs. 111. . Liner Tiements, Chilea' Litrate Fur. 1 .17- ’ rm? & Inc.’ N. Y. ‘ JvL-Q‘I. lawman, C. P., P'u‘wea s, P. U. The effect of confer, zit1c, ixnn, ans lead saTts on am‘av’fi fitf‘nn apl nitrfificatinn in 903‘s. AP9. PEP]. ?in1r LFGMLnR, Cri wan ”*trnfe “Hr. Inc., Y. Y. 1.760 1319, , and Fchnney, G. Prnwf of the asaentia? nafqra of cnhyer for PigPfir green fTanta. 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