o cl c-oflv!‘.’\'”o,.. II‘ RESIDUAL AND CUMULATIVE EFFECTS, : _; ' -_ -_ : - . 0F mmsm APPLéED m ASANDY LOAMQSOIL . :i -' 4 ~ ‘ Thesis for the Degree of. M. 8?. * MICHIGAN STATE UNIVERSETY' .EAMESL STARR 1§70 m:- 1Hs-‘sm ' \ LIBRARY Michigan State 1 University (4 ABSTRACT RESIDUAL AND CUMULATIVE EFFECTS OF NITROGEN APPLIED TO A.SANDY LOAN SOIL By James L. Starr Residual and cumulative effects of three nitrogen carriers. at three rates of application were studied on a sandy loam soil while growing corn (£32 E§l§)- The nitrogen carriers urea. NHQNOB. and NH3 were applied at zero, 8“, 168. and 252 kg/ha with one to four annual applications. Yield benefits from one annual application were observed for three years. These residual benefits were increasingly significant with the two higher rates of application. Upon repeated annual applications of nitrogen fertilizers. a distinct portion of the total response could be identified with each year of application. Cumulative residual benefits increased with rate of application and with carriers in the order urea urea>N113. Repeated annual additions of nitrogen at the higher rates of all three carriers resulted in soil pH values below 5.5 for portions of the growing season. Maximum retention of nitrogen in the soil after three annual nitrogen applications occurred at the 84 kg/ha rate. Maximum retention of carbon occurred at the 168 kg/ha rate. The net effect of increasing carbon retention was a widen- ing of soil CPN ratio from 12.5:1 in control plots to 15:1 for the 168 kg/ha rate. After three annual applications of 252 kg/ha. both soil carbon and soil nitrogen were reduced below the level in the controls. The C:N ratio declined abruptly to 13.531. These results were taken as evidence that fertilizer nitrogen inputs in excess of crop removal were promoting net mineralization and depletion of soil organic nitrogen. A highly significant quadratic relationship between soil carbon and nitrogen was obtained over the 160 plots in the experiment. This relationship was taken as evidence for effects of treatment on the active organic fraction, i.e. on organic materials most recently added to the soil. The first derivative of this function indicated that carbon and nitrogen were being immobilized in a ratio of 30:1 in control plots and 15:1 in plots receiving the highest nitrogen rates. At the highest NHuNO rate, nitrogen applied in excess 3 of calculated crop removal could not be accounted for to a depth of five feet and was assumed lost by leaching or denitrification. VOlatilization losses from surface applied urea were probably responsible for smaller yield responses to residual and current applications of this carrier as compared with NHB' RESIDUAL.AND CUMULATIVE EFFECTS OF NITROGEN APPLIED TO A SANDY LOAN SOIL B! James Li'Starr A THESIS Submitted to Michigan State University in partial fulfillment of the requirement for the degree of MASTER OF SCIENCE Department of Crop and Soil Sciences 1970 - —‘ 3 f. ._ N E) 9n c? 6 C. p k. \1 {3(2) ACKNOWLEDGMENTS The author is grateful to Dr. A. R. Holcott for his continued availability and the giving of encouragement, instruction and advise through all phases of the production of this thesis. This has been an invaluable learning experience that would not have been possible except for the time-consuming interaction between Dr. Wolcott and myself. - This experiment was initiated by Drs. H. D. Foth and J. F. Davis with financial support from the Michigan Agricultural Ammonia Association. Use of the Michigan State University computing facilities was made possible through support. in part, from the National Science Foundation. 11 TABLE OF CONTENTS Page INTRODUC.TION O O O O O O O O O O O O O 0 O O O O O O 1 LITEMT URE REVI E w = O 0 O O O O O O O 0 O O O O O O O O 3 The Effect of Inorganic Nitrogen Application on the Uptake of Soil Nitrogen . . . 7 The Effect of Inorganic Nitrogen Application on 8011 1111111118 0 o o o o o o o c o o o o o o 8 Greenhouse Studies . . . . . . . . . . . . . 11 Nitrogen Losses From the Soil . . . . . . . . . 13 Soil Nitrogen and Corn Growth . . . . . . . . . 21 EXPERIMENTAL PROCEDURES AND METHODS OF ANALXSIS . . 22 Field Treatments 0 O O O O O O O O O O O O O O 22 $011 sapling o o o o o o o o o o o o o o o o o 23 8°11 TeSting O O O O O O O O O O O O O O O O 25 Statistical Analysis . . . . . . . . . . . . . 26 RESULTS AND DISCUSSION 0 O O O O O O O O O O O O O O 28 Yield History . . . . . . . . . 28 Sources of variation in 1967 and. 1968. . . . 31 Residual Effects of Nitrogen on Corn Yields . . 34 Cumulative Effects on Corn . . . . . . . . . 36 Incrementation of Residual Response . . . . . . 40 Relative Efficiency of Carriers . . . . . . . . 45 Forms of Residual N in Soil . . . . . . . . . . 50 KJeldahl N in the soil . . . . . . . . . . 50 Crop residues . . . . . . . . . . . . . . . 59 Mineral nitrogen . . . . . . . . . . . . . 62 Other soil sources of N . . . . . . . . . . 70 Effects on Soil pH . . . . . . . . . . . . . 71 Effects on Soil Calcium and Magnesium Levels . 77 Effects on Soil Phosphorous and Potassium Levels 0 O O O O O O O O O O O O O O O O O O 81 SUMMARY AND CONCLUSIONS . . . . . . . . . . . . . . 85 BIBLIOGI‘UDPHY O 0 O O O O O O O O O O O O O O 0 O O O 92 APPENDIX 0 o o e o o c o o o o o o o '0 o o o o o 98 Table 1. 2. 9. 10. 11. 12. 13. 14. 150 LIST OF TABLES Basal fertilizer and management . . . . . . . . Corn yields over a four-year period in relation to residual and cumulative effects of fertilizer nitrogen . . . . . . . . . . . . Monthly rainfall. average temperatures, and deviations from the norm . . . . . . . . . Approximate significance probabilities of F in 1967 for variance associated with experimen- tal design categories . . . . . . . . . . . Approximate significance probabilities of F in 1968 for variance associated with eXperimen- tal design categories . . . . . . . . . . . Absolute increases in yields of corn over controls which received no nitrogen . . . . Relative increases in yields of corn eXpressed as percent of maximum for carrier or rate of nitrogen . . . . . . . . . . . . . . . . Relative yield responses incremented over years of N application . . . . . . . . . . . . . Soil nitrogen in November 1967 . . . . . . . . Soil carbon in November 1967 . . . . . . . . . Soil CxN ratios in November 1967 . . . . . . . Soil carbon, nitrogen and C:N ratios in relation to annual rates of N application . Nitrate nitrogen in soil sampled August, 1968 . Distribution of ammonium and nitrate with depth on August 14, 1968 . . . . . . . . . Effects of nitrogen carrier and rate of application on soil pH . . . . . . . . . . iv Page 24 29 30 32 33 35 41 42 51 53 55 58 63 64 72 LIST OF TABLES (cont.) Table Page 16. Extractable Ca and Mg in soil sampled November. 1967 o o o o o o o o o o o o o o o 78 17. Effects of nitrogen carrier and rate of application on the November 1967 lime requirement . . . . . . . . . . . . . . . . 80 18. Extractable K in soil sampled November. 1967 and August. 1968 . . . . . . . . . . . . . . 82 19. Extractable P (Bray P ) in soil sampled November, 1967 ana August. 1968 . . . . . . 83 LIST OF FIGURES Figure Page 1. Cumulative effects of annual nitrogen applications on relative yields of corn in 1968 o o o o o e o o e o e o e o o o o c 37 2. Cumulative effects of annual nitrogen applications on corn ear weights in 1968 . 38 3. Cumulative effects of annual nitrogen applications on numbers of fertile stalks in 1968 O O O O O O O O O O O O O O O O O O 39 #. Residual and cumulative effects of N rates on 1968 yield increases over controls . . . 4h 5. Incremented responses of corn in 1968 to residual and current inputs of nitrogen from three fertilizer sources . . . . . . . #7 6. Immobilization ratios in relation to soil carbon and nitrogen contents . . . . . . . 57 7. Soil carbon, nitrogen and CzN ratios in relation to increasing rates of fertilizer N after three annual applications . . . . . . . . . 57 8. Corn yields on residual plots in 1968 in relation to soil N in November 1967 . . . . 60 vi INTRODUCTION Nitrogen efficiency and losses as related to plant growth have been of concern in agronomic research since 1877 when lysimeter studies of nitrate began at the Rothamstead Experimental Station (Russell and Richards, 1920). This problem is more than of academic interest. As is pointed out by Boawn. Nelson. and Crawford (1963), the efficiency with which the current crop utilizes nitrogen and the extent of carry-over into subsequent growing seasons is important for making good nitrogen fertilizer recommendations. Furthermore. as the price per pound of nitrogen goes down and the rate of fertilizer application increases. the potential for pollution of surface and ground waters through leaching of nitrate and for adverse residual effects on soil acidity are also becoming of increasing concern. There is a long history of attempts to identify forms of nitrogen in soils and in plants which could be used as a basis for controlling this nutrient for efficiency in fertilizer practice. In technologically advanced areas of the world. the objective of efficiency in 2 nitrogen use is now coupled with that of identifying criteria and practices which may be used for controlling -hazardous accumulations of nitrate in agricultural lands. The objective of the research reported here was to evaluate residual and cumulative effects of three nitrogen materials at annual rates up to 252 kg N/ha (225 1b N/Acre). .The experimental design permitted an estimate in the fourth year of carryover effects from each of three preceding annual applications. Major residual effects were expressed on the response of corn to the current year's nitrogen -input. Significant effects on soil pH and nitrate levels were noted. LITERATURE REVIEW The literature here reviewed is related to the residual characteristics of fertilizer nitrogen. A detailed survey of the mechanisms by which nitrogen is' lost from the soil is beyond the scope of this review. except as it is brought out in the papers dealing with nitrogen studies. Residual nitrogen studies have been carried out in a variety of ways. both in the field and in the greenhouse. One of the procedures for estimating residual nitrogen as reported by White (1957). Dumenil and Pesek (1958). and White and Pesek (1959). involved the determination of the rate of increase of nitrogen in cats with various rates of nitrogen applied the previous year. With three medium textured soils. 60. 120. and 180 pounds of nitrogen were applied to corn. The residual response represented a carryover of about seven percent of the nitrogen applied to corn the previous year at the 60 lb. rate and about 49 percent at the 180 lb. rate. In soil which had received the latter treatment. 88 pounds of residual nitrogen was found mainly in the form of nitrate at a depth of six to 21 inches. No appreciable quantities of residual ammonium were found. 4 A mineralization test showed that the effect of the residual nitrogen on nitrifiable forms of nitrogen in these soils was negligible. There was also a high correlation between effects of residual nitrogen and plant uptake of soil nitrate. The small amounts of nitrate in the surface layer. according to White (1957). improved the root growth and thus facilitated the utili- zation of residual nitrogen in the subsoil by the plants. In an earlier study by Pesek and Dumenil (1956). under Iowa conditions. the average residual carry-over from #0 to 60 pounds of nitrogen applied to corn. when measured with oats the following year. was about 25 percent. However. following wet seasons the residual effect was usually equivalent to less than a 20 percent carry-over of nitrogen. while following dry seasons it was in the neighborhood of 30 percent. Pesek and Dumenil conclude that the residual response in areas where the rainfall is 30 to 35 inches per year is likely to be of little importance past the second crop-year after application. In an experiment by Broadbent and Nakashima (1968). tagged nitrogen fertilizers were applied to pots in which an attempt was made to eliminate leaching and denitrification losses through a controlled watering system. When nitrogen was applied on the soil surface as ammonium nitrate and ammonium sulfate. the volatilization loss of ammonia ranged from 24 to 39 percent. However. when these were banded at a depth of 7.5 centimeters. volatile losses were negligible. 5 0f the various forms of nitrogen applied. the nitrate sources were decidedly superior to other forms with respect to efficiency of plant uptake by a sequence of sudan grass. tomatoes. and corn over a 31k day period. A comparison of plant uptake of tagged ammonium in ammonium nitrate versus tagged nitrate in ammonium nitrate. showed differences ranging from nine to 20 percent in favor of the nitrate. Since leaching and denitrification were carefully controlled. the extent of selectivity for nitrate over ammonium by the plants grown was likely greater than it would be under field conditions. A study with corn in a fine sandy loam soil by Boawn et al. (1963) showed an average residual response equivalent to #4 percent of the original ammonium nitrate applied during the first year of nitrogen removal. This percentage was expressed in terms of the current season's nitrogen application needed to produce the same amount of nitrogen uptake as by the residual crop. Residual nitrogen reaponse during the third year of plant growth was insignificant. Vista (1960) tells of an experiment in which nitrogen was applied at various rates to grass and to a sequence of crops. All the nitrogen removed in the subsequent crops was measured. without additional fertilization until all residual nitrogen was removed. Erosion and leaching losses were minimized by selection of experimental sites and by careful irrigation. The results were quite variable with seven to 50 percent total recovery on the fine textured 6 soils. One fine sandy loam yielded a total recovery of nearly 80 percent. Viets suggests that denitrification after rain or irrigation may have‘accounted for some of the loss. The effect of residual nitrogen is influenced by the kind of crop grown. according to the findings of Widdowson and Penny (1965). Their experiment employed an alternating wheat-potato rotation on a clay loam soil. Zero. 50. and 100 pounds of nitrogen per acre were applied to wheat. and zero. 75. and 150 pounds of nitrogen per acre were applied to potatoes. Nitrogen applied to potatoes always increased wheat yields the next year. The residue from 150 pounds of nitrogen for potatoes had the same effect as applying about 55 pounds of nitrogen to the following wheat crop. There was less carry-over effect in the following wheat crop when the wheat was topdressed with nitrogen. Potato yields were little affected by the application of nitrogen to the preceding wheat crop. The period of residual benefit from nitrogen fertilizer was just one year. in that there was no gain for either crop from nitrogen applied two years before. The findings of Clark (196“) agree with the findings of these investigators in that he found very little residual effect upon the yield of cotton from nitrogen two years after application. With zero to #00 pounds of nitrogen applied per acre. nitrogen uptake by the cotton varied considerably over the three-year period. 7 Nitrogen uptake the first year increased from 80 to 110 pounds as the application of nitrogen was increased from 100 to 300 pounds per acre. When the application was increased to 400 pounds per acre. the current year's nitrogen uptake decreased. Residual nitrogen taken up during the second year increasedeith each successive increase in the rate of application. until it equaled that taken up the first year at the 300 pound rate. At the 400 pound rate. the second year's residual uptake exceeded the first year's direct uptake. By the third year. uptake of nitrogen dropped to about 45 pounds per acre regardless of the rate of application. Apparently by the third year. the fertilizer nitrogen was lost from the soil through crop removal. leaching. volatili- zation or denitrification. or it had become a part of the organic fraction of the soil through immobilization. The Effect of Inorganic Nitrogen Application on Uptake of Soil Nitrogen The addition of fertilizer nitrogen will usually increase the uptake of soil nitrogen by the crop. This phenomenon has been noted in N15 studies by several investigators. with a number of explanations being given. Broadbent and Norman (1947) suggest that increased uptake of soil nitrogen with increased nitrogen fertili- zation may be due to a rise in the mineralization rate. resulting from a stimulation of the microflora by added mineral nitrogen. In sharp contrast with this explanation 8 is one given by Stewart. Johnson. and Porter (1963). who say that increased uptake of soil nitrogen could be expected if neither immobilization nor mineralization rates changed. simply by fertilizer nitrogen replacing soil mineral nitrogen in the immobilization pool. thus allowing more soil nitrogen to be available for plant uptake. According to Allison (1965). if crop growth is in- creased as applied fertilizer nitrogen is increased. there will be a corresponding increase in the size of the root system. The net result is that more nitrogen will be taken up by the plant. He notes that N15 studies are conducted under conditions of maximum exploitation of the available nitrogen supply. so higher recovery rates can be expected than under normal field conditions. The Effect of Inorganic Nitrogen Application on Soil Rumus The effect of added inorganic and organic nitrogen materials upon soil humus has been the object of much study. Allison (1955) summarizes some of the commonly accepted views by saying that soil humus has a CxN ratio of about 10 or 12 to 1. and that 25 to 35 percent of the initial plant carbon will remain to form humus regardless of whether inorganic nitrogen is applied or not. Thus Allison concludes that added nitrogen will not affect the soil humus very much. but will greatly affect crop growth. High nitrogen applications will often result in higher car- bon content. but this is due to the production of more 9 residues. not because inorganic nitrogen has resulted in the retention of more crop residue carbon. Since the nitrogen content of microbial protoplasm is about 3 to 12 percent. the C:N ratio of the added materials must be below 20 to 25. or about 1.5 percent nitrogen or greater. for any appreciable net mineralization of nitrogen (Harmsen and Kolenbrander. 1965). Jansson (1958) warns against being misled by the I'priming effect" of fresh additions of organic materials to the soil. These , priming effects according to Jansson. may result when an addition of energy-containing material. whether con- taining nitrogen or not. to the soil may extend and speed up cyclic transformations. This may result in a net mineralization greater than that of the untreated check and possibly. even in a net depletion of total soil organic nitrogen. Bingeman. Varner. and Martin (1953) in a study with C3“+ tagged additions of alfalfa insolubles and complete alfalfa. found that there was an initial increase in mineralization of native soil carbon. The greatest in- crease occured in the first two weeks. then a return to near normal mineralization rate. This in itself says nothing of the mineralization of soil nitrogen. According to Harmsen and Kblenbrander (1965). when starting with a high CzN ratio. the carbon is rapidly liberated and lost as 002 while the nitrogen is mainly retained in organic form until the energy per unit nitrogen 10 ratio has become sufficiently reduced to allow for an accumulation of inorganic nitrogen. Only from that moment onward is there a "net mineralization" of nitrogen. During the foregoing stages. the nitrogen of the original substrate may have been mineralized repeatedly. but there was no accumulation of mineral nitrogen. Such temporary. reversible mineralization can be designated as "primary mineralization". whereas the accumulation of inorganic nitrogen is the "net mineralization". Thus the CzN ratio of the added materials must be considered as well as the CzN ratio of the soil organic matter in predicting the net mineralization of soil nitrogen. Bartholomew. (1965) expresses both positive and negative ideas concerning the value of the CzN ratio. Positively. the C:N ratios reflect nitrogen immobilization and mineralization. In decomposition of organic residues. carbonaceous materials supply the major energy source for microorganisms. The nitrogen is assimilated as protein in microbial tissue as a function of the growth of the organisms concerned. Negatively. since the CxN ratio involves the normal errors of determination of both the carbon and nitrogen. it is often less reliable as an index of nitrogen immobili- zation than is nitrogen percentage. Furthermore. inter- pretations are frequently made which go beyond the under- standing of the actual chemical and biological mechanisms of immobilization in the decay process. ll Greenhouse Studies The efficiency of utilization of fertilizer nitrogen by plants in most greenhouse studies is about 85 to 90 percent in the first crop. The residual effect in terms of percent of the initial application is therefore lower than that usually reported under field conditions. In a six-year greenhouse study with tagged nitrogen on an infertile acid sandy loam soil. Jansson (1963) found that eight to 14 percent nitrogen losses occurred when part of the tagged inorganic nitrogen was still in the soil. Jansson proposed that this loss occurred through denitrification. He also found that once the nitrogen had been organically immobilized it was liable to a very slow net mineralization process. The plant availability of the organic and clay fixed nitrogen averaged about one percent of the fertilizer addition per year. When cats were harvested at maturity. nitrogen losses were confined to the year of addition. When the harvesting took place at early stages of growth. then losses also occurred during the second year. Broadbent and Nakashima (1965) have also shown that once inorganic fertilizer nitrogen is incorporated into the organic cycle in soil. it is remineralized only very slowly. The presence of growing plants on the soil during the period of nitrogen application resulted in more efficient 12 utilization of the fertilizer than where planting was delayed several weeks. regardless of whether straw was added or not. In an experiment by van der Paauw (1963). over a seven year period. the residual effect of nitrogen applied in the previous year averaged 5.6 percent of the effect of a corresponding fresh application. The residual effect of nitrogen not taken up in the previous crop averaged 13.5 percent. The results were similar with different crops and soils. The residual effect of nitrogen not removed in the first crop was related to rainfall during the intervening winter. As the November-toufebruary rainfall decreased from 10 to seven inches. the residual effect from nitrogen not accounted for in the first crop increased from two percent to 17 percent. legg and Allison (1967) conducted another greenhouse study in which 50 to 200 ppm of nitrogen was applied for cats. They investigated recovery of the nitrogen by the oats and a following crop of sudan grass. The residual nitrogen taken up by the first cutting of sudan grass. as a percent of the tracer nitrogen which was not removed by the previous crop. ranged from 10 to 41 percent and in- creased with the rate of application. Availability of residual nitrogen to a second cutting of sudan grass dropped to 4.5 percent of the remaining tracer nitrogen. 13 Nitrogen Losses From the Soil Nitrogen losses from the soil occur through erosion. leaching. volatilization of ammonia from plants and soil surfaces. microbial denitrification. and chemical re- duction of nitrite. In a brief review of nitrogen losses from the soil. it soon becomes apparent that the form of nitrogen loss that has been studied the most extensively is leaching. Leaching losses have been studied by use of lysimeters since 1877 (Russell and Richardson. 1920). Allison (1965) states that a general study of the data from lysimeters of the type commonly used. that is. shallow. filled-in lysimeters. seems to justify the conclusion that they do not serve as a satisfactory basis for judging the amount of leaching losses of nitrogen under field conditions. How- ever. he feels that they do bring out the importance of the various factors that affect the magnitude of leaching losses. These factors include the cropping system. soil texture. infiltration rate. and ease of water movement through a soil column. Benson and Barnette (1939) performed a series of leaching studies on four coarse-textured soils after application of several nitrogen sources. Sufficient quantities of water were applied to the test areas to provide three inches of drainage water at intervals of one. four. 10. and 21 days. They found that all the 14 nitrogen that was applied as nitrate was leached. while only one-third of the ammonium applied as ammonium nitrate was leached. The amount of urea leached as urea was dependent upon the time of leaching. with 35 percent removal one day after application and 16 percent when the leaching occurred four days after application. Ammonium nitrogen was retained efficiently until nitri- fication began. then both ammonium and nitrate nitrogen leached. Utilizing isotopic nitrogen. Owens (1960) was unable to account for an average of 33 percent of applied nitrogen two years after 120 pounds per acre had been applied as ammonium sulfate. This loss was assumed to have taken place via denitrification since the soils were maintained at field capacity. thus yielding anaerobic conditions in soil micro- pores. The leaching losses varied from five percent at 12 inches of rainfall over a five-month period to 20 percent at the 24-inch rainfall level. The amount of fertilizer in the soil at the end of the two-year period was 38 percent and was unaffected by the soil moisture treatment. Some guidelines as to the amount of leaching loss in relation to rainfall have been given by Gardner (1965). He notes that the distance which nitrate will move downward depends not upon total rainfall but upon the amount of rain- fall which actually passes through the soil. For this reason. correlation of nitrate leaching losses with rain- fall is not as direct as might be expected. This is 15 especially true under cropping conditions when plants are continually extracting water from the soil. Gardner pro- poses the use of excess rainfall over evapotranspiration to estimate the probability of leaching losses. Nelson and Uhland (1955) point out that the amount of rainfall which passes through the soil is not the only factor controlling the amount of leaching loss. Where percolation occurs. the amount of nitrogen leached from the root zone depends upon the amount of nitrate in the soil. the fertilizer applied. and the rate of formation of nitrate from ammonium. Among other things. this rate is dependent upon temperature. According to Nelson and Uhland. considerable nitrification can occur over a period of time. even at temperatures of 45°F. According to studies by Burns et al. (1965). nitrate formation may take place at considerably lower temperatures than 45°F. Their field data show that nitrification pro— ceeds rapidly in the early fall and that complete thermal inhibition does not occur until the soil temperatures approach freezing. The rate of nitrification however. declined rapidly below 50°F. in the fall. It commenced again rather abruptly when this temperature was reached in the Spring. Another factor controlling the amount and rate of nitrification is the availability of water. Fitts. Bartholomew. and Reidel (1955) found that nitrate production will take place over a fairly wide range of soil moisture conditions. One hundred centimeters of tension. or just 16 less than field capacity. provided the optimum moisture for the production of nitrate. Burns (1969) reports similar findings on a loess-derived silt loam. In the soil moisture tension range of zero to 15 bars. the maximum nitrate accumulation rates occurred at 0.1 bar. which corresponds to slightly more water than that held at field capacity. The importance of factors which control leaching in modifying the residual character of fertilizer nitrogen is apparent in the work of Pearson et al. (1961) in the Scutheastern United States. They report that fall-applied nitrogen was only 49 percent as effective as spring- applied nitrogen when measured by corn yields. In terms of nitrogen recovery. the relative effectiveness of fall vs. spring application was about 62 percent. Under similar conditions where 200 pounds of nitrogen per acre was applied to corn in the Spring. there was a large residual benefit to two succeeding crops during the follow- ing 16 months. Total recoveries of nitrogen amounted to 70 to 77 percent in three crops. Pearson et al. concluded that recoveries can be good even in humid regions. if the nitrogen is applied at a time when leaching is at a min- imum and when a crop is present to assimilate it. The amount of leaching that occurs in relation to rainfall has been examined by Harmsen and Kolenbrander (1965). They report that the vertical downward diaplace- ment of nitrogen in sandy soils at field capacity is about 45 centimeters per 10 centimeters of rainfall entering the soil. This figure drops to about 30 centimeters for soils 17 in which 20 to 40 percent of the particles are less than 20 microns in diameter. They conclude. that complete loss of nitrogen from permeable sandy soils may occur in humid climates even during normal winters. During the summer growing season. nitrate is seldom carried downward beyond the reach of plant roots except during unusually rainy periods. It may be assumed that any infiltration of water will result in some downward movement of nitrate and that later capillary movement will result in some upward movement within the soil (Wetselaar. 1961). It becomes important to ask how deep must nitrate move before "leaching" or actual nitrogen loss occurs. Any answer must consider rate and height of capillary rise and. thus. the texture of the soil profile. Wetselaar (1962) reported that the upward movement of nitrate in a clay loam was restricted to the top 18 inches of soil. This implies that any nitrate leached below this depth. in this soil. cannot be returned to the topsoil by capillary movement. If the root system of a given crop extends below this depth. then nitrate below 18 inches is not necessarily an economic loss. 0n the other hand. any nitrate leached below this depth and below the root zone of crops grown may be considered lost in terms of management and control. This nitrate will. undoubtedly reach the ground water and move to nearby lakes and streams. 18 Another important mechanism of nitrogen loss. especially in humid regions. is denitrification. Allison (1965) states that there are many opportunities for denitri- fication to occur under field conditions if nitrate or nitrite are present. In well-drained sandy soils. oppor- tunities for loss of nitrogen by microbial reduction are negligible. In fine textured soil. such losses may be large since oxygen deficiencies. due to poor drainage and/or rainfall in excess of infiltration. occur frequently for periods of several days. Allison (1963) discusses several mechanisms of chemical denitrification. One such mechanism is by chemical decom- position of nitrous acid. The nitrite ion (N02) is stable. The undissociated acid (RN02) is formed below ph 7.0 and is increasingly unstable with decreasing ph below 6.0. The dismutation in dilute solution may be written: 3hN02 —-) 2N0+HN03+H20 At higher concentrations the following reaction may be observed (Black. 1968): 2hN02——-) N0+N02+320 Black cites data from a Ph.D. thesis by D. W. Nelson in which nitric oxide according to the above reactions. appeared only when the atmosphere contained no oxygen. When small amounts of oxygen were present. nitric oxide was oxidized rapidly to nitrogen dioxide. Lack of oxygen would normally occur in saturated conditions. however. 19 water would be available to form nitric acid: 2 N02 + H20 —-) ENOB + RN02 Thus no loss of nitrogen dioxide was observed. except at extremely acid pH. Another chemical reaction that may be more important in terms of denitrification losses is the chemical reduction of nitrous acid by organic matter. The reaction seems to be related to the amount of lignin or of lignin-derived structures in the soil organic fraction. Brenner (1957) found that nitrous oxide was liberated upon treatment of humic acid or lignin with nitrous acid in the Van Slyke reaction. Black (1968) again reporting from Nelson's thesis. says that extracted soil organic matter. prepared lignins. and soils high in content of organic matter all promoted decomposition of nitrite. Clark and Beard (1960) in earlier experiments obtained similar findings and concluded that since nitrite is an intermediate in the microbial oxidation of ammonium to nitrate and since denitrification of nitrite by soil organic matter is a chemical reaction. then much of the naturally occurring volatile loss of nitrogen from aerobic soils occurs during the nitrification process. These losses may be large. according to Allison (1965). under conditions where considerable nitrogen as ammonia. urea. or green manure is added to acid sandy soils and ammonia oxidation is delayed at the nitrous acid stage. 20 The extent of nitrogen loss as a result of volatili- zation of ammonia is commonly negligible from soils having pH values less than neutral unless there is enough free ammonia to raise the pH locally. These losses increase with increasing pH and temperature and are greatest in soils of low cation exchange capacity (Pesek and Dumenil. 1956). The greatest loss through volatilization of ammonia occurs in most soils as anhydrous ammonia is being injected in soil. According to Pesek (1964) these losses occur when the soil is too wet or too dry. when the application is too shallow. or when the rate of application per volume of soil is too great. The latter may occur through the use of application furrows which are too far apart. Righ potential losses of nitrogen from urea fertilizers may occur if the urea is not mixed well with the soil. or if the surface becomes dry. Urea hydrolyzes rapidly in soil and forms high local concentrations of ammonium carbonate and high ph. The major inefficiencies of urea nitrogen occur through losses of ammonia as a result of surface soils drying out after hydrolysis has taken place on moist soils. These potential losses are magnified. according to Pesek (1964). by high pH. low base exchange capacity. and by high temperatures. 21 Soil Nitrogen and Corn Growth Predicting the soil's ability to supply nitrogen for the growth of crops has been the concern of researchers for a long time. A meaningful prediction cannot be made without considering the needs of the plant concerned in relation to its pattern of growth. Romaine (1965) cites data from Ohio showing quite clearly that the time of greatest nitrogen demand by the growing corn plant is during the time that the ear is being formed. These data show that 48 percent of the nitrogen uptake by corn occurs during the third month. and nearly 60 percent during the third and fourth months together. 0n the basis of field experience in Michigan. Lucas (1969) has proposed that 40 pp2m of nitrate-nitrogen in the plow soil represents a critical level for estimating the adequacy of nitrogen available to corn during the tasseling. silking and pollination period when its need for nitrogen is greatest. EXPERIMENTAL PROCEDURES AND METHODS 0? ANALYSIS Field Treatments In 1965 an experiment was initiated on the Soil Science Experimental Farm at Michigan State University to evaluate residual effects of three different nitrogen carriers at three rates of application. The experiment was designed to follow residual and cumulative effects over a four-year period on continuous corn (Egg mayg). Ten treatments. including the control. were replicated four times in a randomized complete block design yielding a total of 40 plots. Each plot was 14 by 100 feet (4.26 by 30.4 meters). To introduce variation in residual and cumulative effects of fertilizer nitrogen. these main plots were subdivided as follows: The entire plot received the nitrogen treatment the first year. Each succeeding year. 25 feet less of each plot received nitrogen until the fourth year. when each 100 foot plot was subdivided into four 25-foot sub-plots. These sub-unit treatments were randomized within blocks. but not within nitrogen treat- ments. The resulting systematic grid arrangement was taken into consideration in the analysis of variance. 22 23 Four rows of corn were planted on each plot. with the planter set to deliver 17.500 to 19.600 kernels per acre (43.000 to 48.000 kernels per hectare). Michigan 400 hybrid seed was used each year. Basal fertilizer and management were the same on all plots (Table 1). The nitrogen carriers were urea. ammonium nitrate. and anhydrous ammonia. Each nitrogen carrier was side- dressed on knee-high corn at the rate of 75. 150. and 225 pounds of nitrogen per acre (84. 168 and 252 kg/ha). The anhydrous ammonia was knifed in between each two rows. The urea and ammonium nitrate was spread byhand between each two rows and then mixed with the soil by shallow cultivation. The soil has been classified as a Hodunk Sandy Loam which belongs to the subgroup Ochreptic Fragiudalf (Schneider. Johnson. and Whiteside. 1967). See the Appendix for the description. Soil Sampling In November of the third year. 1967. and in early August of the fourth year. 1968. soil samples were taken. The soil sample for each plot consisted of 20 cores taken to a depth of 10 inches with a soil probe. The 20 cores were taken randomly between the center two rows and their fertilizer bands. They were passed through a one-fourth inch screen in the field and thoroughly mixed. Subsamples of the screened soil were spread 24 wwma “Aomnmmlov mmma .Aonummuov $3 £8-95 $3 «Snummuoa «Axlmuz w£\wxv aoao some Hoh.aoudaaphom Amman proa * mumbapazo .moas cum m02.52 m amendmedm . z pomficH n sash me a m eoecmm oom omnomuo unmam m mam . 30.3 S ”mono mom” opmbdpaso mansoo .moas mmmhfiodam m hash nozemzmmmonemedm mm ones 32 pooncH am mass m: a m ececmm om smusmnw weaned“ mom” .om sea £306 dozoan . Asoa ens ammoeeoam 0mm omuomuo Hash use nmuaaapnmc Hmmem coma.n%.>ozN m . one o H as >Hpaso masses .soas one 02:32 mmoade Hm mm mafia mmz poo 2H om «new we a m emezmm oom omuomuo ocean .3oam .mo%mzmomfl opra H30 oandod .ons was oz m2 mmoaomoam 3N «nah mmz poonna ma ones we a m emeesm oom .ommouuo pcmag .3oam Hm seam m a one o H meson. oaom\na omaunommnz maaommm paoaoosam ovum mmmmm o m a doom *amuaadpamc Hemmm : as as 0 open pnoaewdsaa use HoNAHthoh Hmmmm .H canoe 25 shallowly in five-pound paper bags laid on their sides on the drying racks in the soils barn. After one week the samples were ground to pass a two mm screen. The 1967 samples were placed in one-pint icecream cartons for storage while the 1968 samples were sealed in plastic bags for storage. Soil Testing The Michigan State University soil testing lab received approximately one-half of each sample for routine analysis. Soil pH. lime requirement. P. K. Ca. and Mg were determined on the November 1967 samples. The August 1968 samples were analysed only for pH. P. and K. The November 1967 samples were ground to pass a 100-mesh screen in preparation for the total nitrogen and total carbon analysis. A modified version of Bremner's micro-Kjeldahl method (Bremner 1965) for total nitrogen analysis was used to determine total nitrogen. A complete description of the modified semi-micro-Kjeldahl method may be found in the appendix. A high induction furnace. model 750-100 Leco. was employed for making the total carbon determination. A sub-sample of soil ranging from 0.1 to 0.2 grams was com- busted with about 1.0 gram of tin and 1.5 grams of iron catalyst. In this instrument. the carbon is converted into carbon dioxide which is then quantified by the change in 26 thermal conductivity which results when the carbon dioxide is mixed with oxygen. The August 1968 soil samples were exposed to ammonia fumes while on the drying racks. thus the ammonium values were all very high and quite meaningless. Nitrate deter- minations were made on these samples. using the Brucine technique by Greweling and Peech (1965). Statistical Analysis In the field. the nitrogen treatments were randomized within each block while the year of nitrogen application was systematically imposed across N treatments. The appropriate analysis of variance is that for a split plot with sub-units in strips (Cochran and Cox. 1957). V An arbitrary decision was made to consider year of application as the unit category and nitrogen treatment as the sub-unit. This choice has no effect on the analysis. since each main effect and treatment interaction is tested by the corresponding interaction with blocks. Two separate analyses were performed on each observed variable: (1) main effects and interactions with years of ten nitrogen treatments. including the control; and (2) factorial main effects and interactions of carrier and rate (nine treatments). and their first and second order interactions with years. The examined Use Computer from the by Ruble 2? factorial interactions with years were also by multiple correlation analysis. of facilities in the Michigan State University Center was made possible by support.in part. National Science Foundation. Programs developed et al. (1969) were used. RESULTS AND DISCUSSION Yield History Corn yields over the four-year period are given in Table 2. Year-to-year variation in yieldswas influenced by weather. Non-significant responses to applied N in 1965 were due to critical shortages of moisture from early spring through July (Table 3). There was some evidence that the deeper placement of NH3' which was injected. may have made more N available from this carrier at the higher rates than from the_other two. which were mixed with the surface soil by shallow cultivation. Nitrogen not used in 1965 was used effectively in 1966. Residual N carried over from 1965 was adequate for maximum yields and there were no significant differences for residual vs. current applications of N in 1966. Yields in 1966 were the highest for the four years of the experi- ment. This reflects a combination of favorable soil moisture. at planting time. more timely rains in June. July and August and generally higher temperatures in July and August in 1966 than in the other growing seasons. 28 29 00000\snv00.0 a 00\0n* Am.00 «0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 mg 000.0000 0.00 0.00 0.00 0.50 5.00 0.00 0.05 0.000 0.000 0.05 000 0.00 0.00 0.00 0.00 0.50 0.50 0.50 0.000 0.000 0.55 000 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.500 0.000 0.00 00 002 0.00 5.00 0.00 0.00 0.00 0.05 0.00 0.000 0.00 5.00 000 0.00 5.50 0.00 0.00 0.00 0.00 0.00 0.000 0.50 5.00 000 0 0.50 0.00 0.00 0.00 0.00 0.00 5.00 0.000 0.00 0.00 00 02002 0.55 0.05 0.00 0.00 0.00 0.00 0.00 0.000 0.000 5.00 000 0.05 0.00 0.00 0.00 0.50 0.00 0.00 0.000 5.000 5.00 000 0.00 5.50 0.00 0.00 0.00 0.00 0.00 5.00 0.00 0.00 00 0000 0.00 0.00 0.00 5.00 0.00 0.00 0.00 0.05 0.00 0.50 0 0000000 -----unguuunuuuuuuuuunuuuuun-*00\0n u---uuuuuuuuuuuuuunnnnuunuuu 0000 5000 5000 5000 00\00 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 000HQQ0 :o0000wwmmw,z no 0000» 2 0000000 000mlt N000 00m0 w0m0 wimmmulmmmwmmm :0wo0000 00N0H00000 no 0000000 ebdpdasaso 000 00000000 on 00000000 :0 UO000Q 0000u0so0 0 00>o 00H000 a0oo .N OHDdB 30 :000dm 002000: 0:00:00 0:» 00 30o: 0:» com: 00000 000 50o: 0:0 ao00 0:O0000>0Q 0 0o00000 300050 0020003 mmm 0:00:00 000m 000 ao00 0000 0050000080» 000 00000000 * 50.0 00.0 00.0 00.0 00.0 00000000 50:00 .000 0-0 .000 50:00 0000 00-00 0000 00:00 00: maO0000paooaoo 0000:00m .0000 .003054 on has 05.0 50.0 00.0 00.0 00.0- 00.0- 00.0 00.0 00.0- 05.0: 00.0- 00.0- .000 05.0 00. 0 00.0 00.0 .00.0 00.0 00.5 00.0 05.0 00.0 05.0. 00.0 0000 0.0- 0.0 0.0 0.0 0.0 0.0- 0.0- 0.0- 0.0 0.0 0.0- 0.0- .000 0.00 0.00 0.00 0.00 0.05 5.00 .0.00 0.00 0.00 0.00 5.00 0.00 .0000 0000 00.0 05. 0 00.0 00.0- 50.0- 00.0- 00.0 50.0- 00.0 00.0- 00.0- 00.0- .>00 00. 0 00. 0 00.0 00.0 00.0 00.0 00.0 00.0 05.0 05.0 00. 0 00.0 0000 0. 0 0. 0- 0.0- 0.0- 0.0. 0.0- 0.0 0.0- 0.0 0.0 0. 0- 0.0 .>00 0. 00 5. 00 5.00 0.00 0.00 5.00 0.00 0.00 0.50 0.00 0.00 0.00 .0000 5000 00. 0- 00.0 05.0- 50.0- 00.0 00.0- 00.0 05.0- 00.0 00.0 00.0- 00.0- .>00 00. 0 00. 0 00.0 00.0 00.0 00.0 00.0 00.0 00.0 00.0 00. 0 00.0 0000 0. 0- 0.0 0.0 5.0- 5.0: 0.0 0.0 0.0- 0.0: 0.0 0. 0 0.0- .>00 0.00 0.00 0.00 0.00 0.00 0.05 0.00 0.00 0.00 0.00 0. 00 0.00 .0000 0000 00.0 05. 0 00.0: 00.0 00.0 05.0- 00.0- 00.0- 00.0- 50.0- 00.0: 00.0 .>00 00. 0 50. 0 00.0 05.0 05.0 05.0 00.0 50.0 00.0 00.0 05.0 00.0 0000 5.0 0.0 0.0 0.0 0.0: 0.0- 0.0- 0.0 0.0. 5.0- 0.0: 0.0: .000 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 5.50 0.00 0.00 .0000 0000 .oom .>oz .000 .0000 .004 0050 0:50 002 .004 .00: .900 .000 000 000002 0 0*a0o0 on» ao0m 00o0000>00 000 .000500000500 0000000 .00000000 hanuno: .m 00900 31 Yields in 1967 and 1968 were limited by deficiencies of moisture and by abnormally low temperatures during cri- tical growth periods. Nevertheless. significant yield responses were associated with both residual and current year's inputs of fertilizer nitrogen. Sources of variation in 1967 and i968 Probabilities in the first column of tables 0 and 5 show that highly significant components of yield variation were associated with soil variation (replication). years of N application. nitrogen treatment and year 1 treatment interaction. subdivision of treatment variance in the factorial analysis indicates that treatment effects on yield in both seasons were associated with both carrier and rate. In 1968. a significant carrier 1 rate interaction also appeared. the number of fertile stalks (harvested ears) per hectare and the weight per car were strongly influenced by replication. year of N'application and treatment. Treatment effects on car weight included significant effects of both carrier and rate and a significant carrier 1 rate interaction. variance in total soil N in 1967 was not significantly associated with any design category (Table 4). In the case of soil c. variance approaching significance at five percent was associated with replications and years of N application in the plots which received the factorial N treatments. The ratio of carbon to nitrogen varied significantly in association 32 00:. mmm. 000. 00:. 500. 000. mmo. mum. 000. 0mm. 0 H o N 0 000. 500. 000. 000. 500. 000. 005. :00. 00m. 000. 0 a 0 000. 000. m0m. mmm. mno. :mo. 0mm. ,0mm. 000. omo. o H N 5mo. 000. 005. 05m. 050. 05m. m5n. mom. m00. 00m. 0 N o 000. 000. 000. 050. 000. 500. 000. ~00. 00m. 000. 00000 05m. 000. 005. 000. 050. 00:. 00m. 00:. 5mm. moo. 00000000 050. 000. 050. 500. 500. 000. 000. 000. 000. 000. 00000 000. 0 000.v 0 000v 000. 000. 000. 000. 500. 000. 000. 0000000000000 000000000 0000 00000 000000000 N50. 00m. 000. 000. 5mo. moo. 00m. m0m. emu. nooow. a H 0 :00. 00m. :00. 00m. 50m. 000. 000. 000. :m:. mooko 0000000009 000.. 000. 000. 000. 000. :00. 000. 000. 000. 000. 00000 000. moooJV.0oo. 000. 0:0. 500. 000. 000. 000. moo. 000000000000 000000000 0000 00000 02 00 0 0 .0000 0 \ 0 z .IIIAWIIIdmmMflIIII..00004 0000 m z o 000oa 00009 0 0000 000 000 0wwwo 00000000 nllmmmmmmmlmmmm I[, 000000000 000000 00 0000000000 000000 000000000000 0003 00000co000 0000000> 0cm 0000 00 0 0o 0000000000000 000000000000 000500o0004 .0 00009 33 0000000000 0000 000000005 000000 00 I 0000000000 mo00 000. 000. 000. 000. 000. 000. 000. 0 0 0 0 0 000. 000. 000. 000. 000. 000. 000. 0 0 0 000. 000. 000. 000. 000. 000. 000. 0 0 0 000. 000. 000. 000. 000. 000. 000. 0 0 0 000. 000. 000. 000. 000. 000. 000. 00000 000. 000. 000. 000. 000. 000. 000. 00000000 000. 000. 000. 0000.v_ 000. 000. 0000.v 00000 000. 000. 000. 000.. 000. 000. 000. 000000000000 000000000 0000 00000 000000000 000. 000. 000. 000. 000. 000. 0000.v 0 0 0 000. 000. 000. 000. 0000.v 000. 0000.v 0000000000 000. 000. 000. 0000.v 000. 000. 0000.v 00000 000. 000. 000. 000. 000. 000. 000. 000000000000 . 000000000 0000 00000 0 00m; 00 2-002 .0: 00% 00000w0000mM 00m mmwn 00000 00000000 0000000000 000000 000000000000 0003 0000000000 00000000 00% @000 :0 h 00 0000000909000 000000000w00 00080000004 .n 00908 34 with the replications, years and the second order interaction: years I carriers x rates. Other soil tests in Tables # and 5 reflected prin- cipally soil variation among replications. Residual effects on soil ph tended to be additive as N applications were repeated year after year. but a significant interaction between year of application and carrier was expressed in the November 1967 samples. A year I carrier interaction approach- ing significance was indicated for lime requirement. also. The level of available P in soils sampled during the growing season in 1968 reflected a highly significant year x rate interaction. Residual Effects of Nitrogen on Corn Yields Both in 1967 and in 1968. corn yields were increased significantly by residual effects of nitrogen applied in previous years (Table 6). Residual benefit from the 1965 applications was still apparent two years later in 1967 and three years later in 1968. Significant increases over the controls were asso- ciated with the higher rates of anhydrous NH3. Where a second annual application of nitrogen was made in 1966. the level of residual response in the 1967 and 1968 harvest years was increased substantially. A third annual application in 1967 resulted in additionally increased yields on residual plots in 1968. .Hoapsoo Hobo coaches“ pascamaswam a 902 a .psooama n pd economnav no: one Hoppoa mean on» an doasdasooom names .Amnma .saosdnv oosoamfiaswo mo mowsmm o...d sa.m :a.m sa.m :a.m m~.: m~.: m~.s am a ~.e¢ a m.nm a n.n~ a o.mH a o.m¢ a m.m¢ a :.md «mm a m.ms one m.a~ n m.:fi and o.m a n.m¢ nu o.mm pm o.HH mofl m pm a.m= 0 «.0H 9 o.mH Ham o.m a m.m: sane H.Hn and 0.: am 22 on H.Hm on m.mfi an :.a an 0.”: a o.on moon m.fi~ fine 3.“ «mm o :.om one s.mm n fi.mfi and m.m a m.mm one H.nm Ham m.m mos o a.om on H.o~ n a.Hfi and m.m a «.m: oeo m.mfl Ham N.m am mozsmz one m.mm pm H.6m p s.~H an» 5.0 m m.mm eons «.mm Haw m.n mmm one n.mm o m.mfi n H.0H «pm H.s m «.m: we «.mfl an n.o- mod a H.NH Ha o.~ an H.a Haw m.a a m.m: o H.ma Ham «.5 am «on: M» -uu-uu-u-u--u---unnnuuu-uuuuuuu-n a:\as n-uu:uuuuunuunuu-nuunnunuuuuu mom” mwma moma mood w2\wx mom” moms coma coma coma momfi mwmfi mood mom“ mom“ mead moma coaaqao soapooaa o 2 no made 2 aoanamo mom” momm Hue» awobadm somonpd: o: cobdeooa seas: maonpsoo Hobo shoe ho mvaouh ad mommonosd opsdomn< .w canoe 36 Cumulative Effects on Corn The cumulative responses of corn in 1968 to residual and current inputs of nitrogen are depicted graphically in Figures 1. 2 and 3. Actual control values. corresponding to 100 percent on each graph. were “1.2 hl/ha (Fig. i). 128 g/ear (n3. 2) and 22.000 ears/ha (Fig. 3). The last value indicates that only one-half of the planted population survived or obtained sufficient nutri- ment to produce an ear of corn on the control plots. The number of fertile stalks increased with annual increments of residual nitrogen and with nitrogen applied in 1968 (F13. 3). Something less than half of the increased yield in Fig. 1 was due to the increase in number of ears harvested (Fig. 3). The balance was due to a somewhat parallel increase in weight per ear (Fig. 2). Partial correlation coefficients significant at 1360005 were obtained for ear numbers (ryn-w - .979) and for ear weight (ry..n c .98#) in the following regression: ' E! - -55.5 4- .0022214 .3629w (32 «986) where: E! :- estimated yield. nil/ha N a number of ears/ha W’u ear weight. g/ear 37 Carriers 2K)C)" [SFUFI3 CINH4NO3 f; '75- OUREA 2 g I50L o “5 I25~ ‘5 1 1 I L {3 I00 °’ 200 L 3 Rates A252 Kglhc 3 I75- 0 I68 .. E) o 84 " >' I50~ E o C) |2£5" o””””,”’4y_ 1 J l i '00 I965 I965 I965 I965 I966 I966 I966 I967 I967 I968 Years of N Application Figure 1. Relative increases in yields of corn in 1968 in relation to residual and cumulative effects of fertilizer nitrogen 38 Carriers I50 " A NH3 0 NH4NO3 I40 - o UREA g :30 C: o 0 I20 1..— o E HO 8 h p ' l 8, IOO " '50 L Rates (D -o— _. A252 Kglha £3. '40 a |68 " g I30- ° 84 8 I20 I I0 , L I 1 I00 I965 I965 I965 I965 I966 I966 I966 I967 I967 I968 Years of N Application Figure 2. Cumulative effects of annual nitrogen applications on corn ear weights in 1968 39 Carriers |4()" 4§BH13 DNH4NO3 A '30 _ o UREA 3 15 L z . fig IZKDF- f; o o 7) o I l0 - " 'E 8 1* I L l ._ IOO a) 3 '40 ' Rates ‘é’ A 25% Kg/ha .. 0 l6 - “u I13C) C) £94 8 . :3 I53C>" m E .o I I0 - IE 1 L l L '00 I965 I965 I965 I965 I966 I966 I966 I967 I967 I968 Years of N Application Figure 3. Cumulative effects of annual nitrogen applications on numbers of fertile stalks in 1968 40 Although weight per ear was calculated from yields and ear numbers. the two independent variables were not highly intercorrelated (rn. - .227). The probabilities in Table 5. indicate that variation in ear numbers was associated.mainly with soil variation (replication) and with the increasing differential in soil productivity associated with successive annual applications of N. Ear weights and yields. on the other hand. were influenced strongly also by differences in carrier and rate of N application. Incrementation of Residual Response In Table 7. main effects of carriers and of rates are considered in.terms of relative yield responses in 1967 and i968. Yields increased with each successive annual application. The rate at which these year-to- year increases occurred also increased with the amount of N applied and with carriers in the order urea (W03 (N213 . It may be assumed that benefits from nitrogen applied in previous years would have contributed similarly to the yields on.plots which received.additional nitrogen in the harvest year. On this assumption. the relative increases in Table 7 have been incremented by year of N application in Table 8. In 1967. there was little difference in total relative response to the three carriers. However. the extent to which residual and current inputs of nitrogen contributed Lu Table 7. Relative increases in yields of corn expressed as percent of maximum for carrier or rate of nitrogen _Igars of N application LSD(.05) for Carrier 1965 1955 1965 1965 years 1966 1966 1966 within or 1967 1967 N 1968 treatments rate of N ---------------- percent --------------- 1967 harvest year: Urea 8.3 43.1 97.7 26.1 NHuNo3 13.6 51.6 98.7 26.1 LSD(.05) ns 16.7 ns 84(kg/ha) 9.7 43.8 92.4 24.3 168 13.6 59.7 99.8 24.3 252 20.3 66.6 100.0 24.3 LSD(.05) ns 13.0 ns 1968 harvest year: Urea 11.0 21.3 34.8 61.3 18. NE 17.4 39.9 52.6 100.0 18.4 LS%(.05) ns 14.0 14.0 14.0 84(kg/ha) 9.5 26.5 33.9 74.5 24.2 168 18.2 34.2 51.5 99.5 24.2 252 17.9 42.8 74.7 100.0 24.2 LSD(.05) ns ns 21.0 21.0 42 Table 8. Relative yield responses incremented over years of N application Relative yield increases Carrier associated with Total or year of N application relative rate of N increase 1965 1966 1967 1968 -------------- percent -------------- 1967 harvest year: Urea 8.3 34.8 54.6 97-7 NH3 22.? 55.1 22.2 100.0 84 (kg/ha) 9.7 34.1 ’ 48.6 92.4 168 13.6 46.1 40.1 99.8 252 20.3 46.3 33.4 100.0 1968 harvest year: Urea 11.0 10.3 13.5 26.5 61.3 NHuNO3 9.3 14.9 20.2 19.8 64.2 N83 17.4 22.5 12.7 47.4 100.0 84 (kg/ha) 9.5 17.0 7.4 40.6 74.5 168 18.2 16.0 17.3 48.0 99.5 252 17.9 24.9 31.9 25.3 100.0 . .. .- 43 to the total response varied greatly. In the case of N33. about 78 percent of the yield increase could be ascribed to residual N from.1965 and 1966 and only 22 percent to the N applied in 1967. With the other two carriers. approxi- mately half of the response could be assigned to residual sources and half to the current year's application. In 1968. the response to NH3 was much greater than to urea or NH4N03.. The difference was due principally to more effective use of the current year's application of NR3. Circumstances of weather in 1968 were responsible for this difference and will be described in the next section. Increments of residual response in.Table 8 increased with rate of N addition. At the 252 kg rate. residual accumulations accounted for about 67 percent of the total yield response in 1967 and about 75 percent in 1968. The 25 percent relative increase which could be ascribed to the 1968 application.at this rate was equivalent to an actual‘ increase of about 10 hl/ha (Fig. 4). The resulting ratio of 25 kg N per hl (19 lb N/bu) can hardly be considered economic. In previously reported studies of residual nitrogen availability. no consideration has been given to the effect of repeated annual applications. Residual incrementation. as illustrated in Table 8 and Fig. 4. must be given increas- ing attention as more growers use more N year after year on the same acres. 44 mHoApsoo Hobo commenced odes» mood so cocoa sowoauas no maeoumo o>aomassso use Hmsodmam .: oasmam 3&9: 2.82.4 8:34 2 w New _ we. em 0 m . . . w 0 let .m a » II$WI. a . nv_ mm .1 .m. 5 ON m U s 4 mumw “H. Aw I mom. 0 on I < . mmm. .32 6 .mm M $9.82 .89 a own. 8m. New. .82 .89 a 1 w. 20:40:83 2 co mm 45 Relative Efficiency of Carriers Evidence has been presented in Tables 2. 6. 7. and 8 that residual benefits accumulated more rapidly with N33 than with the other two carriers. Also. the total response in 1968 to residual and current year's applications of NHuNO and urea was only about 60 percent 3 of that for NH . These difgerences. however. were expressed as main effects. They lead to erroneous generalizations unless circumstances of application and significant interactions between the carriers and rates and years of application are taken into account. These interactions are not readily apparent in tabular data. A number of mathematical models were examined for their usefulness in describing these interactions in the 1968 yield response data. The function finally chosen made use of a quadratic on number of annual applications to supply a unique constant term for the quadratic on rate of N for each carrier within each application year. The model chosen for the reSponse to N within carrier within year of application had the following form: EX1.a+bA1.cnf. 'FM? 7 2 (d N + e N ) 1 13 i 13 1 46 where: Eli a estimated yield increase for an individual carrier A1 a number of repeated annual applications of the ith carrier Ni 3 rate of application of the ith carrier 3 a rate of application. coded as 1.2 and 3 The coefficient of multiple determination (R2 a .658) indicates that only 66 percent of the total variation in yield response was accounted for. Nevertheless. the plotted function in Fig. 5 provides a realistic picture of sig- nificant interactions between carriers and rate on yield response to successive annual applications of fertilizer nitrogen. The curves in Fig. 5 represent the response observed on separate series of plots which received 1. 2. 3 and 4 annual applications of N. The area between the curves is shaded to represent the incremental contribution from each successive annual application. The assumption is made that similar increments of available nitrogen would have contributed to the total response on plots which received all four annual applications. The percentage points on the vertical axis are relative to the maximum yield increase with N33 taken as 100. p f Three practically important differences among the three carriers are reflected in Fig. 5. 75 UREA « so: \\3\\> 25 '\\\\\\‘ Isé<%6\7\/\/: O /' ///////////////,'9 95/1 84 I68 252 75 P NH4 N03 \\ \ x 50L I968\\ // \ \ \ ,19/6/ 25 \ \\\\I96\6\ FMSBEW \\ 84 I68 252 I00 ~NH3 [1/1<<\\ . .7 ll 2" :\\\<\\ V“ . 9.// o {/////77////./ // / 84 I68 252 N APPLIED ANNUALLY (kg/ha) Figure 5. Incremented responses of corn in 1968 to residual and current inputs of nitrogen from three fertilizer sources CORN: I968 RELATIVE YIELD INCREASE (percent of NH3 maximum) 48 The most striking difference is in the response of corn to the 1968 application of the carriers. At the 84 and 168 kg level. NH3 applied in 1968 was much more effective than urea or NHQNOB. Referring to Table 2. a similar differential response in favor of NH3 had been expressed in 1965. but it did not appear in the case of current year's applications in 1966 or 1967. The 1965 differences were not statistically significant. but they may have reflected a moisture advantage in a dry year for deep placement (injection) of NH3 (of. Table 3). The uniquely greater effectiveness (observed in Table 8 and Fig. 5) of N33 applied in 1968 is readily explained by sequences of rainfall associated with the times of application of the three carriers in 1968 (of. Table 1). The three carriers were applied between two periods of above average rainfall (Tables 1 and 3). The soil remained near field capacity during this period. It may be assumed that the 1.90 inches of rain from July 23-27 and the 1.34 inches of rain from August 5-8 resulted in considerable percolation. The relative inefficiency of urea and NHuNO3 applied in 1968 can be ascribed to leaching of urea and/or volati- lization of N33 released by its hydrolysis and to leaching and/or denitrification of the N applied as nitrate in the salt. 49 .A second feature of difference in Fig. 5 is the evidence that. at the 84 kg level of N application. the residual benefit from urea applied in previous years was less than with the other two carriers. As noted in Table 1. both urea,and NHuNOB were sidedressed (broadcast by hand) and mixed in by shallow cultivation. This is a very inefficient placement for urea (Benson and Barnette. 1939. Pesek and Dumenil. 1956. Pesek. 1964). In 1965. 1966. and 1967. sidedressings were followed by periods of 9 to 16 days before precipitation occurred which might have moved urea down to a safer depth or have (promoted absorption of NH3 released by hydrolysis. Single light rains five days after application in 1966 (.21 inches) and the day after application in 1967 (.25 inches) would have promoted hydrolysis but little movement. Hydrolysis of urea and volatilization of NH3 would have been enhanced . also by periods of high temperature after application (5 to 14 consecutive days with maximums of 80 to 95°F). volatilization losses due to inappropriate placement of urea were not reflected in yield responses to the current application of N in these earlier years (Table 2). Differ- ences in residual response were. however. significant (Tables 7 and 8). ‘A third difference among carriers in Fig. 5 relates to residual behavior at the highest rate of N application. In the case of urea and NH3. the residual contributions to 1968 yields increased with rate of N over the entire range of 50 treatment. With NRQNOB. however. residual benefits reached a maximum and then declined at higher rates of application. The declining residual benefit from NHuNO3 can be explained if residual effects on soil acidity are taken into consideration. At the 252 kg level of N addition. soil pH in August 1968 was 5.3. 5.5 and 5.7 for NH#N03.urea and NHS. respectively. These may be compared with pH 6.0 for control plots. Effects on soil pH will be discussed in greater detail in connection with Tables 11 and 12. It is apparent, however. that unfavorably acid soil conditions had developed more quickly with NH4NO3 and that these would have tended to oppose beneficial residual effects at high rates of this carrier. Forms of Residual N in Soil It may be assumed that residual benefits to corn were due. mainly. to carryover of available nitrogen at depths in the soil within reach of the roots of succeeding crops of corn. Forms of nitrogen which.might have been carried over include organic N in soil humus or in corn residues. nitrate in the soil solution and ammonium.adsorbed on the exchange complex or fixed reversibly by collapsible clay minerals. eldahl N in the soil Values for total N in Table 9 would have excluded nitrate but would have included both organic N and ammonium. 51 ma owe. «me. sac. .z msdbaeoea muoaa sou Amamehvmnsem as as as as no as Anc.vnmq no see. awe. go. one as omo. nmo. ooa. mow n no mmo. nmo. mac. no «mo. moa. omo. am mm on. mac. omo. wmo. «mm as «we. coo. mmo. owe e: “we. Re. :3. a: woo. use. see. 3 mesons _ no «mo. «mo. ewe. «nu ma omo. awe. new. new no «mo. moo. mmo. on mac. moo. «mo. am memo as omo. ”we. moo. o Hoausoo maedaaso hem” announces» mom” £3 a no aeaaamo ovum bwmd nonlbhoz ad flowchudfl Adam .m OHAIQ 52 Analytical and sampling errors in the determination of total N and total C are high relative to variation which may have practical significance in the field. For example. a difference of .001 percent N in Table 9 is equivalent to 30 lb/acre to the 10-inch depth that was sampled. A.differ- ence of .01 percent C in Table 10 is equal to 300 lb/acre. None of the variation in percent N or C was related to treatment or years of application with statistical significance. However. significant year-to-year variations in C:N ratio (Table 11) did reflect net removals of N and/or net addition of C by the large crops of corn which were harvested in 1966 (of. Table 2). A.detailed examination of the relationships between Gland N in these soils will help to evaluate the extent to which N may have been immobilized and carried over in soil organic matter from one year to the next. The relations ships observed also illustrate a number of principles which have been established in the extensive literature on soil nitrogen (Allison. 1955: Bartholomew. 1965: Harmsen.and Kolenbrander. 1965: Jansson. 1958). The quantity of organic matter in the soil is largely determined by the balance between annual inputs of C in plant debris and annual losses of C by respiration. The C:N ratio is an important consideration since it influences the extent to which immobilization of mineral N or mineralization of organic N will occur. A.critical 53 on em.” m~.H em.« .2 msubdoooa ocean Hon Amasehvmnsox as as on as as Ame. Vang as HH.H a~.a aw.“ «mm as n~.a on.« an.“ mod n as H~.H an.a mm.” on ma.« we.” o~.H em mz on a~.a m~.« m~.H mnu 3 2; no; on; s: n no em.“ mm; mm.” 3 8; on; 34 on ones: as as.“ mo. H mm.“ «mm as on.« em. « am.« we" on 3.“ no.“ out“ no 34 on. a an.“ so 8.5 ms Na.u ~a.a n«.a o flamenco masseuse mead announces» swam . :33: on» 33 33 can»? 83 83 33 one case» mead mead mean case» “was woman nmma Rosana 3343 “3.33 .33 zoo cognac modes aeaaaso moses acemfiseaau ovum mead wannabe: ca sconce Haom .oa canes 54 ratio for normal crop residues is C:N - 30 or 35 to 1. which corresponds to an N content of about 1.5 percent. The linear regression of C on N for the 120 plots sampled in the fall of 1967 was highly significant (r u .663) and indicated that there was. on the average. a 600-lb/acre change in soil C for each 30-lb change in soil N. The ratio of change was 20:1. which is wider than the C:N ratio of the soils themselves (Table 11). This ratio reflects changes in the more active fractions of soil organic matter -—those portions most recently derived from decomposition of corn residues in which the C:N ratio was of the order of 45:1 or higher. The change in proportion of Cato N was not linear. A highly significant (P s .007) quadratic term was expressed in the polynomial of Fig. 6. The derivative of this function dN/dC . -.089 + .110 c was used to calculate the ratios of C to N immobilized in the active soil organic fraction at each level of soil C. As seen in Fig. 6. this immobilization ratio. at the lowest C and N contents. was about 30:1. This would have been the situation in control plots where no inputs of fertilizer N were made and where inputs of C were limited by reason of low yields and restricted production of corn residues (of. Table 2). 55 mo.o o.nu n.3H ¢.na .z mnahdoooa uuoam you Aun¢Ohvna¢ox an a: an an a: an Amo.vnmq a: «.nu 0.3“ o.m« «mm as m.n« a.a« o.n« mod n so.“ v.3 Ti «.3 3 mad 3: 3.3 an ma an m.m« n.m~ n.n« «nm 3 3: m. a w...” 3: a: 3: as: YE mm.” 3: or: v.2 3 mafia: nu e.md s.nd s.ma «mm mm.” a.¢a «.na M.NH we“ mo.a o.mfi ~.¢H s.m« mm.“ o.~a m.ma .m« an comb mm.a ¢.NH o.¢u «.n« o Honunoo uncanndo swag mane-ouch» uwma can»? an» 33 33 was»: 3: 3m." 1&3 and name» “can mom” mvaa undo» nwma nwmfi home 3953 $933 n___o.a..».3__.._..nmm.¢_.a.”Icing z «a $238 |HmmdmmWMfldmmmu ymmMMHMJmmmmmmmmfllllllll. ovum swan Hussite: nu weapon 3.0 Adam .«a oaaea 56 0'230" “JO E ~_—v Q) .9 8 ¢- a) a? 25 _ 3 c: .f._.> -09 g E: 20- .8. '5 '2 <3 2 E ~=.us-.asec+.055 c :5 g l5- L R3588 1s-.009 L 1 -.08 a, m I.2 l.3 |.4 Sail Carbon (percent) Figure 6. Immobilization ratios in relation to soil carbon and nitrogen contents 4.5.4“. S“)lL.'V Soul Carbon (percent) 00 CM 02 "’ t C) F: C) 3 _ z £3 a 5 00 (O at 0 Soul Nitrogen (percent) 2! (fl l CD CD CD O r I l2.5 I35 I45 Soil C:N Ratio Figure 7. Soil carbon. nitrogen and C:N ratios in relation to increasing rates of fertilizer nitrogen after three annual applications (No a control; N1.N2.N3 - 8“. 168. 252 ng/ha) 57 The immobilization ratio in Fig. 6 decreased with increasing C and N contents. approaching the C:N ratio of the soils themselves as a limit (of. Table 11). When inputs of fertilizer N exceeded the capacity of the crop to respond by producing an appropriate excess of residual C. the balance in favor of immobilization and increasing C and N contents was abruptly reversed (Fig. 7). In relation to theory. the 30:1 ratio at low N and 0 contents in Fig. 6 is in the critical range where an increase in C would promote net immobilization of N. whereas an increase in N would permit net mineralization. Over the range of Fig. 6. increasing C was accompanied by increasing retention of N. The increase in C. however. was due to increased growth of corn in.response to fertilizer N which also increased the size of the microbial population and the annual rate of decomposition. This increase in respiratory loss of C was responsible for the narrowing immobilization ratio. Maximum.quantities of N were retained in humified soil organic matter when fertilizer N was used at the 8“ kg rate (Fig. 7. Tables 9 and 12). Additional increases in C occurred at the 168 kg rate. The increased C pro- duced by corn at this rate. however. was insufficient to maintain a balance in favor of immobilization and retention of N. At the 252 kg rate. residual levels of both N and C declined sharply. 58 Table 12. Soil carbon. nitrogen.and C:N ratios in relation to annual rates of N application Rate Year of N's licatian Average of i 9 for N 1966 1966 ~ rate of 1967 N kg/ha Percent total N in soil 0' .087 .081 .090 .086 84 .092 .097 .091 .095 168 .099 .090 .088 .092 252 .093 .087 .085 .088 18D(.05) ns ns ns ns Percent total C in soil 0 1.132 1.123 1.121 1.125 8“ 1.231 1.383 1.210 1.276 168 1.302 1.286 1.246 1.278 252 1.230 1.200 1.102 1.191 L8D(.05) ns ns ns f us 8011 C:N ratio 1 14.0 12.0 13.2 h 14.0 12.3 13.7 168 13.3 14.5 i .3 1 .0 It 10.0 13 5 13.6 L8D(.05) ns ns ns ns 59 The sharp reversal towards narrowing C:N ratios in. Fig. 7 is evidence that the annual balance between inputs of C and N at the 252 kg rate now favors netndneralization and depletion of humified soil organic matter. This depletive balance of C and N may be inferred also from the relationship in Fig. 8 between kJeldahl N in soil samples taken November 1967 and corn yields in 1968 for the 120 plots which received no N in 1968. Only 14 percent of the total yield variation was accounted for. but the overall relationship was highly significant (Pr(.0005) and the coefficient for the squared tern approached significance (P 2.06). Maximum yields were associated with the lower levels of residual N in the plow soil. It is clear that the higher rates of N which produced maximum.yields of corn did not produce increases in resid- ual organic or ammonium forms of N in the plow soil. as determined by the kJeldahl procedure. Rather. the reverse was true. ‘ The question remains. where did the N come from to produce the residual responses observed at high rates of urea or NH3 in Fig. 5 ? Crop residues The soil samples taken in the fall of 1967 did not include surface residues from the 1967 corn crop. These were avoided in sampling or were removed by screening. 6O .umma acnae>oz ca somoapas Haom on soupaaoa ca mom“ :a mooaa Hasuumoa so amass» saoo 2:853 5m. 5 2 am .338. .m 8.. mac. omo. mmo.‘ .mo. mw.mw_“umw swanmwdv_.nu wk N2 8872 m6. . cents. onsmam N ID was co <1- to ID (DU/N) 896| U! SPIGM Q In 61 No measurements of stover production or N content were made.‘ A.tentative estimate of N that might have been carried over in the stover can be calculated from the. yields of grain. Romaine (1965) notes that a 150-bushel corn crop grown under optimum.fertility will contain.135 pounds of N in the grain and cabs and 65 pounds in the stover(abput 1 percent N). On this basis. stover left on the control plots in 1967 would have contained about 20 pounds of N per acre (cf. Table 2). The carryover from plots which produced 90 hl/ha or more (80 bu/acre) would.have been about double this. if no allowance is made for the fact that the stover on these plots probably would have conp tained a higher percentage of N. If it is assumed that N content of stover at the higher rates of N application was 1.5 percent (Cook. 1962). the carryover would have been about 60 pounds (67 kg/ha). With their low N content. the stover from control plats would be expected to immobilize additional N during their decomposition whereas the high N residues would be expected to release some N to the 1968 crop. A.re1ease of 25 or 30 percent (15 to 20 pounds of N) would have :nroduced the 12 to 13 bushels of corn which is represented in Table 8 as a 31.9 percent incremental increase attri- butable to carryover from the 1967 N application at the 252 kg rate. 62 These calculations are illustrative only. They do indicate that significant residual benefits from fertilizer N may be carried over in the form of increased quantities of stover of increased N content. Mineral nitrogen Data in Table 13 show that nitrate in the plow soil (0 to 10 inches) at the time of tassel appearance was uniformly low in all plots except those which received fertilizer N in 1968. Ammonium concentrations in these same samples were unusually high. but there were reasons to suspect that this was due to contamination from atmos- pheric sources during storage in paper bags. According to Lucas' (1969) proposed "critical nitrate- nitrogen" level. all of the nitrate values in Table 13 are in the positive response range except that for the highest 1968 application of N. Comparison with Table 7 shows that. in fact. a significant increase in yield of corn was obtained with the 168 kg application in 1968 but no further reSponse was obtained with 252 kg. The fact that corn yields should be related to the capacity of the soil to maintain a moderately high level of nitrate in the plow soil is surprising in view of the quantities of nitrate and much larger quantities of ammonium which were present in the root zone (surface 20 inches) of these soils (Table 10). 63 Table 13. Nitrate nitrogen in soil sampled August. 1968 Averages Years of N a lication Rate 1963 1953 1933 1933 Carrier of N 1966 1966 1966 Treatment Carrier 196? 1967 kg/ha 1968 -------------- pp2m --_—--—---—-----_ Control 0 17.0 17.0 16.0 16.5 16.6 Urea 84 17.3 15.3 18.8 32.5 21.2 22.9 168 18.8 18.8 21.3 3 .5 23.3 252 15.3 17.8 15.8 7.8 20.1 168 16.3 23.3 15.0 39.3 2 .h 252 18.8 18.8 19.5 01.8 2 .7 NH3 84 15.3 20.0 17.3 30.8 20.8 22.1 168 19.5 15.3 19.3 35.5 22.4 252 16. 17.5 19.3 39.5 23.2 LSD(.05) ns ns ns ns ns. ns 61+ «use madness A.c “mm Amman am: new .z« oo on o nausea mma Amov mes om .e« cm on smuaasoa won me mum no“ .:a em on o ”Mecca on an .aa am Aooumsc «.mna . man as A*c was as Amsnenv «ma . n.am as am an on Aemnsmv n.Hm u do on as on on Asmtmav «e a n.om ms es «mm mm” Amauo . n.om u 0 11111111111111: poomtoaom Ham 2 .AQ tuttttuttttntt (Imozsmz ms mozemz as 2 msxms mnm Honscoo z an\ma «mm Hospeoo A.adv so zropsnsaz zaasaeosas space Haom moms .sa sasma< no ensue and: oneness ens addsoaaa so nonsenansuan .sa canes 65 Soil samples for Table 14 were stored in sealed glass containers to avoid contamination by atmospheric NH . The unusually high ammonium levels in the surface 12 inches must. therefore. be taken seriously. They can be explained in terms of effects of unusually wet soil conditions asso- ciated with several periods of rainfall concentration in 1968 (Table 3). The surface soils of this experiment are underlain by a moderately impermeable sandy clay loam B horizon at about 16 to 25 inches (Appendix A). Theyvere periodically sat- urated and remained near field capacity for periods up to two weeks after each of the rainfall concentrations in May. June. July and August. Higher than normal temperatures were associated with each of these periods. Nitrification is retarded by restricted aeration under conditions of high moisture to a much greater extent than are heterotrophic processes of organic matter decom- position. A.maJor effect of restricted aeration on decom- position is to reduce the extent to which N is immobilized in thepresence of carbonaceous substrates (Bartholomew. 1965; Harmsen and Kolenbrander. 1965). The residues from the 1967 corn crop would have decomposed under conditions favoring rapid decomposition with minimal immobilization and restricted nitrification of released ammonium. Conditions favoring denitrification would have occurred also from time to time. 66 The quantities of ammonium in the surface 12 inches (Table 14) greatly exceeded the amount added as NH4N03 or the quantities that might have been carried over in stover from the 1967 corn crap. This indicates that soil humic N had been extensively ammonified. The normal immobilizing effect of corn residues during early stages of decomposition was not expressed with either treatment. Instead. its rapid decomposition may have supplied energy to support microbial attack on humified organic materials which are not normally utilized because of their low energy content. This is the phenomenon referred to in the liter- ature as the "priming action" of fresh residues on decom- position of soil organic matter (Bingeman. et al.. 1953; Uinsor. 1958; Jansson. 1958). Below the 12-inch depth. there was essentially no difference in quantities of either ammonium or nitrate in either profile. except for a marked.accumulation of ammonium in the 36 to 48-inch layer under the NHuNOB treatment. This indicates that considerable ammonium had leached to this depth. It was detained by sorption in the clay loam.B horizon and protected against nitri- fication because this horizon remains saturated or near saturation for much longer periods of time than upper horizons after heavy rains or during seasons of low evapotranspiration. Except for the surface 0-12 inches. the two profiles are analogous to two chromatographic columns with 6? essentially similar capacities for retaining ammonium or nitrate. Since they were not loaded the same. it must be assumed that much more mineral nitrogen had.moved to depths greater than five feet under the NHhNO3 treatment than in the control plot. Major movement would have been as nitrate. but ammonium has leached also as indicated by the buildsup at 36 to 48 inches. Total mineral N (NH: plus N03) in the control profile was 374 pounds per acre to a depth of five feet. The total for the NHuNOB plot was 722 pounds. A.total of 900 pounds of N per acre had been applied as NEuNOB over the 4-year period. A.calculated 200 pounds had been removed in the 25? bushels of grain and cabs harvested over the previous three years. This plus the 722-pounds found in the profile would account for all of the fertilizer N that had been applied. However. it must be assumed that additional mineral N was released from.soil sources. This release from soil sources would have been at least as great as in the control plot since the analyses for kJeldahl N. which would have included.ammonium. were similar (Table 9). The estimate of soil release in the control plot must take into account the 130 pounds of N in 168 bushels of corn and cabs harvested over the first three years. This plus 374 pounds found in the control profile gives an estimate of 504 pounds of N which must have been.mineralized from soil sources. since no fertilizer N had been applied. 68 If a similar release from.soil sources had occurred in the NHuNOB plot. then an equal quantity must have been.lost by denitrification or by leaching to depths greater than five feet. On first thought. a loss of 500 pounds of N per acre is staggering. On an annual basis. however. it is only 125 pounds per year. This is the difference between the 225 pound annual rate used on this plot and 100 pounds. which is the maximum recommendation to farmers for corn on soils of similar productivity without irrigation in Michigan (CES Bul. E-550. 1966). Thus. 125 pounds more N was applied each year than could be expected reasonably to enter into the crop or into biological systems involved in its decomposition. The crop and biological systems associated with it in the surface horizons appear to be the only mechanisms for retaining N in the soil for any period of tune. Data in Table 13 indicate that these systems are mainly oper- ative in the surface 12 inches. Foth (1962) has shown that this is where 80 to 90 percent of the corn root system is to be found. It includes the plow soil (0 to 10 in.) where decomposition of surface residues takes place after plowing. It may be concluded that the plow soil dominates the nutritional environment of the corn plant. In turn. the crop and the microflora of the plow soil. which are supported by the crop. dominate the N economy of the total 69 profile. Some recycling of mineral N from the 12 to 24-inch depth can be expected to occur by capillarity and by root uptake. since eight to ten percent of the corn root system is to be found.here. Recycling from the 24 to 36-inch layer will be minor since corn roots extend only randomly to this depth and.mass capillary movements upward from this depth occur infrequently (Netselaar. 1962). Most of the mineral N below 24 inches has. therefore. moved beyond.recovery. How much of the N above 24 inches may yet be recovered will depend upon crop and climatic factors affecting its uptake. conversion from one form to another and its vertical movement. If 50 percent of it were to carry over usefully to the 1969 season. as Pesek (1964) suggests. a 60-bushel corn crop could be predicted on the control plot. This is a reasonable expectation (of. Table 2). The predicted 1969 yield on the NRuNO3 plot would be 135 bu/acre. This exceeds the yield potential for this soil without irrigation. Residual yields of 95 to 105 bu/acre were obtained at this level of N addition in the favorable 1966 season. Data in Table 14 indicate that mineral N in excess of crop response will be quickly lost beyond recovery. Only N which is retained in the upper 24 inches of the soil by recycling through the crop and its associated microflora can contribute significantly to residual 70 carryover for the benefit of succeeding crops. Under the soil and climatic conditions of this experiment. beneficial effects of fertilizer N were carried over by these systems for three years. It appeared. however. that beneficial residual effects of the 1965 applications would not have been detected in a fourth season. Other soil sources of N The data and discussion in the previous section suggest that as much as 500 pounds of mineral N were released from soil sources. If this all came from organic matter in the plow soil. it would represent a decrease in organic N of.017 percent. Changes this great were observed in plots which received N treatments. if allowance is made for up to .005 percent ammonium which have been included in the kJeldahl N determinations of Table 9. Since these samples were all taken at the same time. there is no basis for inferring any trend over time in the control plots. The data in Table 14. however. show that extensive release of mineral N has occurred. The release must be at a substantially high rate in order to maintain nitrate concentrations in the soil solution equal to those under NH4N03 through the entire profile below 12 inches. Mineralization of soil organic matter probably has resulted in declines in soil organic nitrogen. The rate 71 of depletion has been less rapid at lower N rates than the heavier N applications. This reflects more efficient recycling and immobilization due to lower N content of corn residues. The possibility exists. also. that non- symbiotic fixation of atmospheric N may be supported by these low N residues (Jensen. 1965). another possible source of N in these soils may have been ammonium previously fixed by clay minerals. Preliminary analysis of surface soil from a control and an NfluNOB plot indicated the presence of vermiculite to the extent of five to 20 percent of the clay fraction. Since the clay fraction represents only 18 percent of the surface soil. fixed ammonium must be dismissed as a significant source of N. Effects on Soil pH Probable sources of soil pH variation were noted in connection with tables 4 and 5. Soil pH variation in relation to N treatments for the November 1967 and the August 1968 samplings is shown in table 15. Increases up to 0.5 pH units occurred on most plots between the November 1967 sampling and the following August sampling. A decrease in soil pH during the summer months has been observed by several investigators (van der Paauw. 1962: Collins. Whiteside. and Cress. 1970). Although reasons for seasonal and year-to-year changes in soil pH are not well understood. there is agreement on some of the fundamental processes involved. 72 mm m: m: as on m: as Ano.vmnq om.m na.n nm.m no.8 mm. m «mm me.m mm.“ mm.“ mo.m me. n mod n om.m sm.m .oa.n mm.m mm.m mm. m em. mz «o. m mm. m mo.m om.“ mm. m «mm mm. m mm. m mo.e mm.n ma. m men n Hm.m mm. n me. n oo.e no.0 .mm. m am ozssz ma.“ me. n me. n ma.n ma.m ma. m «mm ma.m mm. n me. n mm.m nm.m mm. m was mm.n ma.m mm. n ma. n mm.n mm.m om. n :m sons 00.0 mm.n mm.m ma.o ma.e o Honssoo moms smswsa me me a: mm.o mn.o we Amo.vomq en.n om.n oa.m mo.n mmm me.m o~.n me.m ne.n men mn.n so.“ an.“ on.n as.“ as mmz mm.m ma.m mm.m mm.m «mm as.m ma.n ma.m mo.n we” m an.“ no.“ oe.m ne.m ma.“ as ozssz es.m as.m mm.m mm.m n:.m «mm m:.m me.m m:.m mm.n mm.n we” mo.m mo.m mm.m mm.m mw.m mu.n :m sea: ma.m mm.m ma.m ma.w o Honseoo moms Honaoboz z memm sexes so when mom” 2 seem Hosanna sessssona coma coma mean no comm acaaaao newswoa< soaamoaa a 2 no mama» ma Haom so soapmoaaaam mo cams and Hosanna camoupdn no muoemum .ma canoe 73 Initiating processes of soil acidification involve differential accumulation of anions in excess of basic cations in the soil. Plants tend to take up cations and anions in approximately equivalent quantities. However. nitrate and sulfate are reduced to amino and sulfhydryl forms when they are assimilated by the plant. Protons and anions are produced when they are released by decom- position and are oxidized again to nitrate and sulfate. Because of the great reactivity of the R ion. the protons which appear initially with surplus anions in solution quickly react with the exchange complex or with soil minerals to release bases. A cation-anion balance in the soil solution. and a buffered pH. are achieved through this release of soil bases which accumulate as residual free salts in the absence of leaching. The decrease in soil pH with time during the growing season is usually attributed. in part. to the effect of these free salts. Thus in the absence of leaching. soluble salts tend to accumulate through the growing season. This increasing salt concentration shifts cation exchange equilibria in the direction of increasing h ion activity (the "salt effect"). For this reason. soil ph determined in water tends to reach a minimum in temperate climatic zones in the fall of the year. It tends to return to a higher level. characteristic for the soil. in the spring or early summer as surplus salts are removed by leaching. 74 The leaching of residual free salts is the essential process whereby soils are depleted of bases and made residually more acid. The development of residual acidity is expressed by an increase in buffer acidity (lime requirement) and/or by the failure of soil pH each year to return to the previous year's pH. That seasonal soil pH variation is controlled by mechanisms other than the "salt effect" has been shown by Collins et al. (1970). Just what these other mechanisms are is not clearly understood. The normal acidification process is greatly affected by nitrogen fertilization. The three N carriers used in this experiment are considered to have essentially similar residual acidifying effects. on soil pH (Nolcott. 1964). however. the initial reactions of these carriers are not the same. Urea and N83 have an initial basic effect whereas the NH4N03 has an initial acidic effect. The reactions by which these initial effects take place may[ be written as equations (1) to (3). The initial increase in soil pH with urea and N33 is due to the formation of the ammonium ion upon hydrolysis: N83 3883 11341103 q-h NH; . 03" (1) (NH2)200 —-> (NH#)2C03 iii-i N848003 + Na; . 011' (2) NHhNOB. the salt of a weak base and a strong acid upon hydrolysis results in an immediate decrease in ph: NfluNOB .flQfla. NHuOH + 8* + N03 (3) av.- --..-. 75 The initial akalizing effect of urea and NH} is reversed as the basic cation. N83. is oxidized by nitrifying bacteria to nitrate. disengaging two protons in the process. Under most humid soil conditions. nitrite is oxidized to nitrate by Nitrobacter faster than ammonium is converted to nitrite by Nitrosomonas. thus the complete reaction may be written as: N112; 4103—9 23" . N0} + 8011 (4) Adams and Pearson (1967) point out that the ultimate acidity that develops from fertilizer in a particular horizon is realized only after the residual salts are removed from that horizon by leaching. The comparison of the August 1968 pH values in the current year's N addition plots (Table 15) with the residual N treatment plots supports this statement. The most pronounced effect in terms of soil pH variation occurred in the current year's N addition for both the 1967 and 1968 samplings. The residual acidifying effects of the N carriers may be seen in the plots receiving N treatments in other than the year of sampling. In addition to the N carrier. the rate of N application is also an important factor in the potential acidification of the soil. Increasing acidification with rate of application is expected within each carrier as the rate of application exceeds the ability of the crap to reSpond in additional growth. and with the increasing production _of h ions from reactions (3) and (4). .--..--A4 76 Within the current year's N addition in 1967 and 1968. ph was sharply depressed by high rates of urea and NfluNOB. This was true for NH3 in 1967. but not in 1968. Due to the weakly to moderately developed fragipan in the B- horizon of this soil. water movement through the profile is restricted. The upper profile was saturated during abnormal rainfall concentrations in May and June of 1968 (Table 3). The soil remained unseasonably wet and was periodically saturated above the B-horizon during the more normal rainfall concentrations in July and August. Thus. for two-thirds of the growing season the soil was much wetter than normal. hence less well aerated. As a result. the higher ph values for N33 in August 1968 are likely due to the inhibition of nitrification of injected NH} to a greater extent than in the case of surface applied urea or ammonium in NH4NO3. It should be noted from equation (N) that N from urea or N33 must be 50 percent nitrified to neutralize alkalinity released when they are hydrolyzed. equations (1) and (2). In the non-current year's N addition plots. the greatest acidifying effects were associated with the highest rates of application. This buildup in residual acidity was highest with N34N03 and the lowest with N33. Annual increments of acidity which exceed the capacity of more readily decomposed soil minerals to release bases will accumulate in the soil in the form of aluminohexahydronium and protonated hydroxy aluminum and iron (Coleman and 77 Thomas. 1967). This in effect increases the potential acidity (lime requirement) of the soil. The rate of annual accumulation of potential acidity is greatly accelerated at pH levels below 5.5 and becomes a principle buffering mechanism below pH 5.0 (Wolcott. et al.. 1965). It is apparent in Table 15. that plots receiving the higher rates of N in the form of any of these carriers are experiencing pH's of 5.5 or less for at least portions of the year. Accelerated increases in lime requirement can be expected. even if pH is seasonally restored to higher levels by leaching of surplus salts arising from nitrifi- cation and mobilization of soil bases (Wolcott. et al.. 1965; Coleman and Thomas. 1967; Schafer. 1968). Soil pH's associated with current year's treatments in Table 15 are in a range where toxicities of Mn or other nutritional derangements can be expected to begin showing up. Such effects on corn nutrition may have contributed to the lower yield responses to NH4N03 than to the other two carriers. effects on Soil Calcium and Magnesium Levels According to the F statistics in Table 4. the only factor associated significantly with Ca and Mg levels was soil variation (replications). A carrier x rate inter- action approaching significance (P - .087) was eXpressed for Mg. Some of the variations associated with treatments in Table 16 are of interest. 78 Table 1.6. Extractable Ca and Hg in soil sampled November. 1967 Years of N a lication I963 1935 1933 Carrier Rate Treatment of N 1966 1966 means kglha _;2§7 ------------— pp2m ------------- Calcium _ Control 0 920 1240 800 980 Urea 84 1120 1040 1120 1090 168 1280 1320 1280 1290 252 1000 1000 1000 1000 NH4N03 84 1360 1240 1200 1270 168 1360 1280 1240 1290 252 800 800 760 790 NH3 84 1120 920 1160 1070 168 1080 1000 960 1010 252 1200 1240 1040 1160 LSD(.05) . ns ns‘- ns‘ ns. Magnesium Control 0 89 106 83 93 urea 84 105 96 106 102 168 96 116 89 100 252 73 83 .71 75 N34N03 84 115 99 93 102 168 121 141 109 124 252 86 74 64 72 NH3 84 102 86 86 91 168 86 74 74 78 252 121 119 80 107 LSD(.05) ns ns ns ns 79 Irreversible declines in soil pH are due to base depletion. Acidity produced by a process such as nitrifi- cation results. not only in displacement of exchangeable bases. but in release of bases by mineral decomposition. In the absence of leaching. displaced and released bases accumulate in the soil solution as free salts of surplus anions. Ammonium acetate extraction as used in this study makes no distinction between exchangeable bases and their free salts. It is not surprising. therefore. that extractable Ca and Mg as determined here were frequently higher in soils receiving N fertilizers than in the controls. This increased level of extractable Ca and Mg also affected the lime requirement (Table 17). resulting in a less pronounced increase in potential acidity for many of the treatments than might have been expected. The accumulation of surplus free salts and their subsequent removal by leaching is closely related to the production of surplus nitrate and its removal from the soil profile by leaching. It was estimated earlier (p. 68) for the 252 kg/ha rate of NH4N03 addition that as much as 125 pounds of N per acre could not be accounted for. If it is assumed that this was entirely lost by leaching of nitrate. the equivalent associated annual leaching loss of Ca would have been 180 pounds. or 98 pounds of Mg. The low values for Ca and Hg in Table 16 at the 252 kg/ha rate of NH4N03 suggest that their annual rate 80 as me mfi.o am.o am.o an.o Ano.vamq H~.~ ma.a mm.~ om.~ mmm ma.m om.n on.m om.~ mod n mn.m mm.m ma.~ na.~ em nz so.m mo.m mm.m mo.m «mm an.m oo.~ me.~ oo.m mos m : om.~ om.a no.“ m~.m oo.~ am oz mz on.~ mn.~ na.m mm.~ n~.~ «mm os.m w~.~ oo.m mm.~ ma.m we“ om.~ n¢.~ an.~ om.~ mm.~ ma.~ em «on: 0H.~ oo.~ oo.~ on.m o Hoapeoo 2 co moms «sums ovum Hosanna peoapeona mom” coma 2 co $9.8m HOHHHmU mommao>< sodwmoaa a Ziwm mama» useseadswcn cswa mead nonaoboz on» so soapmoaadmc we open and aoaaamo sowoaua: no mpocumm .ma canma 81 of loss with this treatment exceeded the rate at which these bases are released by mineral decomposition. The sum of exchangeable plus soluble bases extracted with ammonium acetate represents a balance between removal by crops or leaching and release by mineral decomposition. The data in Table 16. therefore. do not reflect base depletion as reliably as the evidence for irreversible pH changes in residual plots discussed in connection with Table 15. or the evidence for displacement of bases by exchangeable Al in Table 17. Effects on Soil Phosphorous and Potassium Levels The effects of N treatment on extractable K and P are shown in Tables 18 and 19. The primary factor related to changes in soil K.and P was soil variation (replication) according to the probabilities shown in Tables 4 and 5. However. there was a high probability for a significant year by rate interaction for P in 1968 (Table 5). Due to the close relationship between soil pH and the solubility of various Al. Fe. and Ca phosphate compounds it would be expected that extractable P would be directly related to soil pH. A comparison of Tables 15 and 19 shows this not to be the case. This lack of correlation is likely due to the complications introduced by soil variation and to the time lag for phosphate solubilities to come to equilibrium with changing soil pH. 82 Table 18. Extractable K in soil sampled November. 1967 and August. 1968 ears of N a lication Averages Rate 1933 1935 1965 1933 Carrier of N 1966 1966 01966 Treatment Carrier 1967 1967 kg/ha __;968 _ November 1967 ------------- PPZm --"---'-’--'---- Control 0 126 102 119 117 Urea 84 127 130 106 117 112 168 124 104 97 106 252 118 122 109 115 mum3 84 126 114 113 117 117 168 129 108 103 111 252 134 124 118 123 NH3 84 122 136 115 123 114 168 118 114 105 111 252 126 104 103 109 LSD(.05) ns ns ns ns ns August 1968 Control 0 136 119 109 113 119 urea 84 127 130 121 126 126 119 168 127 111 113 121 118 252 128 102 113 111 114 NH4N03 84 132 111 108 113 116 115 168 134 109 104 102 112 252 132 128 104 106 117 NH3 84 117 123 115 121 119 115 168 123 113 96 100 108 252 126 148 95 106 118 LSD(.O5) ns ns ns ns ns ns '\)§1} 83 Table 19. Extractable P (Bray P1) in soil sampled November. 1967 and August. 1968 Years of N a ication Averages Rate 9 5 9 19 f 1 Carrier of N 1966 1926 1926 Treatment Carrier 9 7 19 7 ks/ha $968 November 1967 * =- -=----- PPZm -=*—- ‘ —==- —— Control 0 93 86 95 92 urea 84 92 90 92 91 89 168 90 78 85 84 252 97 94 90 90 NHuN03 34 71 78 79 77 79 168 82 72 7o 74 252 91 95 81 87 NH3 84 94 90 85 88 89 168 93 96 101 98 252 83 81 79 80 Lsn(.05) .ns ns ns 1‘18. ns August 1968 . Control 0 67 74 67 78 71 Urea 84 81 86 83 89 85 85 168 90 84 83 103 90 252 91 75 83 70 80 N84N03 84 7o 66 66 76 69 72 168 75 61 60 63 65 252 91 88 79 72 82 NH3 84 83 91 76 84 83 81 168 87 9o 95 89 90 252 79 73 70 56 69 LSD(.05) .ns ns ns ns ns ns 84 There is no evidence for depletion of K in Table 18. The leaching equivalent of 125 pounds N per year would be 350 pounds K per acre. It must be assumed that K as well as Mg and Ca accompanied nitrate into drainage. Fertilizer inputs of 60 pounds per year plus release of K by decom— position of soil minerals apparently offset leaching and crop removal of exchangeable plus soluble K. SUMMARY AND CONCLUSIONS Information from earlier experimenters indicate that in most years one can expect approximately 50 percent residual benefit in the crop year following N additions and no significant residual benefit thereafter. These reported experiments have had one serious limitation. though. in view of the common practice of monoculture. That limitation is the lack of more than one year of N application. The field experiment used here was designed to determine the effects of three N carriers at three rates of application. with systematically incremented and systematically deleted annual N additions over a four- year period. Variation in yields of corn and soil tests were noted in response to these treatments. Residual benefits to corn were observed in these experiments in each of the three years following Just one annual application of N. These benefits were highly significant with the two higher rates of application of N83. with repeated annual N additions. residual yield benefits were cumulative. A portion of total residual response could be identified with each year of application up to the fourth year. 85 86 Cumulative carryover benefits increased with the carriers in the order urea