A WHEY OF THE AVAELAMLETY OF MxTWE ANS AWUED‘ FHGSFEï¬QEï¬UE‘: TQ GREG-{RES AND: PCTATQES‘ GRQWN GIVE A HQUGHTQN MUCK Tim.“ {at- Hm Doqm a»? M. & MCEEMN STATE UHEVERSETY Lo-Tuug Wang 2:957 ngEsas ICHI IIIIIIIIIIIIIIIIIIIIIIIIIII QS‘QMSI ‘ LIBRARY Michigan State University ,i W — ‘— “-- F. _i - s-fl— - 2 ‘_.~.-_ ‘A‘K‘AL ’ i' .. ABSTRACT A STUDY OF THE AVAILABILITY OF NATIVE AND APPLIED PHOSPHDRUS TO ONIONS AND POTATOES GROWN ON'A HOUGHTON MUCK by Lo-Tung Wang Field and laboratory investigations were carried out to determine the response of onions and potatoes to native and applied fertilizer phosphorus, and to evaluate the importance of organic phosphorus as a source of available inorganic phOSphorus to plants grown on a newly reclaimed Houghton muck. The response of potatoes to applied fertilizer phOSphorus on a virgin HOughton muck, was less than that of onions. The depression in potato yields resulting from high rates of applied fertilizer P may possibly be associated with a decrease in plant uptake of zinc. The Baule units of soil and fertilizer P were ob- tained for onions and potatoes according to the following equation: log (A-Y) = log A-clb-cx where, A = the maximum yield of onions and/or potatoes; Y = the yield where no P is applied but other nutrients are present in adequate amounts; cl = proportionality constant; b = the amount of soil P present as determined by the Bray Pl Lo—Tung Wang soil test; c = the efficiency factor of the method of applying the fertilizer; and x = the quantity of fertilizer. of the form of nutrient b, that need be added for a desired percentage yield. In general, the Baule units of soil and fertilizer P for potatoes and onions grown on a virgin Houghton muck were less than the cultivated muck soils. An increase in the total phOSphorus content of all soils was obtained with the application of fertilizer phosphorus: however, the inorganic phosphorus content of the virgin soil was less than the cultivated and fertilized soils. The percent organic phosphorus decreased with in- creasing levels of fertilizer phosphorus, being highest on the virgin soil (75 percent) and lowest (50 percent) on the soils receiving 88 pounds of phOSphorus per acre for a 3— year period. Soil incubation studies indicated that virgin muck may be a source of phosphorus for plant growth. There was no evidence to indicate, however, that the release of in- organic phosphorus was dependent upon the amount of applied phosphorus. Water-extractable and .05 g HCl—extractable P32 indicated that cultivated muck soils retained more phoSphorus than the virgin organic soil. , The data suggest that the efficiency of fertilizer phOSphorus in muck soils would differ depending upon the extent of cultivation and phosphorus treatment. Accordingly, the response of crops to fertilizer phOSphorus would also change. A STUDY OF THE AVAILABILITY OF NATIVE AND APPLIED PHOSPHDRUS TO ONIONS AND POTATOES GROWN ON A HOUGHTON MUCK BY Lo-Tung Wang A THESIS Submitted to Michigan State University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Department of Soil Science 1967 ACKNOWLEDGEMENTS The author wishes to express his sincere gratitude to Dr. J. C. Shickluna for his guidance, earnest assistance and constant interest during the course of this study. The author is also indebted to Dr. A. R. Wolcott and Dr. B. G. Ellis for their valuable advice during the early phase of this investigation. He is thankful for the constructive suggestions and criticisms offered by Dr. R. L. Cook, Dr. J. F. Davis, Dr. C. J. Pollard and Dr. R. E. Lucas. Special appreciation is extended to Mr. T. M. Lai for his assistance in the study with radioactive phosphorus. He also appreciates the kind help from his fellow graduate students. The blessings and encouragements from home were always a source of enthusiasm. ii TABLE OF CONTENTS Page INTRODUCTION . . . . . . . . . . . . . . . . . . . . . 1 LITERATURE REVIEW . . . . . . . . . . . . . . . . . . 3 Brief Review of Composition of Organic Soils 3 Level of Total and Organic Phosphorus in Soil 4 Major Forms of Organic Phosphorus and Inorganic Phosphorus and Their Availability 6 Immobilization and Mineralization of PhoSphorus lO Fixation and Solubilization of Phosphorus and the Role of Organic Matter 12 EXPERIMENTAL PROCEDURE . . . . . . . . . . . . . . . . 16 Field Experiment 16 Laboratory Experiment 18 Determination of Total, Inorganic and Organic Phosphorus 18 Incubation Study 20 Leaching Study 21 RESULTS AND DISCUSSION . . . . . . . . . . . . . . . . 24 GENERAL DISCUSSION . . . . . . . . . . . . . . . . . . 53 SUMMARY AND CONCLUSIONS . . . . . . . . . . . . . . . 57 LITERATURE CITED . . . . . . . . . . . . . . . . . . . 60 APPENDIX 0 O O O 0 O O O O O 0 O O O O O O O O O O O O 68 iii LIST OF TABLES Table Page 1. The effect of applied phosphorus on the yield of onions in 1963, 1964 and 1965 .. . . . .. . . . .. . . .. . . .. 25 2. The effect of applied phosphorus on the yield of potatoes in 1963, 1964 and 1965 . . . . . 25 3. The effect of phOSphorus treatments on the yield and amount of phosphorus in green onion tissue 6 weeks after planting, 1963 . . . . . . . . . . . . . . . . . . . . 29 4. The effect of phosphorus treatment on the amount of phOSphorus in green potato petioles 6 weeks after planting, 1963 . . . 29 5. The influence of phosphorus treatment on the yield and iron, copper, boron, molybdenum and zinc content of potatoes, 1963 . .1; . . 32 6. The calculated cl values for onions and potatoes grown on a Houghton muck in 1963, 1964 and 1965 . . . . . . . . . . . . 35 7. Baule units of soil phosphorus (Bray P extractable) for onions and potatoes grown on a Houghton muck over a 3-year period . . . . . . . . . . . . . . . . . . . 35 8. Phosphorus requirement for onions grown on a virgin HOughton muck, 1963 . . . . . . . . . 4O 9. Phosphorus requirement for potatoes grown on a virgin HOughton muck, 1963 . . . . . . 4O 10. Phosphorus requirements for onions grown on a Houghton muck, 1965 . . . . . . . . . . . 41 11. Phosphorus requirement for potatoes grown on a Houghton muck, 1965 . . . . . . . . . . . 41 12. Calculated c values for onions and potatoes grown on a Houghton Muck, 1963, 1964, and 1965 . . . . . . . . . . . . . . . . . . . . 42 iv Table Page 13. Total, inorganic and organic phosphorus status of virgin and cultivated HOughton Muck . . . . . . . . . . . . . . . 46 14. Changes in the inorganic phosphorus content of incubated virgin and cultivated Houghton Mucks . . . . . . . . . . . . . . 46 15. The effect of soil cultivation and phosphorus treatment on the retention of applied P32 on a Houghton muck using water as the extractant . . . . . . . . . . 51 16. The effect of soil cultivation and phosphorus treatment on the retention of applied P 2 on a Houghton muck using 0.05 g HCl as the extractant . . . . . . . . . . . . . . 51 17. The evaluation of inorganic phOSphorus on three Houghton muck soils by three methods. 56 18. Moisture loss from an incubated Houghton muck contained in a small test tube and covered with polyethylene paper . . . . . . 56 Figure 10. 11. LIST OF FIGURES Experimental plots located on a HOughton The The The The The The The The The The muck at the Michigan State University NMck Experimental Farm, Clinton County . . relationship between the yield of onions and applied soil phosphorus in 1963, 1964, and 1965 . . . . . . . . . . . . . . . . . relationship between the yield of potatoes and applied soil phOSphorus in 1963, 1964 and 1965 . . . . . . . . . . . . . . . . . relationships among phosphorus applica- tions, phosphorus in the green tissue (6 weeks), and the yield of No. 1 potatoes, 1963 . . . . . . . . . . . . . . relationships among phosphorus applica- tions, phOSphorus in the green tissue (6 weeks), and the yield of onions, 1963 . relationship between Bray P1 extractable soil phosphorus and the yield of onions, 1963 O O O O O O O O O O O O O O O O O O O relationship between Bray P extractable soil phosphorus and the yie1d of potatoes, 1963 O O O O O O O O O O O O O O O O relationship between Bray P extractable soil phosphorus and the yieId of onions, 1964 . . . . . . . . . . . . . . . . relationship between Bray P extractable soil phosphorus and the yieId of potatoes, 1964 O O O O O O O O O O O O O O O O relationship between Bray P1 extractable soil phOSphorus and the yield of onions, 1965 . . . . . . . . . . . . . . . . . . relationship between Bray P1 extractable soil phosphorus and the yield of potatoes, 1965 . . . . . . . . . . . . . . . . . . . vi Page 26 27 3O 31 36 36 37 37 38 38 Figure Page 12. The effect of incubation on the release of inorganic phosphorus on virgin and cultivated HOughton muck . . . . . . . . . 47 vii INTRODUCTION A hungering world is facing an imminent shortage of food and a surplus of people. The food-people situation is alarming scientists and economists. Each year a new nation is born-—the current birth rate adds nearly 70 million people to the world each year. And the numbers are increas- ing. More food must be produced at an alarming rate if the needs are to be met. Organic soils constitute important potential soil reserves for the nation and the world. Of the 4-1/2 to 5 million acres of organic soils in Michigan, representing 1 acre in 8, less than 5 percent is farmed. However, they represent an important economic part of the agricultural production of the state and will play an even greater role in world food production. A large percentage of organic soils in the United States was formed in potholes, lakes and river beds follow- ing glacial action. Glacial action is the most important causal agent in the development of organic soils in Michigan and other northern states (16). It is important that we have a knowledge of the fertility problems associated with these soils if good quality food is to be produced with adequate economic returns. The fertilization of new or reclaimed organic soils presents management problems different from those that have been cultivated and cropped for many years. Since organic soils are formed from plant materials, it is not surprising that from 30 to 85 percent of the total phosphorus in virgin organic soils is in the organic form (85a). Five forms of organic phosphorus--phospholipids, nucleic acid, inositol phosphates, "metabolic" phosphates and phosphoproteins— have been suggested as components of organic soils. Of course, organic phOSphorus has to be mineralized before it can be utilized by plants. This investigation was initiated and carried out at the Michigan State University Muck Experimental Farm in Clinton County to correlate the response of onions and potatoes to native and applied fertilizer phosphorus, and to evaluate the importance of organic phosphorus as a source of available inorganic phosphorus to plants grown on newly reclaimed mucks. LITERATURE REVIEW Brief Review of Composition of Organic Soils Organic soil deposits Spread over a large area of the United States, but only a small percentage is farmed. In Michigan, 4.5 millions acres of land are classified as organic soils which include the soil series of Carlisle, Rifle, Lupton, Rbrkey, Rollin, Carbondale, Houghton, Linwood, Ogden, Palms, Adrian, Willette Cathro, Lake Marsh, Tawas, Kerston, Greenwool, Dawson, Loxley, and Spalding. These organic soils contain at least 20 to 30 percent organic matter but differ in various properties such as texture, color, botanical composition, etc. (16, 24). Houghton muck, on which this research was carried out, is black to dark brown in color, granular and very friable in structure. It is composed of fibrous plant remains which consist of grasses, sedges, reeds, and other non—woody water tolerant plants over a depth of 42 inches. Its pH is about 6.0. The soil is poorly drained due to its low elevation, and hence its permeability is moderate (86). Virgin Houghton muck, prior to drainage, has a grass—type vegetation. After the land has been drained, however, a forest—type vegetation may predominate. Before a virgin muck can be cultivated, the vegetation must be removed and put in pasture for several years. A virgin muck is rarely considered a fertile soil. A newly reclaimed muck usually receives very high rates of fertilizers in order to obtain good yields. Harmer (25) reported that in the beginning, applications of potassium and phosphorus for most crops were thought to be sufficient for satisfactory production; but later on, it was known that under certain conditions, nitrogen as well as copper, manganese, boron, zinc, molybdenum and sodium were also important for high crop yields. Subsequent investigations showed that deficiencies of the micronutrients could occur in many cases (52). Roe (66) indicated that the fertiliza- tion problem of peat and muck soils was very complex. He further suggested that fertilizer requirements of these soils were dependent on lime content. Level of Total Phosphorus and Organic Phosphorus in Organic Soils Considerable work has been done to evaluate the P status of soils. Early investigations were carried out primarily on mineral soils. Schollenberger (70) working with Ohio soils, reported that the total P content of virgin soils was considerably higher than the corresponding value for cultivated soils, and only a small percentage was attri- buted to organic P. Auten (2), Pearson and Simonson (62), examined Iowa soils with respect to organic P and found that the organic P content decreased with depth. Recently, Kaila (37) analyzed hundreds of Finnish soils with her modified method (36) and reported that the organic P content ranged from 100 ppm to» 940 ppm corresponding to 17 and 68 percent, respectively, of the total P content of these soils. She also pointed out that the total P content of virgin mineral soils was markedly lower than that of the correspond- ing cultivated soils. As far as the P contents of organic soils are con— cerned, systematic investigation did not start until recently possibly due, in part, to the difficulties encountered in the chemical analysis. Paul (60), investigated the P status of virgin and cropped peat soils of British Guiana and found that the total P content of the virgin soil was higher than that of the cultivated soil; and after cropping, the yield obtained on the virgin peat was generally higher than that obtained on the cultivated soil. It appeared that virgin peat soils possessed greater available P than the cultivated soils. Additional evidence was obtained from Kaila's reports. She investigated 217 samples of virgin peat soils in Finland (34). The results showed that the total P content varied from 190 ppm to 1180 ppm between samples in the same group, it was as high as 2050 ppm in another peat. However, a larger part of P in the peats investigated occurred in the organic form. Her data showed that the organic P content varied from 57 to 93 percent of the total P content. These data indicated that the organic form of P predominated in the virgin peats studied. Similar results were reported by McCall et al (54). Kaila (33) So: 1’18] the also pointed out that the percentage of organic P increased with depth amounting to about 70 percent of the total P in the surface layer, and approximately 80 percent at.a depth of 50 cm. But whether the total P also changed with depth was not mentioned. Maipr Forms of Organic and Inorganic Phosphorus in Soils and Their Availability Three organic phosphorus compounds—-phospholipids, nucleic acids and phytin, were ascertained to be present in soils. Schreiner (71) made a general sketch of the compo- nents of organic P. Later work was carried on to isolate these components from soil and to estimate their amounts (20, 88, 89). Other researchers studied the reaction of organic P compounds with soil contents and their subsequent derivatives. Dyer and Wrenshall (21) pointed out that phytin was likely to accumulate in soil, especially in acid soil. It combined with sesquioxides and became resistant to enzymatic hydrolysis. They also believed that nucleic acids released from microbial bodies were easily decomposed and were the main source of inorganic P. Jadkman and Black (31) further indicated that Al and Fe could precipitate with inositol at a low pH. So far as we know, it could be true that a part of the organic P can supply P for plant growth. Several previous investigations have shown that either native organic P or incorporated organic P can be utilized by crops (4, 6, 35, 63, 88). Pierre and Parker (63) first proposed that crops planted in soils with a high total P content had less reSponse to phosphate fertilization. The total P repre- sented the sum of the organic and inorganic soil P. But, they were unable to distinguish between organic and inorganic P. Bertramson and Stephenson (4) compared the efficiency of organic P compounds and water soluble superphosphate and found that the latter was in general more available than the former, whereas lecithin or nucleic acids were better suppliers of P than the other organic P compounds studied. They suggested that relative efficiency of organic P was correlated with the simplicity of molecular structure and ease of decomposition. Bower (6) obtained the same conclusion as Jackman and Bladk (31) that phytin was least available in acid soil due to precipitation with Fe and Al, but he pointed out, on the other hand, that phytin derivatives were more avail- able than phytin per se. The availability of organic P was based on the fact that the Iowa soil produced high yields with a small amount of phosphate fertilizer, far less than the recommended amount as determined by soil test. Based on the finding that the rate of mineralization of organic P was dependent on temperature (22, 79), Bid et a1 (22) assumed that organic P would be more available at higher temperature, and they suggested that a portion of available organic P should be included in the soil test. Kaila (37a) has shown that virgin peat soils could supply a fairly large amount of P to the first cropping in a pot experiment, but larger amounts of P were obtained from soils with the highest content of inorganic P. Nonetheless, it was hard to stress the importance of organic P in this case. Inorganic forms of P were present mainly as Fe, Al and Ca phosphates. These compounds included monocalcium phosphate. monophosphate monohydrate, dicalcium phOSphate, dicalcium phosphate dihydrate, calcium octaphosphate, apatite, hydroxy apatite, variscite and strengite. According to Stelly and Pierre (72), fluorapatite was predominant in the soil. A fractionation method of the three major forms was developed by Chang and Jackson (12). In fact, the relative amounts of these compounds will change from time to time due to environmental influences such as pH, activities of Ca, A1 and Fe ions in soil solution and solubility products of the various phOSphates (13, 43, 45, 50, 58). The availability of these compounds essentially depends upon the activities of orthophosphates dissociated from these phosphates, since the orthophosphate ions are generally considered readily available to the plant. Hsu and Jadkson (29) pointed out that in a calcareous soil, the variation of total P was much less than the Ca phosphate fraction, and that the leaching loss and plant uptake were less significant than Ca phosphates transformations in soil. A very thorough understanding of phosphate trans- formations in soil has recently been achieved. Hsu also reported that the Al and Fe phosphates had approximately the same solubility as Ca phosphate between pH 6.0 and 7.0, depending upon the magnitude of cation activities from various solid phases such as gibbsite, alumino—silicates, hydrous Fe oxides, Ca carbonates, exchangeable Ca, and other soluble Ca phOSphates, and that they became more stable above pH 7.0. Generally, Ca phosphate is more soluble at lower pH. whereas Fe and Al phosphates are more soluble after the pH is raised to 6.0 or higher. Aluminum and Fe phosphates could be dissolved to a certain extent before they became occluded by newly formed Fe oxides (12). Haseman, Lehr and Smith (26) classified the products of Fe and Al phosphates into nine groups. Accord- ing to Taylor, Gurney and Lindsay (78), these Fe phosphates were considered more or less available to plants. The phosphate reaction products have been widely studied. Although dicalcium phosphate dihydrate was the major product of applied soluble monocalcium phosphate. various forms of Ca compounds were produced in the soil solution under the influence of pH and Ca activity. To indicate the equilibrium among various phosphate compounds, certain solubility diagrams such as phosphate potential (1, 87), and solubility isotherm (8, 9, 43, 44, 56) were established. Lindsay and Stephenson (46, 47, 48, 49) obtained a metastable triple point wherein monocalcium phosphate solution was in equilibrium with newly formed dicalcium phosphate dihydrate and undissolved monocalcium phosphate, by means of dissolving monocalcium phosphate in 10 water. On the other hand, they sampled wet monocalcium phosphate after it was band applied to soil and was moistened by the moisture in the vicinity of the band, and found that the composition of the sample was very close to that of the above-mentioned metastable triple point solution. According to their point of view, the metastable triple state was dynamic; phosphate gradually moved out and precipitated with Fe, Al and Mn in the order Fe > A1 > Hm. Immobilization and Mineralization of Phosphorus Immobilization and mineralization are among the major processes occurring in soil wherein soil P is transformed from inorganic form to organic form, or vice versa. Nevertheless, these phenomena are mainly attributed to the biological activities, of which plants and micro- organisms play a major role. There is no doubt that micro- organisms are the mainspring of these transformations, and therefore, in this regard, microbial activities in soils have been studied for many years in an attempt to under- stand the relationship between their activities and the transformation of soil P. Investigations were undertaken to establish constant C/P and N/P ratios in the soil, assuming that these ratios would shed considerable light on the understanding of microbial immobilization and mineralization of P. Certain tentative constants as C/P = 100, N/P = 10 were proposed after a broad investigation on various soils (35, 37, 61, 62, 11 70,82). The C/P and N/P ratios in microorganisms were also studied by a number of researchers (3, 35), and it was found, in general, that the P content of soil microorganisms was higher than that of the plant. Incubation studies were widely adopted by many researchers to explore this phenomenon (10, ll, 53, 59, 61, 81, 83). Chang (10, ll) conducted several incubation experiments to study the trans- formation of P during the decomposition of plant material obtained from young and mature tissues. The results showed that organic P was synthesized at first, and then was mineralized. Pearson et a1 (61) reported that nucleic acid, phytin and manure when applied to soil would decompose and was likely followed by mineralization. Thompson and Black (79), studying the effect of temperature on minerali- zation, found that the amount of P mineralized increased rapidly with an increase in temperature up to 150°C. In other words, higher incubation temperature benefited release of organic P. Subsequent work (80) indicated that the quantity of organic P mineralized in virgin soil was more than that mineralized in cultivated soil. Based on the results of previous work, Kaila (35) then postulated that biological immobilization and mineralization during decomposi— tion of organic matter seemed to be analogous to those of N. Working with muck soil, McCall et al (54) reported that mineralization of organic P was increased by means of applying large amounts of soluble inorganic phOSphate and incubating for a period of four months. It was also mentioned 12 that besides microbial activities, the action of certain soil catalysts could be a driving force of transformation from organic P to inorganic P (5, 64, 67, 68, 77). Fixation and Dissolution of Phogphorus and the Role of Organic Matter in Soil When soluble phosphates are applied to soils, most of the applied phosphate will be fixed into insoluble forms due to many existing factors in the soil and are rendered unavailable to plants. The phosphate ion remaining in soil solution may be as low as 2 to 10 parts per million. The so-called phosphate fixation probably results from three mechanisms, that is, chemical precipitation, physiochemical adsorption, and biological absorption. The third mechanism is designated as immobilization. In acid soils, the soluble phosphates are likely to react with certain metal ions such as A1, Fe and Mn, and the resulting compounds may be precipitated or adsorbed on the surface of clay particles which contains a great deal of Fe and Al oxides, or exchangeable Al (15, 26, 31, 38). It was also reported that silicate-clays, which contain larger amounts of hydroxyl groups, will fix a portion of phosphate by means of substitution of phOSphate ions for hydroxyl groups on the clay surface, or forming a clay-Ca- phosphate complex linkage when saturated with Ca (84). A completely different mechanism has been proposed for alkaline soils. As the pH increases to 7.0, the activity of Ca increases rapidly, and large amounts of phosphate are 13 precipitated in the form of dicalcium phosphate (14, 44), and subsequentlyymore stable, complex forms as HK 6 3A15(PO 4)8°18H20, and H28K(A1,Fe)3(PO4)6 Moreover, the phosphate ion can also be adsorbed on .6 H20 (48, 49). the surface of calcium carbonate particles or Ca—dominated clay particles. It appears that the activity of P will be lowered in those soils having a high Ca activity, either as a result of a large amount of finely divided calcium car- bonate or due to a large amount of Ca-saturated clay. On the other hand, although soil phOSphates are fixed into insoluble forms, the fact that a large amount of fixed P becomes available to plants implies that certain mechanisms occurring in soils can solubilize the phosphates to a significant extent. The mechanism which is considered as the most important one in this respect is the chelating action of organic acids, which originates from the decomposi- tion of organic matter and the excretion of microorganisms. It was reported that humic acid, the final product of de- composed plant residues, can reduce the fixing ability of certain metal ions such as Fe and Al (57); and it was also believed that this kind of organic acid complex in soils can hold the P in exchangeable form (7). Many researchers were in agreement that organic matter reduced the amount of P fixed by certain acid soils (18, 19, 27, 32). Conversely, other work has shown that removal of the humus from soil by leaching with NaOH did not reduce the fixing capacity of the soil (69). 14 Dean and Rubins (17) studied the replacing power of various anions and suggested that the order was hydroxide > citrate > fluoride > tartrate > arsenate > acetate. Swenson et a1 (76) suggested the fixed P was released by anions in the following order: fluoride > oxalate > citrate > bicarbonate > boraté>acetate > thiocyanide > sulfate > chloride. They further supposed that the ability of organic matter to replace P originated from organic acids, and that the ability of these organic acids to extract phosphate from soil particles was due to their properties of forming stable complexes with Fe and Al. Struthers and Sieling (74) proposed that the beneficial action of organic matter in the soil could be attributed to several sources: a. The protective action of organic colloids in preventing soluble P from coming into contact with the active Fe and Al. b. The action of CO2 produced during the decomposition of organic matter in dissolving certain P material or in "tying up" the active Fe. c. Formation of organic phosphate compounds, which are less firmly fixed by soils than are inorganic phosphate compounds. d. Decomposition of organic matter containing P accompanied with the release of P for plant use. They chose several organic acids of agricultural importance such as citric acid, tartaric acid, oxalic acid, malic acid and succinic acid, to determine whether the 15 organic anion would affect the fixation of P in solution at different pH values. Their results showed that the presence of hydroxyl groups was an important factor in the ability of a dicarboxylic acid to prevent P from precipitation by Fe and Al, whereas organic acids with one hydroxyl group had greater effects on the solubilization of P when it contained three carboxylic groups. Therefore, tricarboxylic acid, such as citric acid was tremendously effective in preventing P from precipitation at pH 4.0 to 6.0. Swaby and Sherer (75) and Louw and Webley (51) pointed out that microorganisms could dissolve mineral phosphates in soil. In fact, it was very likely that the organic acids excreted by microorganisms solubilized the phosphates by the same mechanism previously described. However, microorganisms play an important role in peat formation and decomposition (28, 73, 85). EXPERIMENTAL PROCEDURE Field Experiment A virgin Houghton muck located at the Michigan State University MuCk Experimental Farm in Clinton County was broken up in 1963. It was divided into two blocks with eight plots in each block, as shown in Figure l. Onions and potatoes were planted with different rates of P. All plots, except the "no fertilizer†treatment, received 415 pounds of K, 50 pounds of N and 20 pounds of Mn per acre. The P treatments designated as Po' P1' P2, P3 and P4, correspond to 0, ll, 22, 44, and 88 pounds of P per acre. All treatments were randomized and replicated two times (Figure l). Onions (var. Downing Yellow Globe) and potatoes (var. Sebago) were planted in May and harvested the latter part of September in 1963, 1964 and 1965. -The yields were obtained and recorded in hundred weights per acre. The green potato and onion tissue were sampled six weeks after planting in 1963 and P determined on the green tissue. Approximately 40 potato petioles and 40 onion leaves per plot were taken to represent a composite sample. The petiole of the fourth potato leaf from the growing tip was selected in all cases. The soils were sampled in the spring of 1963, 1964 and 1965. Available 16 l7 O 3"“ O P H r- o--—— o-« ---ru --.-_ rd.-. _--ru-_.._ --.ru --._- '0'“ b .3 P2 Virgin Area I R 'ï¬/ Figure 1. Experimental plots located on a Hbughton muck at the Michigan State University Muck Experimental Farm, Clinton County. All plots except the control plot (designated as 0) received 50 pounds per acre of N, 415 pounds per acre of K and 20 pounds per acre of Cu and Mn. The following P treatments were randomized and replicated two times: P0 = 0 pounds per acre P1 = 11 pounds per acre P2 = 22 pounds per acre P3 = 44 pounds per acre P4 = 88 pounds per acre (X) and the experimental plots. Soil samples were obtained from.the virgin area 18 P (0.025 N HCl + 0.03 N NH F extractable) was determined by 4 the Nuchigan State university Soil Testing Laboratory on a composite sample consisting of 20 subsamples per plot. Total P was determined on a representative sample of the potato tissue (petiole) in 1963. The oven-dried tissue was ashed at 550°C. and P determined Spectrographically. Laboratory Experiment Determination of Organic and Inorganic Soil PhOSphorus Sample Seventeen soil samples were obtained from the virgin area and the plots receiving the different P treatments (Figure 1). These samples represented seven different areas, namely, virgin, "no fertilizer†treatment, and P0, P1' P2, P3, P4 treatments. The soils were air-dried and sieved through an 80-mesh sieve. Extraction One gram of air-dried soil was placed in a beaker to which 10 m1 of 6.3 HCl were added. The beaker was heated at about 90°C. on a steam plate for 10 minutes, and then allowed to stand for one hour at room temperature with an additional 10 m1 of 6.3 HCl. The acidified suspension was collected and washed with 50 ml 0f distilled water into a 100 ml centrifuge tube, centrifuged at high speed and the supernatant liquid decanted into a 250 ml volumetric flask. The sediment was washed with 30 ml of distilled water and 19 added to the supernatant liquid, and 30 m1 of 0.5 N NaOH were added to the washed residue, shaken for 10 minutes, centrifuged, and the supernatant added to the acidified portion. The residue was then suspended with 60 ml of 0.5’ .N NaOH and heated at approximately 900C. in a waterbath for 8 hours. After digestion the suspension was centrifuged and the supernatant was decanted to the volumetric flask, and made to volume with distilled water. Digestion for Determination of Total PhOSphorus The extract was thoroughly mixed anui 20 ml aliquots were placed in tall—form beakers, and 10 m1 of concentrated HNO followed by 5 ml of 72 percent perchloric acid were 3 added. The solution was heated on a hot plate at a temperature below 160°C. until most of the concentrated HNO3 had been dispelled, covered with a ribbed—watch glass, and the temperature increased. The solutions were removed from the hot plate as they approached dryness, distilled H20 added and made to a final volume of 50 m1. A 10 m1 aliquot was taken for the determination of total P. Inorganic Phosphorus Determination In the Extract Solution The original extract was allowed to stand until all of the flocculates sedimented. A 5 ml aliquot of the super— natant liquid was taken for the determination of inorganic P. 2O Phosphorus Measurement by the Chloromolvbdate Methgd The standard curve was prepared by pipetting l, 2, 4 and 8 ml of 5 ppm P solution into four 50 m1 volumetric flasks containing a small portion of water. The pH was adjusted to 3 with 4 NuNH OH and 0.5 N HCl using para- 4 nitrophenol as the indicator. The blue color was developed by adding 10 ml of 1.5 percent ammonium molybdate reagent and 5 drops of 5 percent freshly prepared stannous chloride. The solution was made to volume and the percent transmission read on a Spectronic 20 colorimeter at a wavelength of 620 millimicrons. The same procedure was followed for the determination of total P and inorganic P except that 5 drops of 1000 ppm citric acid solution were added before the pH was adjusted for the inorganic P determination. Organic Phosphorus Determination The organic P was obtained by subtracting the inorganic P from the total P. Organic P = Total P - Inorganic P Organic P Total P x 100 % Organic P = Incubation Study Soil samples were obtained from the uncultivated (virgin) and cultivated areas of the experimental plots (Figure l). The sample from the cultivated plots had 21 received 264 pounds of P per acre over a three—year period. The virgin mudk soil was treated with 0, 25, 50, 200, 400 ppm of P and incubated for l, 2, 4, 6 and 8 weeks. All treatments were carried out in triplicate and each treatment received 300 ppm of N as (NH4)2804 and 20,000 ppm of sucrose. Two levels of P, 0 and 400 ppm, were added to the sample of cultivated mudk soil and incubated for the same period as the virgin soil samples. One gram samples of the air-dried soils were placed in flat-bottomed test tubes and raised to 50 percent water holding capacity. The tubes were covered with a thin layer of polyethylene and incubated at 30°C. The five groups of samples were analyzed for P at 1, 2, 4, 6 and 8 week periods. Similar analysis for the check samples (without incubation) was carried out in duplicate following the same procedure. Leaching Study This study was initiated to determine the relative P fixing capacities of the uncultivated (virgin) soil and cultivated soils. Four soil samples were chosen for this study. In addition to the virgin soil sample, one sample was obtained from the plot receiving no fertilizer, and the other two samples were selected from plots that had been cultivated for 3 years and approximately 25 years (aging muck) which had received a high annual rate of P application (Section C). The soils were sieved through a lO-mesh screen and 22 kept moist in sealed polyethylene sacks. The moisture content of each soil sample was determined and an amount of soil equivalent to 500 grams on a dry-weight basis was prepared. The soils were placed in four glass columns, 4 inches in diameter and 17 inches long. The bottom end of the column was tapered to facilitate the attachment of rubber tubing. A layer of glass wool was placed at the bottom of the column, and a rubber tube equipped with a pinch-clamp was used to regulate the flow of water. The soils were placed in the columns, the top of which was sealed with a sheet of polyethylene paper while a small hole, large enough to facilitate a rubber tube, was bored in the polyethylene. Distilled water was delivered into the column and the rate of flow adjusted to 1 drop every 2 to 3 seconds. Leaching was discontinued after a total of 1000 ml of leachate had been collected. Excessive free water in the columns was released. About 0.1 millicurie of radioactive P32, which was carried in 100 ppm of P in the form of phosphoric acid, was incorporated into a lOO-gram portion (on a dry weight basis) of each of the four soils. Each soil was moistened, thoroughly mixed and placed on top of the soil contained in the respective columns. The columns were covered with polyethylene and allowed to incubate at room temperature for 7 days. At the end of this period, the soil was leached with distilled water as described previously. Four additional 23 soil columns were leached with 0.05 N HC1 in the same manner as was described for the water leachate. However, the leaching was carried out after the soils had incubated for 20 days. Each 100 m1 of leachate was collected as a fraction, and 20 fractions from each soil were gathered. To determine the radioactivities of these fractions, 2 ml of the leachate was pipetted into a small aluminunlplanchet, and then evaporated to dryness on a hot plate. Radioactivity was counted on a NMC Model DS-L Decade Scaler. If the counts were very low, several fractions were combined,and a larger aliquot of the leachate was taken. Due to the extremely low counts of the leachates, the twenty fractions were combined. Exactly 1000 ml of the leachates were placed in 1000-ml beakers, and 20 ml of concentrated nitric acid added. The solutions were evaporated until only 50 ml remained, and then transferred to 50-ml beakers. The leachates were concentrated to 20 ml by heating, and transferred dropwise into aluminum dishes on the hot plate and evaporated to dryness. The dry leachates were counted. RESULTS AND DISCUSSION The effects of applied P on the yield of onions and potatoes grown on a virgin Houghton muck in 1963, 1964, and 1965 are shown in Table l and Figures 2 and 3, respectively. Onion yields obtained from the plots receiving 22 and 88 pounds of P per acre in 1963 were significantly great— er than those obtained from the plots receiving no treatment; and the 88 pounds of applied P per acre gave significantly higher yields of onions than did the 11 pound P treatment (Table 1). In 1964, however, no significant differences were observed in the yield of onions and the various P treatments. The plots receiving 22 and 44 pounds of P per acre in 1965 gave significantly higher onion yields than the plots receiving no P application. The application of 88 pounds of P per acre in 1963 significantly depressed the yield of potatoes over the 11, 22 and 44 pound application rates (Table 2). No significant differences were obtained among P treatments and potato yields in 1964. While in 1965, the 44 pound P application rate gave significantly higher potato yields than the plots receiving the Po treatment. The relationships among the soil applied P, the parts per million of P in the green potato and onion tissue 24 25 Table l. The effect of applied phosphorus on the yield of onions in 1963, 1964 and 1965. Treatment* 1963 1964 1965 N-P-K Yield Yield Yield Pounds per Acre th. per Acre th. per Acre th. per Acre 50- 0-415 497 416 417 50-11-415 540 356 639 50-22-415 596 392 651 50—44—415 559 333 651 50—88-415 639 377 597 L.S.D. (5% level) 84.6 111.5 233.8 *All fertilizers except 11 pounds of phOSphorus were broadcast. Table 2. The effect of applied phOSphorus on the yield of potatoes in 1963, 1964 and 1965. —_1 4‘ Treatment 1963 1964 1965 N-P-K Yield Yield Yield Pounds per Acre th. per Acre th. per Acre CWt. per Acre 50- 0-415 256 227 240 50-11-415 270 227 301 50—22-415 269 239 322 50-44-415 266 272 355 50-88-415 228 189 314 L.S.D. (5% level) 38.2 106.4 90.9 26 - moma paw wood .moma CH manonmmonm HHOm pmflammm tam mcoflao «0 name» may cmmBqu mflnmcoflumamn one .N muzmflm whom son A mpcsom mm _ s. mm a o x“ T. \ “W. a m l ..... .. 3. Ho $53365 \_\ p Hmmceq _ W o f oom u 1 m. iiifl, _ u -v\......|--- ,,/:/ \Q S 36m: ~50 u u .3. K--- ,, X, ,x, m. G . 03. a. m . 1 d 8 I .E D 1 a Amwaav mh.o n H ‘7. -, B ‘II‘IIII‘ .l a l’3’0DI'IIAI-"'I"I'IIB ““““ Amomav om.o u u 27 .mmma cam voma .mmma me msuonmmonm HHom pmï¬ammm paw mmoumuom mo came» mnu cwm3um£ magmGOHumHmH one muom Mom m mpcsom mm ï¬g mm Ma 0 .\\\ mucflom HmsoH>HUGH - ..... \\ Hmmcï¬q l A $1.1! . oom remade move u a - ,,,,/ .x1:---1 II M Ammmav os.o oom ll Ll Amomav ss.o , 00v 8132 Jed-1M3 ur seoqeqoa go pterx .m musmflm 28 and the yields of these two crops in 1963 are shown in Tables 3 and 4 and Figures 4 and 5, respectively. It is apparent from these data that the onions grown on a virgin muck low in available P (9 pounds per acre of BrayPl, extractable) responded to P much better than potatoes. Receiving 11 and 22 pounds of P per acre, No. 1 potatoes increased by 10 and 11 hundred weight per acre respectively over plots receiving no P. Onions receiving these levels of applied P increased 43 and 99 hundred weight respectively. The plots receiving no fertilizers produced onlYl6l and 36 hundred weight per acre of potatoes and onions, respectively (Tables 3 and 4). When 415 pounds of K per acre was added, yields increased 191 and 336 cwt.per acre, respectively. The soil test level of K was approximately 50 pounds per acre (1.3 NH OAc extractable). 4 As shown in Tables 3 and 4 and Figures 4 and 5 the P in the green plant tissue of both onions and potatoes generally increased with increasing levels of applied P. A decrease in potato yield resulted from the 88 pounds P application rate. This was accompanied by an increase of P in the green potato tissue (Figure 5). It is possible that the high levels of applied P created an unbalanced soil condition and induced a deficiency of some other element or elements essential for growth and optimum yields. As shown in Table 5, increased levels of applied P generally resulted in a decrease of Zn in the potato tissue.- The 29 Table 3. The effect of phosphorus treatments on the yield and amount of phosphorus in green onion tissue 6 weeks after planting, 1963. Poundsgper acre P in green oniOn leaves Yield in cwt. P + K* Partsgper million per acre 0 + 0 34.0 161 0 + 415 31.5 497 11 + 415 37.5 540 22 + 415 42.5 596 44 + 415 33.5 559 7“ 88 + 415 39.0 639 *All plots exclusive of the unfertilized plots received 50 pounds of N and 20 pounds of Mn per acre as a broadcast application. All values are averages of two replications. Table 4. The effect of phosphorus treatment on the amount of phosphorus in green potato petioles 6 weeks after planting, 1963. Pounds per acre P in green potato petioles Yield in cwt. P + K* Parts per million per acre** 0 + 0 118.5 36 0 + 415 61.0 227 11 + 415 60.5 237 22 + 415 57.0 238 44 + 415 80.5 238 88 + 415 129.0 193 *All plots exclusive of the unfertilized plots received 50 pounds of N and 20 pounds of Mn per acre as a broadcast application. **No. 1 potatoes low yields caused by June frost, 1963. 30 1 Potatoes — cwt per Acre Yield No. CH mCHosmmonm muoï¬ Com pwHHmm< m mpCCom mm TV NN HH 0 p - r — \W, \ \1x\ .A\ mummHB CH m.Emm1iii Tom omHi UHOHM on: A in. nnnnnnn c .05 OON. .Om CNN1 9 .OHH Oflmn \\\ \\ oomi .momH .mmoumuom H .02 mo pHmHh map UCm .AmxmmB ov owmHu Cmmum we» .mCoHumUHHmmm mCHOCmmOCQ on» mCOEm mmHCmCOHDMHmH one enssrm users u: a mdd .w mHCmHm 31 cwt Per Acre Yield Onion ome \ 9639 5. m. 5mm ii oom 0mm ooo 0mm . .mCOHCo mo UHmH> OCH pCm .Amxmm3 0V mCmme Cmmum OCH CH mCHOCQmOCm .mCOHHMOHHmmm mznonmmonm mCOEm mQHCmCOHHMHmH one whom Hmm pmHHmmé m mUCCom mm dg mm HH 0 ' ‘\ om OHOHN-‘ B anssrm users ur a mdd .m mHCmHm 32 Table 5. The influence of phosphorus treatment on the yield and iron, copper, boron, molybdenum and zinc content of potatoes, 1963. Treatment P Mn Fe Cu B Mo Zn Yield [1 Pounds P - cwt. g per acre Percent ppm per acre “7 0 0.486 687 267 12.4 31.3 5.5 81 256 11 0.501 614 266 12.9 29.5 5.8 79 270 22 0.471 712 256 12.0 33.0 6.5 71 269 44 * * * * * * * 266 88 0.502 627 200 12.0 26.0 5.2 54 228 *No sample taken. 33 tissue obtained from the plots receiving 88 pounds of P per acre contained about 33.3 percent less zinc than those ob- tained from the plots receiving no phOSphorus. The total P in the tissue, however, did not vary appreciably (Table 5). The tremendous response of both onions and potatoes to soil applied K in 1963 is shown in Tables 3 and 4. The application of 415 pounds of K per acre on the PO plots 3 increased the yields of onions and potatoes from 161 and [ 36 cwt. per acre to 497 and 227 cwt. per acre, respectively. L4 The application of 11 pounds of P per acre, on the plots receiving 415 pounds of K, increased onion yields by almost 9 percent. Only a slight increase (about 4 percent) was obtained in the yield of potatoes with this rate of applied P (Table 4) even though the soil contained only 9 pounds of available P. The response of potatoes to 11 pounds of P per acre appeared to be a â€starter†effect. No additional response resulted from the 22 and 44 pound application rates and a decrease in yield resulted, as pointed out previously, where 88 pounds of P was applied per acre. An attempt was also made to apply the mobility or elasticity concept to these data as proposed by Bray (8a) according to the following equation: log (A-Y) = log A - clb (1) where A = the maximum yield of onions and/or potatoes. Bray defined A as the yield possibility when all nutrients are present in adequate quantity but not in harmful excess, provided all other immobile nutrients remain unchanged and 34 nitrogen is adequate; Y = the yield of onions and/or potatoes when no P is applied but other nutrients are present in adequate amounts: b = the amount of soil P present as deter- mined by the Bray Pl soil test; and C1 = proportionality constant which was determined experimentally. The C1 values obtained for onions and potatoes are shown in Table 6; and the relationships between BrayPl extractable soil P and the percentage yield of onions and potatoes for 1963, 1964 and 1965 are shown in Figures 6, 7, 8, 9, 10 and 11. The value for one Baule unit of soil P (Table 7) was determined from equation (1) using the experimentally determined Cl values, as shown in Table 6. A Baule unit of soil P may be defined as the amount of soil P necessary to produce a yield that is 50 percent of the maximum possible yield. The Baule units of soil P for the onion crop varied from 2.7 to 4.8 with an average value of 3.5. There was less variation in the Baule units of soil P for potatoes (2.0 to 3.4) with a mean value of 2.6. The interpretation of these data indicate that 50 percent of the maximum yield of onions and potatoes would be obtained at P soil test levels of 4.1 and 2.0, respectively on the virgin muck (1963 data). While in 1965, after 3 years of cultivation, 4.8 and 2.6 pounds of Bray P1 extractable soil P would be required to obtain 50 percent of the maximum yields of these crops. The equivalent yields (percent) for 35 Table 6. The calculated c1 values for onions and potatoes . grown on a Heughton muck in 1963, 1964, and 1965. r C1 vaIEes* CIOP 1963 1964 1965 Onions 0.0732 0.1110 0.0627 Potatoes 0.1470 0.0870 0.1170 *Average of 8 values. Table 7. Baule units of soil phosphorus (Bray P extractable) for onions and potatoes grown on a Houghton muck over a 3-year period. Pounds of soil P per Baule unit of soil P Crop 1963 1964 1965 Onions 4.1 2.7 4.8 Potatoes 2.0 3.4 2.6 For further references, see lSpurway, C. H. 1948. Soil Fertility Diagnosis and Control for Field, Garden and Greenhouse Soils. Edwards Brothers, Inc. Ann Arbor, Michigan. 2Willcox, D. W. 1937. The ABC of Agrociology. W. W. Norton and Company, Inc., New York. 36 100 90‘ 80‘ 70- 60‘ 50* Log (100-Y) = Log 100 - .073b 40: 30( 20. 104 Percent maximum yield of onions I I 7* 0 5 10 15 20 25 30 Pounds 8011 P per Acre Figure 6. The relationship. between Bray P1 extractable soil P and the yield of onions, 1963. 100. U) (D B m 90. 4.) 8. 80. 14.4 0 70‘ 3 60‘ 0) ">1 50. Log (100-Y) = log 100 - .l47b 5 40 E '§'< m 30‘ E 5 8 10« (D Q: 1- I I I I W 0 5 10 15 20 25 30 Pounds Soil P per Acre Figure 7. The relationship. between Bray P1 extractable soil P and the yield of potatoes, 1963. 37 100 J 90 * 7O 6O 40 . Log (lOO-Y) = log 100 - .lllb 30 - 20 . Percentage of Maximum Yield m o U I I I T 0 5 10 15 20 25 30 Soil P test Pounds per Acre Figure 8. The relationship between Bray Pl extractable soil P and the yield of onions, 1964. 100- 90' 80- 704 60* 50‘ 40‘ Log (loo-y) = log 100 - .087b 301 20' 105 Percentage of Maximum Yield 1 I r '0 5 10 15 20 25 30 Soil P test Pound per Acre. Figure 9. The relationship between Bray P extractable soil P and the yield of potatoes, 1964. 38 100+ 90' 80. 70‘ 601 50* 40‘ Log (100-Y) = log 100 - .063b 30' 20‘ 10* Percentage of Maximum Yield q T 1 I T T 0 5 10 15 20 25 30 Soil P Test Pound per Acre Figure 10. The relationship between Bray P extractable soil P and the yield of onions, 1965. 100* 90‘ 80* 70. 60- 50‘ log (lOO-Y) = log 100 - .1l7b 40‘ 30* 20‘ 10 Percentage of Maximum Yield 1 l I I 0 5 10 15 20 is 30 Soil P Test Pound per Acre Figure 11. The relationship between Bray P extractable soil 9 and the yield of potatoeS, 1965. 39 onions and potatoes relative to the pounds of Bray P1 extractable soil P for 1963 and 1965 are shown in Tables 8, 9, 10, and 11. These data indicate that 97 percent of the maximum yields of onions and potatoes could be obtained on a virgin muck with soil P levels of approximately 20 and 10 pounds per acre, respectively, and with 24 and 13 pounds per acre, respectively in 1965. According to Bray, the Mitscherlich equation could L ._.d be expanded to permit the calculation of the amount of fertilizer needed to raise the percent yield from any given starting level to any other desired upper level for which fertilization was desired (8a). He derived the following equation: Log (A-Y) = log A - Clb - cx (2) where, C = the efficiency factor of the method of applying the fertilizer, and x = the quantity of fertilizer, of the form of nutrient b, that need be added for a desired percentage yield. The yield of onions and potatoes obtained in 1963, 1964, and 1965 from the P rate experiments were substituted in equation (2) as a basis for determining c, the fertilizer P efficiency factor. The following equations were derived and the calculated c values for onions and potatoes for the 3-year period are shown in Table 12. Log (A—Y) log A - .0732b - .0265 x (3) 0 - '63* Log (A-y) = log A - .1470b - .0163 x (4) P - '63* Log (A-Y) log A - .lllOb + .1679 x (5) 0 - '64 40 Table 8. Phosphorus requirement for onions grown on a virgin Houghton muck, 1963. Fertilizer Reguirement Soil P Test* Equivalent Yield Pounds per Acre Pounds per Acre . Percent P P205 4.1 50 47.6 109.5 8.2 75 35.7 82.1 12.3 87 23.8 54.7 16.4 94 11.9 27.4 20.5 97 0 0 *BrayPl extractable. E1 1 Baule unit of soil P (soil test) = 4.1 pounds per Ej acre. 1 Baule unit of fertilizer P = 11.9 pounds per acre. 1 Baule unit of fertilizer P205 = 27.4 pounds per acre. Table 9. Phosphorus requirements for potatoes grown on a virgin Houghton muck, 1963. Fertilizer Reguirements Soil P Test* Equivalent Yield Pounds per Acre Pounds per Acre Percent P P205 2.0 50 74.0 2170.2 4.1 75 55.5 127.7 6.1 87 37.0 85.1 8.2 94 18.5 42.6 10.2 97 0’ 0 *Bray P extractable. 1 Baule unit of soil P (soil test) = 2.0 pounds per acre. 1 Baule unit of fertilizer P = 18.5 pounds per acre. 1 Baule unit of fertilizer P205 = 42.6 pounds per acre. 41 Table 10. Phosphorus requirement for onions grown on a Houghton muck, 1965. Fertilizer Requirement Soil P Test* (Equivalent Yield Pounds per Acre Pounds per Acre Percent P P205 4.8 50 41.2 94.8 9.6 75 30.9 71.1 14.4 87 20.6 47.4 19.2 94 10.3 23.7 24.0 97 0 0 *Bray P extractable. ._1 BaUlé unit Of 5011 P (8011 test) = 4.8 pounds per acre. .3 1 Baule unit of fertilizer P = 10.3 pounds per acre. 1 Baule unit of fertilizer P20 = 23.7 pounds per 5 acre. Table 11. Phosphorus requirement for potatoes grown on a Houghton muck, 1965. Fertilizer Requirement Soil P Test* Equivalent Yield Pounds per Acre Pounds per Acre Percent P P205 2.6 50 94.0 216.2 5.2 75 70.5 143.2 7.8 87 47.0 108.1 10.4 94 23.5 54.0 13.0 97 0 0 *Bray P extractable. l Baule unit soil P (soil test) = 2.6 pounds per acre. 1 Baule unit fertilizer P = 23.5 pounds per acre. 1 Baule unit fertilizer P205 = 54.0 pounds per acre. 42 Table 12. Calculated c values for onions and potatoes grown on a Houghton Mudk, 1963, 1964 and 1965. c values* Crop 1963 1964 1965 Onions 0.0265 -0.1679 0.0293 Potatoes 0.0163 -0.0129 0.0128 *Average of 8 values. Log (A—Y) = log A - .0870b + .0129 x (6) P - '64 Log (A-Y) = log A - .0627b - .0293 x (7) 0 - '65 Log (A-Y) = log A - .1170b - .0128 x (8) p - '65 *0 = onions, 1963; P = potatoes, 1963 From equations 3 through 8 the Baule units of fertilizer P were calculated, and the fertilizer P require- rnent for 97 percent maximum yield of onions and potatoes at various soil P levels were determined (Tables 8, 9, 10 and 11). The experimentally determined c values for 1964 were negative (Table 12). This is the result of the negative response of onions and potatoes to applied fertilizer P (Tables 1 and 2). For this reason the Baule units of soil and fertilizer P were not determined. The crops were hit by frost on June 2 and 16 and on August 28, 1964. This undoubtedly affected the growth and subsequent yields of both crops, particularly potatoes. Similar frost periods occurred in 1963 and 1965. Air temperatures of 32°F and 30°F occurred on June 21 and 22, 1963, reSpectively. This resulted 43 in lower potato yields. Frost also occurred on May 30 and August 3, 1965 with temperatures of 28°F and 31°F, respective- ly. Observations by Lucas* at the Michigan Muck Experi- mental Farm have indicated that onion seedlings can with- stand temperatures as 1ow as 25°F. The modified Mitscherlich concept, as proposed by Bray (8a), claimed that crop yields Obey the percentage sufficiency concept of Mitscherlich for such elements as P and K which are relatively immobile in the soil. This concept was based on Bray's nutrient mobility concept which states that as the mobility of a nutrient in the soil decreases, the amount of that nutrient needed in the soil to produce a maximum yield (the soil nutrient requirement) increases from a variable net value (determined principally by the magnitude of the yield and the optimum percentage composition of the crop) to an amount whose value tends to be constant. The magnitude of this constant is independent of the yield of the crop provided the kind of plant, planting pattern, and rate and fertility pattern remain constant and that similar soil and seasonal conditions prevail. The variations among the C1 and C values for both onions and potatoes over the 3-year period may possibly reflect seasonal variations as well as differences resulting from soil sampling, fertilizer application and harvesting of the crops. *Personal communication. 44 The fact that the crops were subjected to frost damage at different intensities and at different stages of growth may have differentially retarded the growth of the plants with a subsequent effect on the yield of the crops. Too, this may have affected the plants, to a greater or lesser extent, growing under inadequate or adequate P levels. The variation that occurred between the Cl values obtained for potatoes and onions (Table 6) is to be expected since.this constant is mainly a function of the rooting pattern of the crop. As shown in Tables 8, 9, 10, and 11, the P require- ment for various yield levels of both onions and potatoes was less on the virgin muck (1963) than on the muck that had been cultivated for 3 years. The work of Kaila (37a) and Paul (60) has explained that mineralization of the organic P present in a virgin organic soil is more rapid than that of a cultivated soil. This would increase the amount of soil P available to the growing p1ant_and subsequently decrease the need of fertilizer P. The total, inorganic and organic P status of virgin and cultivated Houghton muck is shown in Table 13. An increase in the total P of all soils increased with the application of fertilizer P. The inorganic P content of the virgin soil was less (293 ppm) than the cultivated and fertilized soils. The organic P content of the cultivated soils did not vary appreciably, except for the soils receiving an annual application of 88 pounds of P per acre. 45 However, the percent organic P decreased with increasing levels of fertilizer P, being highest on the virgin soil (75 percent) and lowest (50 percent) on the soils receiving 88 pounds of P per acre for a 3—year period (Table 13). The yield of potatoes in 1963, as shown in Table 5, were about equally as good on the non-P fertilized plots as those receiving 11, 22, and 44 pounds per acre. The slight increase in yield (14 cwt. per acre) resulting from the 11 pounds of applied P per acre appeared to be a "starter" effect. The plant composition values for the potato petioles taken in 1963 show that the percent P did not vary appreciably between the plots receiving no P and those receiving up to 88 pounds per acre (Table 5). This possibly indicates that plants growing on the PO plots were receiving adequate P for optimum yields even though the extractable Bray Pl phOSphorus was low (9 pounds per acre) and that available soil P was the result of the mineralization of organic P to inorganic P. Nutrients including sucrose were added to all soils before incubation to assure a high level of microbial activity. Changes in inorganic P from one sampling to the next were quite variable. Nevertheless, the linear regressions in Figure 12 show that the general trend was for inorganic P to increase with time. The average increase over an 8-week incubation period was about 100 ppm in virgin muck. In cultivated muck, the rate of release was considerably less. There was no evidence that the increase was dependent upon the amount of soluble P applied. 46 Table 13. Total, inorganic and organic phosphorus status of virgin and cultivated Houghton muck. Parts per million P Percent Treatment* Total Inorganic Organic Organic P Virgin 1156 293 863 75 No Fertilizer 1413 460 953 67 PO 1425 500 925 65 P1 1407 490 917 65 P2 1464 548 916 63 P3 1584 625 959 61 P4 1736 874 862 50 *For a 3-year period. Table 14. Changes in the inorganic phOSphorus content of incubated virgin and cultivated Heughton mucks. Incubation period Treatment weeks Soluble P Added O l 2 4 6 8 (ppm) ppm PH 0‘ 230 244 300 275 363 330 ‘Virgin Soil* 25 252 320 324 338 420 359 50 302 346 352 371 400 422 200 444 459 448 447 556 552 400 640 602 716 641 708 738 Cultivated Soil* 0 618 617 639 571 692 607 400 1061 929 1028 975 1108 990 *Virgin soil refers to sample 18; cultivated soil refers to sample 4 which received 264 pounds of P over a three-year period. **Extractable in 6‘N HC1. Inorganic PhOSphorus -— ppm 47 1100} O = 1000- o r 0.78 (400P) 9007 = 0.52 (4009) = 0.78 (OP) = 0.83 (200P) = 0.84 (SOP) 0.84 (25P) = 0.85 (OP) A 0 cultivated soil 200 1 Virgin so1l 100 - U V V V I- ’ 0 i 2 3 4 5 6 7 8 Incubation time -- weeks Figure 12. The effect of incubation on the release of inorganic phosphorus on virgin and cultivated Houghton muck soils. 48 The extensive release in 8 weeks from virgin muck indicates that organic P in this soil when first brought under cultivation may be a significant source of P for plant growth. Thus, the rate of mineralization of organic P, may have been sufficient to adequately supply inorganic P to the plants during the 1963 growing season. This would account for the lack of response of potatoes to fertilizer P. The work of Larsen et a1 (39, 40, 41) has shown that the sesquioxides present in organic soils play an important role in the fixation of soil P Larsen also indicated that organic soils extracted with distilled water gave a better measure of plant available P than dilute hydro- chloric acid, and that very little of the inorganic P present in virgin mucks is held in an insoluble form. The increase in soil fixation of P with an increase in its sesquioxide content has been shown by Larsen et a1 (41). Muck soils that have been cultivated for long periods of time have higher sesquioxide contents than virgin soils or soils that have been subjected to less cultivation. These phenomena are important in determining the fertili- zer efficiency of phOSphorus. As shown in Tables 9 and 11, to obtain 97 percent maximum yield of potatoes the phosphorus requirement increased from 74 pounds per acre in 1963 to 94 pounds per 49 acre in 1965. It is known that for many mineral soils, due to their high P fixing capacities,the large amounts of fertili- zer P are required to obtain optimum yields, and yet, only 20 to 30 percent of the amount applied is recovered. It is believed that the same conditions exist for organic soils but the extent to which the applied P is fixed and the percentage of applied P recovered is not thoroughly understood. These data have indicated that the P fertilizer requirements of virgin muck are apparently different from those which have been cultivated. The incubation study also indicated that the Virgin soil possessed a greater potential to release P. The virgin soil represents an extreme case where both physical and chemical changes have been less altered than that of cultivated muck soils. The latter group of muck soils have undergone gradual changes as a result of cultivation and management. The leaching study (Table 15) was initiated to study the effects of varying periods of cultivation and P treatment on the fixation of soil applied P32. As shown in Table 15, the soils that were cultivated for 3 and 25 years fixed more P32 than the virgin muck. The P32 obtained in the water leachate from the cultivated soils was only one-fifth to one-third of that obtained in the virgin soil leachate. A comparison of the 3—year .IB" 50 cultivated soils shows that the mucks receiving a total of 264 pounds of P per acre fixed less P than the non-fertilized soils. Also, the 25—year cultivated muck soil fixed more of the applied P32 than either of the soils that were culti- vated for three years. It is also obvious that most of the applied P32 was retained in the soil since the counts per minute of the water leachate were quite low. An interesting point is how tight the P is held by the reSpective soils. According to pre— liminary measurements wherein 100-m1 fractions of the water leachates were measured, the applied P32 was removed with a nearly constant rate. The average rate of P32 removal from the virgin soil was higher than that from the cultivated soils. The .05 N HC1 extract of the applied P32 shows a 27-fold increase in the retention of P32 by the 25-year cultivated soil over the virgin muck (Table 16), while a lO-fold increase in P32 retention over the same soil was obtained for the 3-year cultivated muck that had received a total of 264 pounds of fertilizer P per acre. As shown in Table 16, the increase in P32 retention by the 3—year cultivated soil receiving 264 pounds of P per acre over the muck that had been cultivated for 3 years but had received no fertilizer P appears to be due to the difference in the amount of applied P. It appears that the fertilizer P efficiency in 51 Table 15. The effect of soil cultivation and phos horus treatment on the retention of applied P 2 on a Houghton muck using water as the extractant. Radioactivity of P32 Cultivated period Total P applied in water leacheate* Years Pounds per acre Counts per minute 0 (virgin) 0 5046 3 0 1202 3 264 1706 25 high rates annually 928 *Obtained by taking half the leachate (1000 ml) to dryness. Table 16. The effect of soil cultivation and phosphorus treatment on the retention of applied P 2 on a Houghton muck using .05 N HC1 as the extractant. Radioactivity of P32 Cultivated Period Total P applied in .05 N HC1 leachate* Years Pounds per acre Counts per minute 0 (virgin) 0 24,356 3 0 3,162 3 264 2,234 25 , high rates annually 900 *Obtained by taking half the leachate (1000 ml) to dryness. 52 muck soils would differ depending upon the extent of cultiva— tion and previous P treatments. Accordingly, the reSponse of crops to fertilizer P would also change. GENERAL DISCUSSION The method of determining organic P is based on that proposed by Mehta (55). Several steps, however, have been modified in order to adapt it to organic soils. It is still a combination of acid pretreatment and alkaline extraction. The organic soil samples were extracted with lZIN HC1, and due to the coagulated slurry that was found at the bottom of the acid extract after standing for a few days, a comparison was made between 6.N HC1 and 12.3 HC1. The following soils were extracted by the three methods indicated below: 1. Add 10 ml of 12‘N HC1 to 1 gm of soil and heat on hot plate for 10 minutes. Add additional 10 ml of 12.3 HC1 and let stand for 1 hour at room temperature. 2. Add 20 ml of 6.3 HC1 to 1 gm of soil and heat on steam plate for 10 minutes. Add additional 10 ml of 6.H HC1 and let stand for 4 hours. 3. Add 10 ml of 6.N HC1 to 1 gm of soil and heat on steam plate for 10 minutes. Add additional 20 ml of 6.3 HC1 and let stand for 4 hours. The results shown in Table 17 indicate that the amount of P extracted by the three methods are in good agreement, and, 6.3 HC1 appeared acceptable. 53 54 In addition, the final acidity of the extract was considered. The use of 20 m1 of 6 N HC1 and 90 ml of 0.5 .E NaOH provided an acidity that assured one hundred per- cent flocculation of the humus (23). Since organic soils contain larger amounts of organic matter than mineral soils, it was necessary that the samples be treated as plant material in the perchloric acid digestion. The mixture was pretreated with 10 m1 of concentrated HN03, and°then digested with 5 m1 of 72 percent perchloric acid. In the process of P measurement, the acidified solution was brought to pH 3 which causes the formation of Fe(OH)3. A small amount of citric acid, based on previous studies, was added to prevent this tendency (74, 76). Pre- liminary tests have shown that the addition of this organic acid will not adversely affect the results. Many researchers believe that available forms of P can be released from organic soil compounds due to extensive microbial activities. Incubation studies were carried out, therefore, to evaluate the rate of mineralization of organic to inorganic P. Some doubt was shed on the massive soil incubation method, which was used in a large number of previous studies. The results obtained from the small amount of incubated soil that was periodically taken from the larger amount of soil for the measurement of P. However, at least two factors had tO be considered: First,if the nutrients were not well distributed through the bulk of the soil, there would be no 55 way to insure that the smaller aliquots were homogeneous and good enough to represent the whole sample. Second, it was difficult to handle the wet soil sample and weigh it on a dry-weight basis. If the sample was air-dried, the incuba- tion period was ultimately prolonged. To obtain a favorable condition for the incubation of a one-gram soil sample, a 10 ml flat-bottom test tube was chosen to facilitate a 1:1 surface to volume ratio and of uniform depth. The moisture was maintained at a satis— factory level with the aid of polyethylene paper. Loss of moisture at 30°C after eight weeks only amounted to 10 percent (Table 18). After the incubation period, the microbial activity was subdued by the addition of 10 ml of 6.N HC1. The pro— cedure previously described was employed for the measure- ment of P with the following exception: the first 10 ml of 6.N HC1 was heated in a water bath and alkaline extraction for the total P was omitted since there would be no change in the total P content of the soils (42). Inorganic P measurements employing this technique were carried out in triplicate. The samples were arbitrari- ly numbered to prevent bias. Good reproducability was obtained (Tables 4 and 5 in Appendix). 56 Table 17. The evaluation of inorganic phosphorus on three Houghton muck soils by three methods. Partsgper million P Extraction Sample 1 Sample 2 Sample 18* 10 ml lZ‘N HC1 + 10 ml 12.3 HC1 332 462 250 20 ml 6.§ HC1 + 10 ml 6_N HC1 310 462 304 10 ml 6.3 HC1 + 20 ml 6.3 HC1 332 490 268 *Sample 1 virgin (non-cultivated) Sample 2 = virgin (cultivated) Sample 18 = virgin (non-cultivated) Table 18. Moisture loss from an incubated Heughton muck contained in a small test tube and covered with polyethylene paper. Incubation period Weeks Moisture loss 1 2 4 8 Loss in weight (gram) 0.03 0.063 0.108 0.213 Loss in percentage 1.5 3.2 5.4 10.2 Moisture loss is the average value for weight decreases of 21 test tubes. S UMMARY AND CONCLUS IONS Field and laboratory investigations were carried out to correlate the response of onions and potatoes with native and applied fertilizer phosphorus, and to evaluate the importance of organic phosphorus as a source of avail- able inorganic phOSphorus to plants grown on newly reclaimed Houghton muck. The results can be summarized as follows: 1. The response of potatoes grown on a virgin Houghton muck, to applied fertilizer P was less than that of onions. 2. The depression in potato yields at high levels of applied fertilizer P may possibly be associated with a decrease in plant uptake of zinc. The potato tissue obtained from the plots receiving 88 pounds of P (200 pounds of P205 per acre) contained 33.3 percent less zinc than those obtained from the plots receiving no P. 3. Baule units of soil and fertilizer P were obtained for onions and potatoes according to the following equation: log (A-Y) = log A - c b - cx 1 l Baule unit of soil P for onions = 4.1 pounds per acre (1963) l Baule unit of fertilizer P for onions = 11.9 pounds per acre (1963) 57 58 l Baule unit of soil P for onions = 4.8 pounds per acre (1965) l Baule unit of fertilizer P for onions = 10.3 pounds per acre (1965) 1 Baule unit of soil P for potatoes = 2.0 pounds per acre (1963) l Baule unit of fertilizer P for potatoes = 18.5 pounds per acre (1963) l Baule unit of soil P for potatoes = 2.6 pounds per acre (1965) l Baule unit of fertilizer P for potatoes = 23.5 pounds per acre (1965) The calculated cl values for onions and potatoes in 1963 and 1965 were as follows: Onions - .0732 and .0627, respectively. Potatoes - .1470 and .1170, respectively. The calculated c values for onions and potatoes in 1963 and 1965 were as follows: Onions — .0265 and .0293, respectively. Potatoes - .0163 and .0128, respectively. An increase in the total P content of all soils was obtained with the application of fertilizer P. The inorganic P content of the virgin soil was less than the cultivated and fertilized soils. The percent organic P decreased with increasing levels of fertilizer P, being highest on the virgin soil (75 percent) and lowest (50 percent) on the 10. ll. 12. 59 soils receiving 88 pounds of P per acre for a 3-year period. The incubation studies indicated that the virgin Houghton muck may be a source of P for plant growth. During the 8—week incubation period the inorganic P increased by approximately 100 parts per million. There was no evidence to show that the increase in inorganic P was dependent upon the amount of applied P. The studies with radioactive P indicated that the cultivated mucks retained more applied P32 than the virgin mucks. Water leachates from the 25-year cultivated muck revealed a 5-fold increase in P32 retention over the virgin soil while a 27-fold increase in retention of this element was obtained when the same soils were leached with .05 N_HC1. The data suggest that the efficiency of fertilizer P in muck soils would differ depending upon the extent of cultivation and P treatments. Accordingly, the response of crops to fertilizer P would also change. LITERATURE CITED 1. Aslying, H. C. 1954. Yearbook, Roy. Vet. Agr. Coll. Copenhagen, Denmark. 2. Auten, J. T. 1922. The organic phosphorus content of some Iowa soils. Soil Sci. 13:119-124. 3. Barthlomew, W. V., and C. A. I. Goring. 1948. Microbial products and soil organic matter: I. Some characteristics of the organic phosphorus of microorganisms. Soil Sci. Soc. Am. Proc. 13:238-241. 4. Bertramson, B. R., and R. E. Stephenson. 1942. Comparative efficiency of organic phosphorus and of superphosphate in the nutrition of plants. Soil Sci. 53:215-216. 5. 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Studies on organic phosphorus compounds in soil: Isolation of inositol. Soil Sci. 50:81-88. APPENDIX 69 Table l. The relationship between soil treatment and Bray P1 extractable phOSphorus, 1963, 1964 and 1965. Onions Potatoes Pounds per acre Pounds per acre Year Treatment* BloCk 1 Block 2 Block 1 BloCk 2 PO 6 11 6 11 P 6 12 6 12 o P 7 9 7 o 1963 P1 8 6 8 6 P2 11 8 11 P3 8 12 8 12 P 8 14 8 14 4 PO 9 29 9 29 PO 6 36 6 36 PO 6 41 6 41 1964 P1 10 20 10 20 P2 16 10 16 10 P3 30 11 30 11 P4 12 29 12 29 PO 9 11 10 3 P 9 6 7 3 o P 10 3 4 o 1965 P1 9 9 6 7 P2 10 6 9 3 P3 14 6 .11 9 P4 30 36 27 15 P * of P1' P2: P3 and P4 designate 0, 11, 22, 44 and 88 pounds of phosphorus per acre, respectively. 70 Table 2. Yields of onions and potatoes grown on a Houghton muck, 1963, 1964 and 1965. Onions Potatoes th. per acre th. per acre Year Treatment* Block 1 Block 2 Block 1 Block 2 PO 434 537 269.5 237.5 PO 400 546 270.5 229.3 PO 565 502 280.9 246.4 1963 P1 562 517 283.2 256.2 P2 589 603 292.7 244.4 P3 557 561 296.0 236.2 P4 631 647 240.3 215.8 PO 361 348 232 237 PO 387 395 226 194 PO 458 546 229 243 1964 P1 324 388 189 265 P2 364 419 252 .226 P3 334 332 242 302 P4 397 356 186 192 PO 381 507 327 297 PO 311 515 221 233 Po 387 398 201 161 1965 P1 590 688 288 314 P2 644 657 345 298 P3 664 637 360 350 P4 673 521 346 281 *PO’ P1; P2, P3 and 88 pounds of phosphorus per acre, respectively. and P4 designate 0, 11, 22, 44 71 Table 3. Total, inorganic and organic phosphorus in virgin and cultivated HOughton mucks. Total Inorganic Organic Treatment ppm P Virgin 1156 293 863 No fertilizer 1413 608 805 PO 1400 560 840 PO 1413 928 847 PO 1356 463 950 PO 1400 530 939 PO 1469 625 813 PO 1513 528 828 P1 1413 543 870 P1 1400 530 870 P2 1469 450 950 P2 1456 860 828 P3 1438 463 1006 P3 1731 565 891 P4 1775 533 980 P4 1688 625 1106 72 Table 4. Inorganic phosphorus content of virgin and cultivated Houghton mucks prior to incubation. i:2§::* Ppm P added** Inorgggic P 1 (V) 0 230 2 (V) 0 230 3 (V) 25 250 4 (V) 25 254 5 (V) 50 304 6 (V) 50 300 7 (V) 200 446 8 (V) 200 441 9 (V) 400 640 10 (V) 400 640 11 (C) 0 616 12 (C) 0 620 13 (C) 400 1044 14 (C) 400 1078 *"V" designates virgin muck; "C" designates cultivated muck;samp1es run in duplicate (e.g., 1 and 2, 3 and 4, etc.). **300 ppm of N and 20,000 ppm of sucrose were added prior to incubation. 73 Table 5. Inorganic phosphorus content of virgin and culti- vated Houghton mucks after 1, 2, 4, 6 and 8 weeks incubation. Incubation period Samp1e* ppm P added 1 2 4 6 8 number PPm~P 1 (V) 0 274 .300 290 366 330 2 (V) 0 248 294 254 360 330 3 (V) 0 240 300 260 374 316 4 (V) 25 320 298 336 420 370 5 (V) 25 320 286 350 412 300 6 (V) 25 300 350 340 420 348 7 (V) 50 324 322 368 400 380 8 (V) 50 350 334 400 404 432 9 (V) 50 342 370 374 400 412 10 (V) 200 438 448 466 586 552 11 (V) 200 480 454 474 560 552 12 (V) 200 500 448 480 552 488 13 (V) 400 600 716 652 672 634 14 (V) 400 604 716 678 716 776 15 (V) 400 590 728 630 ~700 700 16 (C) 0 622 640 574 700 660 17 (C) 0 636 638 592 732 614 18 (C) O 612 764 576 684 600 19 (C) 400 926 950 978 1116 1032 20 (C) 400 986 1030 1032 1150 1000 21 (C) 400 932 1026 972 1100 980 *"V" designates virgin muck: "C" designates cultivated muck. Samples run in triplicate, e.g., 1, 2, 3 or 4, 5, 6, etc. "I17111111111111"11111“