This is to certify that the thesis entitled SPRINKLER IRRIGATION WITH SIMULATED SECONDARY WASTEWATER EFFLUENT OF A TILE DRAINED SOIL CROPPED IN BROMEGRASS AND CORN presented by STEVEN ALEXANDER GRANT has been accepted towards fulfillment of the requirements for M.S. degreein Crop and Soil Sciences Major prof Date November 14, 1980 0-7639 M-J UnIVCl'uu'V -,. V...- LIpra RY ‘- m “‘1! ELQKV ,.__r- -~' ~ .nct UVtRDUt rlflt): 25¢ per day per item RETURNING LIBRARY MATERIALS: Place in book return to remove charge from circulation records SPRINKER IRRIGATION WITH SIMULATED SECONDARY WASTENATER EFFLUENT OF A TILE DRAINED SOIL CROPPED IN BROMEGRASS AND CORN By STEVEN ALEXANDER GRANT A THESIS Submitted To Michigan State University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Department of Crop and Soil Sciences 1980 ABSTRACT SPRINKLER IRRIGATION WITH SIMULATED SECONDARY NASTEWATER EFFLUENT OF A TILE DRAINED SOIL CROPPED IN BROMEGRASS AND CORN By Steven Alexander Grant A tile drained soil cropped in bromegrass and corn was irrigated with simulated secondary municipal effluent at 100 and 200 cm/year. The efficacy of additional N and K fertilization was tested. The dry matter production, grain yield and nutrient content of the crops were measured. The concentrations of nutrients were determined in the soil and in water from drainage tiles, wells and irrigation. The flow rates of water in the tile drains were monitored continuously. Corn took up more nutrients than bromegrass, mainly because the dry matter yield of corn was greater. The tile drainage water concentration of NOS-N and P, however, was typically less under grass than that under corn. Crop yield and nutrient removal by corn were increased with N fertilization. Fertilization with N and K increased yield and nutrient removal by grass. THIS THESIS IS DEDICATED TO ROGER NEWELL ii ACKNOWLEDGEMENTS First, I would like to thank the Michigan State University Agriculture Experiment Station for the funds to support this research. Second I wish to record my appreciation of the generous donation of time and expertise by the members of my advisory committee; Drs. F. B. Dazzo, B. G. Ellis, B. D. Knezek and M. L. Vitosh. Special appreciation and affection is expressed to the committee chairman Dr. R. J. Kunze, whose patience and consideration was severely tested by the author. Many other faculty have been greatly helpful, especially Drs. J. M. Tiedje and F. H. Horne. All these men provided the intellectual guidance but theory is worthless without experimental evidence. Tremendous help in the laboratory was provided by Mrs. E. Shields, Miss T. L. Hughes, Mr. J. C. Grove and Miss N. Leeman. Expert and steady help was provided in the field by Mr. D. A. Hyde. Finally, I wish to thank the cadre of graduate students with whom I held innumerable, and some seeming to them interminable, conversa- tions, especially Mr. T. E. Schumacher and Mr. G. Asrar. TABLE OF CONTENTS INTRODUCTION . ......................... Chapter I. LITERATURE REVIEW ..................... Waste Disposal on Land .................. Movement of Water and Ions Through the Soil ........ Flow of Water and Ions to Tile Drains ........... Nitrogen Transformations in Soil ............. Management of Irrigated Soils to Maximize Nitrogen Removal ......................... 11 MATERIALS AND METHODS ................... Introduction ........................ Description of the Site .................. Size, Relief and Soil .................. Plots and Subplots .................... Tile Lines ........................ Sampling Wells ..................... Description of the Simulated Nastewater .......... Preparation ....................... Irrigation ........................ Sampling. . ........................ Soil ........................... Water in Tiles and Wells ................. Phosphate and Potassium vs. Pressure Experiment ..... Plants ......................... Laboratory Analysis .................... Soil ........................... Soil Nitrogen Determinations for the 1978 Growing Season .................. . ..... Denitrification Incubation Experiment ......... Denitrification Assay by Acetylene Inhibition ..... Soil Organic Carbon .................. Hater .......................... Plants .......................... Statistical Analysis .................... III RESULTS AND DISCUSSION ................... Concentration of Ions in Irrigation, Tile Drainage, and Soil Water ...................... Concentration of Ions in Irrigation Water ........ Water and Ions in the Tile Drains ............ iv 56 56 59 Plant Response ...................... 77 Changes in the Soil .................... 87 The Depressive Effect of Grass Upon the NOS-N Concentration 90 IV SUMMARY AND CONCLUSIONS .................. 106 Table 10. 11. 12. 13. 14. 15. LIST OF TABLES Effluent Composition ............... . . . . Mean concentration of ions in simulated wastewater and in water draining from tiles in 1977 and 1978. ..... Annual water drainage from the tiles in 1977 and 1978. . . Estimates of leaching fraction of the individual tiles . . Linear regression and correlation coefficient for the concentrations of PO4-P and K in tile drainage water . . Calculated mean concentration of NOE-N in the solution of soils sampled at indicated depths and water from tile drains,_l978 ................. Influence of fertilization and irrigation rate on the nutrient concentration of grass in two cuttings, l977. . Influence of fertilization and irrigation rate on the nutrient concentration of grass in two cuttings, l978. . Influence of fertilization and irrigation rate on nutrient concentration of corn silage in 1977 and 1978 . Influence of fertilization and irrigation rate on dry matter yield of bromegrass in 1977 and 1978 ....... Yield of corn, as silage and grain in T977 and 1978, as affected by fertilization, effluent application rate and corn hybrid. . . .................. Effect of crop and corn variety on uptake of N, P and K in 1977 and 1978 ................... Effect of irrigation rate and additional fertilization on uptake of N, P and K by corn and bromegrass in 1977 and 1978. . . . . . ................ Concentrations of extractable P and exchangeable K, Ca, Mg and Na in soil samples at given depths (Fall, 1978) . Extractable phosphorus concentrations in the soil profile for Spring of 1973 and Spring and Fall of 1977 and 1978. vi Page 57 58 60 62 66 78 79 8O 82 83 85 16. 17. 18. 19. 20. 21. Mean organic N concentration in soil sampled at three depths and cumulatively to 60 cm ........... 95 Mean NH -N concentrations in soil sampled at indicated depth? for three periods of the 1978 growing season. . 96 Estimated gains and losses of nitrogen by the soil in 1978 ......................... 100 Mean Organic carbon content of surface soil (0 - 15 cm) in 1978 ........................ 103 Mean percent NOS-N lost after 7 days of incubation . . . 104 Comparison of denitrification rates as determined by CZHZ inhibition .................... 105 vii LIST OF FIGURES Figure 1 Page 1 Theoretical distribution of streamlines and equi- potential lines in a tile drained soil (After Kirkham, 1956) .................... 23 2 Simulated secondary municipal effluent experimental area 42 3 Comparison of two equations to describe the relation between height behind a weir and tile water flow rate 45 4 Plot of phosphate and potassium concentration in tile water drainage for the 1977 growing season ...... 67 5 Changes in tile flow rate and concentrations of PO4-P and K in the water draining from tile #11, for a single flow event, 10-24-1978 ............. 68 6 Concentration of NO'-N in the tile drainage water under two crops at two irrigation rates in l977 ....... 91 7 Concentration of NO'-N in the tile drainage water under two crops at two rrigation rates in 1978 ....... 92 8 Mean NO'-N/C1 ratio in soil at indicated depths, Sprin , 1978 . . ................... TOT 9 Mean NOS-N/Cl ratio in soil at indicated depths, Fall, 1978 . . . . . .................... 102 viii INTRODUCTION As every agronomist knows, a weed is a plant growing out of place. Similarly, pollutants are chemicals which find their way into environments where they do not belong. As with weeds, man must determine the anomalousness of the chemicals which make them pollutants. Unlike weeds, man determines, consciously or not, the distribution of pollutants. With this role in deter- mining the fate of pollutants goes both the responsibility and the ability to separate pollutants from the environment. One form of pollution is municipal wastewater. The general problem of the disposal of municipal wastewaters is that when released to rivers and lakes they stimulate growth of aquatic flora. If the chemicals in wastewater could be used to fertilize crops rather than aquatic algae, then effective land disposal could have the additional benefit of increased crop production. This is the strategy behind land application of municipal wastes. Of course, systems in the real world do not always work as they do in theory, but if the idea is sound, a place can be found for the idea. This study is one small part in the process of bringing this promising idea to fruition. CHAPTER I LITERATURE REVIEW Waste Disposal on Land Though the application of various kinds of sewage to land is the object of current scientific investigation, the concept is hardly new. The current interest in land application of sewage is reexamina- tion of an older, though probably less well understood, practice. Holman (1977) cited two earlier examples of land disposal: (l) The use of night soil as fertilizer, an ancient practice that is still observed widely in Asia; (2) in nineteenth century Europe many communi- ties disposed of their sewage by irrigation of crop land. Virtually none of these irrigation systems are in operation today. The encroach- ment of the expanding cities upon the disposal sites was a factor in their disappearance. Though there has been some application of sewage waters to crop land in the United States, the spread of the method was spurred by Congress. In response to growing public concern about water pollu- tion, the Congress enacted the 1972 Amendments to the Federal Water Pollution Control Act which set a national goal to eliminate the discharge of pollutants into navigable waters by 1985. One of the several types of pollution the Amendments addressed was municipal sewage, which is wastewater of residential and non-industrial commercial origin (Metcalf and Eddy, Inc., 1972). The Amendments required 3 municipalities, if they were to receive federal funds for sewage treatment, to consider land application as a possibility (Jacobs, 1977). Many of the wastewaters put on croplands are treated prior to application. There are two general objectives of wastewater treatment: (1) primary treatment is the removal of particulate matter from the wastewater; and (2) secondary treatment is the reduction of the bio- logical oxygen demand (B.O.D.) of the organic compounds in the waste- water by microbiological consumption (Jacobs, 1977). Untreated wastewaters may be very different from city to city. Once treated, however, these wastewaters are remarkably similar among municipalities. For example, in a survey of 809 municipal wastewater treatment plants, Gakstatter and Allum (1978) reported small standard errors of the mean concentrations of phosphorus (P) and nitrogen (N) in treated wastewaters. They identified two basic types of communities, those which attempted to restrict P pollution and those which did not. In communities which did not take measures to limit P pollution, the mean phosphate P concentration was 4.5 ppm and the total P was 6.1 ppm. In those that did, the mean concentration of phosphate P was 1.2 ppm and the mean total P concentration was 1.8 ppm. In the same study, the mean inorganic N content was 6.1 ppm, while the mean total N con— tent was 15.0 ppm. Jacobs cited 25 ppm as a typical organic carbon (C) content in treated municipal wastewater. May and Feinmesser (1977) listed possible advantages of irrigation with wastewater. Three advantages were presented: (1) treated wastewater is an inexpensive source of irrigation water; (2) it 4 can also be a source of nutrients in addition to fertilizer; and (3) wastewater irrigation is an inexpensive final treatment of wastewater. They cite five disadvantages to this approach: (1) whereas irrigation demand is seasonal, municipal wastewater supply is continuous; (2) particulates in the wastewater may clog irriga- tion equipment and soil pores; (3) some soluble constituents of wastewater may be toxic to plants; (4) the range of crops which receive sewage may be limited by health regulations; and (5) the combination of the crop and soil may be unable to remove enough of the nutrients to prevent contamination of the groundwater. Movement of Water and Ions Through Soil Almost all non-gaseous substances that move through soil do so in solution. Hence, to understand the movement of various solutes, including possible pollutants, the flow of water in soil must be considered. In the following review, flow in water saturated soils is emphasized since most solutions to tile drainage problems assume water saturation of the soil. No doubt one motivation of this assumption is to make the problem more tractable. Unsaturated flow problems are more difficult to handle mathematically. It is doubtful that the assumption of saturated flow is much in error, since drainage tiles are inserted to reduce the height of the water table, below which the soil is saturated. } Water moves along gradients of potential energy. Taylor and Ashcroft (1972) have summarized the basics of soil water energetics. The total soil water potential energy (Wt), the relative ability of the water to do work, is the sum of the water's chemical potential 5 (pw or WW) and the potential due to the water's height above a datum, the gravitational potential (wt = WW + W2). The chemical potential, in turn, is the sum of the matric, solute and pressure potentials w m of attraction between soil and water. Since these forces restrict (v = W + vS-rwp). The metric potential (Wm) is due to the forces the soil water, Wm is usually negative, and Wm becomes more negative as the water content decreases. The solute potential (W5) is that due to the presence of solutes. In general, the solute potential decreases as the concentration of solutes increases. In the absence of membranes, solutes have little effect on the total water potential and water flow because their contribution, relative to the other components of water potential, are usually small. In addition, the ability of the soil to restrict the migration of solutes is limited and the effect of solute concentration differences are lessened. The pressure potential (WP) is due to the weight of the overlying water. Unsaturated soils exert no pressure potential other than that due to atmospheric pressure. Water in soils generally is thought to move along gradients of hydraulic potential (Rh), the sum of the matric, pressure and gravitational potentials (Rh = Wm + W + W2). P The cornerstone of the theory of water flow in soil is Darcy's Law (Childs, 1957) A‘l‘h K3: ‘Kw'Zs— (1) where: Q = quantity of water passed across A in time t A = area t = time Kw = hydraulic conductivity 5 = distance This may be rewritten as dWh V=-KWa'§—— (2) where V is the darcian velocity (=Q/At) and the hydraulic gradient is written in its derivative form. Equation (2) can be broken down to its various vector components: BWh 3Tb 3Tb Vx--KW'a—x—,Vy-.-KW‘a‘y—gVz--KW8—z—. (3) The equation of continuity can be written as d_e=_EYE .15. .3_V_z_ t (3x By 32 ) (4) where e is the soil moisture content. Substituting (3) in (4) assuming that Kw is constant and that the soil is saturated (%%-= 0), then azvh + azvh + azvh = 0 ' (5) 3X2 3y2 322 which is Laplace's equation (Kirkham and Powers, 1972). In deriving Laplace's equation, three explicit assumptions have been made, the violation of any brings to question the applicability of the equation for flow through soils. It has been assumed that the soil in question is saturated, that the hydraulic conductivity is uniform throughout the soil and that Darcy's Law, with its associated assumptions, com- pletely describes the flow of water in the soil. These assumptions are true of few if any soils in either the laboratory or the field. Since the equation is widely used to describe water flow through soil, the benefits must outweigh the errors inherent in its use. The advantages of using Laplace's equation are considerable. The equation is used in many other disciplines, so that a problem with the same boundary conditions as a soil problem may have already been solved. Another benefit of the wide, interdisciplinary use of Laplace's equation is that many different approaches are available to aid in its solution to a specific problem. Some solutions of flow to drains using Laplace's equation will be presented later. In order to adequately describe the movement of solutes through soils, a formula must contain an approximation of both the movement of substances through soil without reaction and the interaction of the ion with the soil. One way to do this is to add a term representing this interaction to the differential equation describing flow through porous media. One—dimensional flow of a non-reacting solute in porous media may be represented by — 21.9 JS - vC - D as solute flux darcian velocity solute concentration disperson coefficient distance. where: MUO omsfi .Eaa mp mm: cmpmzmummz Low 2 Peace + Ammv _NN New oem mom ANN _u A__v mmp mpp omp mpp amp az A~.mv m.em “.mm otmm m.ee ~.Ne a: Amy _m_ Nap amp Ne, map ac Aa.ov N.e m.m ~.N o.m e.a x Aao.ov Ne.o N~.o ep.o ep.o am.o a-eoa Amm.Fv mm.w mm.a Ne.m mN.m mp.m z-moz .MMmH Aemv ~_N mom _e~ New mpm _u Ao_v PF. ao_ mm, N_P wep az Am.mv m.mm F._e e.~e 3.5m e.,e a: Amzv mom New m_N N_N mom a8 AN._V ~.m a.m m.m a.m ~.m x Am_.ov ee.o me.o om.o mm.o Ne.P a-eoa AN_._V ea.m Ne.e e~.m oo.~ +me.~ z-moz “mmwfl AEQQV +Amo.oc ems Ea oom-eaau so oo_-eeou Ea oo~-mmaau so oop-mmaee 4, cope: ummcwmco whee cmumzmgmmzi .wea_ eea Reap cw mm—wp Eocw mcwcwecu Lopez cw use copezoummz umme:E_m cw meow mo mcowumcucmucoo com: .N opnmh 59 Since Cl' was used as a tracer to estimate the leaching fraction leaving the root zone of the soil, this variability was unwelcome. Hence, the leaching fraction estimates in 1978 must be considered more valid than those in 1977. As was noted earlier, virtually all N passing through the drainage tiles was in the form of N03. The majority of the N in the irrigation water was non-NOS-N, primarily urea and MHz. The makeup and amount of the non-NOE-N in the irrigation water was not verified and this is a major failing in any interferences or con- clusions made about the behavior of this nutrient once applied to the soil. The indications in the literature are that the urea in soil was rapidly hydrolized to NH: (Tabatabai, 1972) and that NH: was completely and quickly nitrified to NO} in sewage amended soils (Broadbent et al., 1977). In this thesis, it is assumed that the concentration of total N applied was 15 ppm and that the N present as urea and NH: was rapidly converted to N03. The concentration of phosphate P in the simulated secondary wastewater was below the projected soluble P concentration of 2.2 ppm. This discrepancy may have been due to precipitation of P when the salt, fertilizer and water were mixed. How much of the P which was applied to the soil either as a phosphate precipitate, as non-phosphate precipitate or as non-phosphate soluble P is conjecture. Water and Ions in the Tile Drains The calculated volume of water draining through the tiles in 1977 was less than 1978 (Table 3). The difference was substantial and 60 Table 3. Annual water drainage from the tiles in 1977 and 1978. Plot or Block 1977 1978 liters 1 729,173 1,102,998 2 198,909 156,300 3 586,360 937,632 Grass - 100 cm 1,514,442 2,196,930 4 509,099 1,062,535 5 40,977 48,956 6 100,334 110,382 Corn - 200 cm 650,410 1,221,873 7 64,640 77,561 8 407,151 405,758 9 771,707 1,175,193 Corn - 100 cm 1,243,498 1,658,512 10 565,652 968,220 11 535,171 477,438 12 448,023 791,992 Grass - 200 cm 1,548,846 2,237,650 Total 4,957,196 7,314,965 61 cannot be explained by the use of different calibration formulas for the two years, because over the typical range of flow the two formulas are very similar. Another possibility is that the positioning of the floats used to measure tile water height was altered. This explanation is less probable because the increases in 1978 were con- sistent in most tiles with 1977 flow, which suggests an arithmetic variation during data manipulation rather than a physical variation in the field. The results indicate that between 50% to 75% of water applied by irrigation left via the tiles. The theoretical development of tile flow does not allow lateral movement of subsurface water from the area about one tile to another tile or flow beyond the domain of the tiles altogether. Not much lateral movement out of the experimental area was indicated by the data. The high volumes of flow in tiles #1 and #12 did not indicate great amounts of water loss by flow east or west. That the flow east and west was probably small suggests that water movement north and south was also limited. There were wells placed north of the boundary of the experimental area. The water level in these wells was considerably less than that in the wells in the experimental area. Apparently, the loss of irrigation water by lateral movement out of the experimental site was limited. The leaching fraction calculated using the ratio of Cl' con- centration is presented in Table 4. The leaching fraction, the volume of water leached below the tile drains during the portion of the growing season when water was sampled in the tile drains, was calculated by the following formula: Table 4. 62 Estimate of the leaching fraction of the individual tiles (liters/year) Number 1977 1978 0'1wa oxooowcn 11 12 Total 704,347 (123)+ 739,130 (129) 733,096 (128) 1,490,527 (130) 1,952,266 (170) 1,718,741 (150) 925,817 (161) 863,502 (150) 831,521 (145) 1,589,456 (138) 1,454,320 (127) 1,436,868 (125) 14,439,591 (140) liters 669,953 (117) 634,522 (111) 616,732 (107) 1,113,761 ( 97) 1,293,928 (113) 1,189,015 (104) 695,456 ( 83) 592,425 ( 97) . 573,829 (100) 1,061,941 ( 93) 1,079,864 ( 94) 1,057,553 ( 92) 10,587,979 (103) +Number in parenthesis is leaching fraction expressed as a percentage of the amount of irrigation water applied over the year. 63 C1 v=1v L CIL I where: VL leaching fraction (liters) < N I total irrigation volume for the Season (liters) n .....1 II I mean concentration of C1' in the irrigation water (ppm) 0 ._a I L - mean concentration of C1. in the tile drainage water (ppm) The estimates of the leaching fraction during 1977 should be viewed with caution. If we accept the estimates of leaching in 1978, then the amount leached was approximately equal the volume applied. If this is true, then the amount transpired from a plot was about equal to rainfall, which makes sense intuitively. The estimates of leaching volumes were used to calculate nutrient loss by leaching. 2 2, Na+ and Cl', Seven ions: phosphate, N03, K+, Ca+ , Mg+ were monitored weekly in the tile water. Ammonium was evaluated intermittently. The typical NHZ-N content was well below 1 ppm and apparently not above the error inherent in the analytical method. The concentrations of the other seven ions in the tile water were analyzed statistically by irrigation rate and crop. This analysis is presented in Table 2. The differences in the concentration of C1' in the tile water were not consistent from year to year. Given the fact that Cl' is poorly retained by the soil and hardly taken up by crops, attempts to draw conclusions from this data is bound to be spurious. On the other hand, the tendency of Na+ in tile water is clear. The concen- tration of Na+ under plots irrigated at 200 cm per year was higher than those irrigated at 100 cm. This behavior is probably due to 64 the higher amount of the ion which passed through the exchange complex of the soil. 2 2 The concentration of Mg+ , Ca+ , and K+ was significantly different in plots 1, 2 and 3, which were cropped in bromegrass and received 100 cm/year, than in the rest of the experimental area. There is no similar behavior of the other plots irrigated at 100 cm or the other grass plots. Under these three plots, Mg+2 and Ca+2 tended to be lower, whereas the concentration of K+ was substantially elevated. The concentration of NOS-N was less in tile water under grass and also less at the lower irrigation rate. The depression of NOS-N concentrations under grass will be examined in more detail later in this thesis. The concentration of phosphate in tile water was less under grass than under corn. As will be shown later, the corn crop took upmore P than grass and one can only speculate on the mechanisms responsible. Lance (1977), in a study of the removal of sewage water P from soil columns, suggested that plant roots act somehow to keep P compounds in solution. Lance did not demonstrate or suggest how the plant roots were capable of doing this. We have observed, as Karlen (1975) first demonstrated, that the concentration of phosphate in the tile drainage water rose as the flow rate of water in the tile increased. This behavior is con- trary to any model in which sorption-desorption reactions of P in the soil are time dependent. This behavior was so peculiar that I investigated it further. Here, I will present the facts about the 65 [dynamic behavior of phosphate—P in the tile water. Following that, I will evaluate various hypotheses to explain this egregious phenomenon. 1. The phenomenon was the increase and decrease of phosphate P concentration during the tile flow subsequent to an irrigation. 2. The rate of water flow in the tile was highest about 30 minutes after the cessation of irrigation. 3. In 9 of the 12 plots the concentration of phosphate P in the tile drainage water was linearly correlated with K+. (see Table 5 and Figure 4) 4. The concentration of phosphate P in the irrigation water was not similarly related with K+. 5. The concentration of phosphate P and K+ rose together as the flow event progressed. The maximum concentration of both ions fell after the peak. The maximum flow rate was not coincident with the phosphate P and K+ concentration maxima (Figure 5). ‘ 6. This behavior was observed in tiles under both bromegrass and corn. 7. Both the linear correlation between phosphate P and K+ and the flow related vagaries of the two ions, though marked, were less noticable early in the season and became progressively more distinct as the year progressed. 8. Returning to Table 6, the correlation was not significant between the concentration in tile water under plots 1, 2, and 3. The slopes of the regression lines relating the concentration of phosphate P with that of K for these tiles are much less than the other tiles. Unlike most other tile lines in the experiment, we Tabl 66 e 5. Linear regression and correlation coefficient for the concentrations of PO4-P and K in tile drainage water (umoles liter") Tile No. of Samples A+ B r2 1977 l 12 -TTTO4 .007 .011 2 13 - 5.32 .074 .304* 3 13 11.11 -.005 .003 4 l4 - 27.44 .373 .820** 5 13 - 5.10 .242 .644 6 ll - 7.10 .220 .723** 7 12 9.00 .085 .380* 8 13 4.75 .113 .435** 9 10 - 0.90 .157 .871** 10 ll - 4.97 .188 .614** 11 ll - 5.03 .258 .659** 12 12 — 3.54 .234 .700** 1_Z§_ 1 9 .10 .027 .543* 2 9 - .08 .021' .234 3 9 .50 .016 .244 4 9 3.29 .023 .006 5 8 - 3.18 .182 .441* 6 8 - 29.80 .361 .721** 7 7 - 17.74 .240 .688* 8 9 - 11.03 .202 .895** 9 9 - 4.73 .129 .862** 10 8 - 6.71 .145 .940** 11 8 - 2.17 .118 .571 12 8 - 5.65 .169 .653 +(P04) = A + B (K) 67 .commmm mchocm Rump may coo emacwmcu mPTP cw cowpmcucmucoo sawmmmuoq ucm mumcamosa we pope .v mczmwd “Enavx o.o_ o.m_ o.m I o.¢ _ . d o co 00 %@m m m GOOD 0 . . a. . am 6 an N o Ens D DD 0 o o a given. 0 o o L DU 0 .Voo $628 : .62 2.; - a AER: m .02 3:. i o O L m.o ' 50 4O TILE FLOW 30 (Liters/min) 20 10 0 1.0 TILE P04-P (ppm) 0 Figure 5. 68 Changes in tile flow NOD-$50103 I TILE (ppm) rate and concentrations of Fog-P and K in the water draining from Tile #11, for a single flow ev nt, 10-24-1978. 69 cannot say that there is a linear relationship between phosphate P and K+ in tile drains l, 2 and 3. Perhaps part of the lack of correspondence between the two ions in these tile drains is due to the higher concentration of K+ in the tile drainage water. I was unable to find out what caused this behavior of phos- phate P in the tile drainage water. Four hypotheses exist to describe this phenomenon and I will critically examine them below. Whatever mechanism (or mechanisms) is at work clearly involves the soil. The correlation between the concentrations of phosphate and K+ were closer coming out of the soil in the tile drainage water than it was in the irrigation water. In addition, the behavior became more distinct as the year progressed, and the cumulative load of the ions increased. Thus, I discount hypotheses which were based on the thought that water moved through portions of the soil profile with little or no reaction. While the mechanism need not have been instantaneous, it must have accounted for the coincidence of the cessation of irrigation and the peak ion concentration. Adsorption- desorption reactions in soil can be fast, but as far as I know, there is no specific relation between the sorption of P and K. While there are phosphate minerals which contain K, reactions of these minerals tend to be very slow. Since the precision of the behavior increased over the year, I am not inclined to discount the involvement of some sort of adsorption mechanism. Several lines of inquiry can be dismissed quickly. Whatever caused the phenomenon, it was not due to changes in the electrical charge balance of the soil solution. Phosphate and K+ were minor 70 constituents of the soil solution and had opposite charge. Any change in the electrochemical balance that would cause one to increase would tend to decrease the other. The close behavior of the two ions suggests some sort of associated complex with K and phosphate. If an associated complex was the cause, the regression equations suggests that virtually all the P was associated with K and that the molar ratio of phosphate P to K was between 1:6 to 1:5. The 2 association constants for HPO4' and H2P0; with K+ presented by Larsen (1967) suggest only a small fraction of phosphate P would be associated with K. The valences of the three ions, K+, HP04'2, and H2P0£ are not consistent with a ratio of P:K higher than 1:2. Several other suggestions cannot be dismissed so readily. The relative hydrated radius of the two ions would be expected to stay fairly constant. Thus if the two were moving in response to a nonelectrical gradient, one would expect constancy in the ratio of the two ion concentrations. The two ions may be complexed by a larger molecule, possibly organic, which dragged the two ions through the soil solution. Because the organic molecule was larger than most other ions in solution, its flow from soil to tile could be velocity dependent. The first hypothesis to explain the behavior of phosphate P in tile drainage water was developed by Karlen (1975). He argued that the rapid flow of water through sand smears to the drains explained the peak behavior of phosphate in tile drains. In the soil, the argument went, there were sections with a lower ionic adsorption capacity and higher hydraulic conductivity than the rest of 71 the soil. In these smears, the concentration of phosphate and K+ in the soil solution was higher than in the rest of the soil. Since the conductivity was higher, as the irrigation proceeded the contribution of the solution from the smear to the tile drainage water increased. Thus, the concentration of the two ions in the tile water increased during an irrigation. The sand smear hypothesis is consistent with the flow of water through soils which are composed of two commingled portions, each with different hydraulic conduc- tivities. The flow to the tiles, where the maximum flow was found after the cessation of water application is virtually identical to that of flow through macropores in soil (Thomas and Phillips, 1979). In theory, flow through macropores and through sand smears is similar in that the dynamics of flow is governed by two sectors of the soil, each having greatly different conductivities. The hypothesis also poses many considerable failings. The sand smear hypothesis depends upon a convenient geometry in the subsoil. While only two tile drains were studied for the dynamic behavior of phosphate in the water 9 of the 12 tile drains showed significant correlations between phosphate and K indicating that, if the two behaviors were linked, the behavior was common in the field. Therefore, in a very heterogenous soil, if they were the cause of the behavior, sand smears must make a sizable portion of the flow to most of the tiles. Further, the soil used by Sharpley et al. (1977) in which the same behavior is observed was homogeneous probably without smears, sandy or otherwise. The model provides nothing to explain the correspondence of the concentrations of 72 phosphate and K in the tile. Lastly, the model does not explain the repetitiveness of the behavior. To show why the model does not, the behavior of hypothetical model will be examined. Begin with two sectors of the soil, A and B. Both are connected to the tile drain and water flows through each to the tile drain. Assume that the conductivity and ion concentration is greater in A. Also assume that the volume of B is substantially greater than that of A. After one irrigation, the behavior would be that observed in the field, increasing flow and ion concentration in the tile. After irrigation stops, though, we can expect much of the solution in B to replace that in A. Thus, with the second irrigation, no appreciable change in the ion concentration would be observed. There- fore, the explanation is neither internally consistent nor does it adequately explain much of the behavior which has been observed. The second explanation can be called the particulate hypothe- ses. According to this hypothesis, the behavior of P in tile lines was based upon the nature of flow in the tile drain. Phosphorus and K were adsorbed by minerals in the sediment of the tiles. As the flow rate in the tiles increased, so did turbulence, and sediment was suspended in the tile drainage water. Phosphorus and K previously adsorbed upon mineral surfaces were released into solution and the concentration of the two ions increased. This hypothesis was implied by Sharpley et a1. (1977) to explain the increase in P concentration with the increase in tile drainage water flow. The hypothesis was presented obliquely. They noted that several investigators had observed a correlation between flow rate in rivers and runoff and 73 the concentration of ions, including P. This was believed to be due to an increase in turbulence concomitant with the increase in flow. Turbulence caused the sediment to be brought into suspension. Their presentation may be faulted on two counts. (1) One of the articles they cite about the correlation of flow and ion concentration (the only one I was able to locate) showed a decrease in ion concentration in a river with an increase in flow. (2) While they present the general observation that "...an increase in suspensionate was obser- ved in the tile," they failed to demonstrate that P associated with particulate matter was responsible for the increase in P concentra- tion in tile water. This criticism is due largely to the fact that the Sharpley article is the only one on this aspect of tile flow to appear, and I have scrutinized it on an aspect fairly far removed from the main theme of the paper. The hypothesis was presented in passing and probably was not considered in great detail by the authors. Aside from the objections of the hypothesis inherent in the presentation of the article, there are two other criticisms. (l) The maximum tile flow rate, and I assume the maximum turbulence, and the peak concentra- tions of P and K do not coincide. (2) Since the chemistry of the ad- sorption or precipitation of P and K in sediments has not been shown to be related, the correspondence in the tiles draining the Conover study soil is unexplained. A third hypothesis of the ion behavior in the tiles is based upon different path lengths of the soil water must have traveled to the tiles drains. Water and phosphate flowing from portions of the soil near the tile moved quickly into the tile. The concentration 74 of phosphate in the soil solution flowing from portions near the tile drain was higher than in solutions flowing from portions further from the tile drain. This quickly flowing, high concentration solu- tion caused a spike in the tile water concentration of phosphate during an irrigation. This theory, like the sand smear theory, depends upon con- tributions of water from different sectors of the soil with different P and K concentrations. Two facts weigh in its favor. (l) P concen- tration in soil solution decreases with the increase in distance traveled and (2) according to models presented by Childs (1947) and Kirkham (1964) most of the water which is delivered to the tile along the shortest path lengths enters the tile soon after the end of water application. There is nothing to explain such persistent correlation between the phosphate and K+ in the tile drainage water. The last hypothesis to explain the peak beahvior of phosophate assumes that the soil about the tile drain acted as a semipermeable membrane allowing water to pass more freely than ions in solution. In the soil near the outside of the tile, the water pressure dropped dramatically from that due to the hydrostatic head to atmospheric pressure. This difference in water pressure increased as the irri- gation proceeded and the water table rose. Increases in the pressure difference decreased the ability of the soil to act as a membrane, to restrict the passage of ions relative to water. More ions passed through the portion of soil close to the tile relative to the flux of water and the concentration of the ions in the tile drainage water increased. All ions behaved this way, only the behavior of 75 phosphate and K were discernable because their concentrations were so much less than the rest. Because little is known about the subject, it is difficult to evaluate the possibility that the soil about the tile acted as a semipermeable membrane. But, if one discounts macro-physical explanations such as the sand smear hypothesis and is unable to find satisfactory explanations in the sorption behavior of phosphate, there are few avenues left to follow. Studies in soils and clays have shown changes in the relative flux of ions to the flux of water due to changes in hydraulic head. To test this possibility, I measured the concentration of phosphate and K in leachate from soils maintained at four different hydraulic heads. No tendency was observed. The soil had been screened, the phosphate adsorption capacity had increased and the phosphate concentration in the effluent was very low. The field data has shown that the behavior was more pronounced the longer the soil has been irrigated with phosphate solution. Perhaps not enough P had passed through the soil in the laboratory to really test if hydraulic head has an effect upon ion concentration in the effluent water. I suspect that the variable head experiment did not adequately test the effect of pressure on phosphate and K+ concentration in the effluent. A second fact supporting membrane hypothesis is that the concentrations of phos- phate and K+ were strongly and consistently related. No other expla- nation presented here, save the existence of a complexing molecule, can explain this fact. We can expect that the hydrated radii of 2 HP04' , H2P04 and K+ remained consistent in the soil solution and if 76 they are moved by non-electrical gradients, the ratio between them .in solution would be consistent. If the cessation of irrigation affected the concentration of ions in the tile, and all information I have gathered supports this argument, then whatever mechanism was responsible, it must explain the speed and consistency of the soil system response. Looking only at the chemistry of P in soil we see that mineral dissolution and chemical desorption are too slow, as is chemical adsorption. Only physical adsorption or possibly membrane behavior of the soil react in times as quickly as we observed in the field. Several formidable arguments go against this explanation. It has not been shown that the membrane behavior of soils is affected by pressure gradients as small as would be found at the tile drain. It has not been shown that soils act as a membrane with mixed electrolyte solutions. Indeed, it has not been shown that soils act as membranes at all, only pure clays have been used in experiments thus far. It has not been shown that the movement of phosphate is affected by this aspect of soil behavior. In fact, few anions have been investigated. The membrane hypothesis and the other three, are unable to adequately explain the peak behavior of phosphate and K+ in the tile drainage water. As noted above, the mean concentrations of N05 in tile drainage water under grass was lower than in those under corn. Thomas and Barfield (1974) have contended that, because flow to tile lines is through aerobic soil, denitrification is reduced and the concentration of N03 is greater in tile drainage water than in other subsurface water. 77 Using the measured soil N03 concentration and the moisture content of soils collected in 1978, I calculated the N03 concentration in the soil solution. The soil solution N03 content calculated by this method should be more accurate than with most other ions in solution because N03 is weakly attracted by most soils. The mean concentration of N03 in soil solution in 1978 are presented in Table 6, as well as the mean drainage water concentration for the ion that year. The tile drainage water concentration were consistently less than those calculated for the soil solution. While these data do not establish the drainage water as a reliable estimate of leachate N03 concentration, they do run counter to the argument by Thomas and Barfield that the N03 concentration is typically much higher in the tile drainage water than in leachate from the soil. Plant Response The application of sewage to cropland has two aims; to remove potential pollutants and to produce a usable crop. The plant response in our experiment must be judged by similar criteria. Here three categories of crop response to irrigation rate and additional fertil- izer will be presented; nutrient quality of the crop, crop production and annual nutrient removal by the crop. The nutrient concentration of the bromegrass was consistently affected only by the irrigation rate (Tables 7 and 8). The calcium concentration of the bromegrass was higher in the plots irrigated at 200 cm/year. 78 Table 6. Calculated mean concentration of NOR-N in the solution of soils sampled at indicated depths a drains, 1978. d in water from tile NOS-N Concentration Depth Grass-100 cm Grass-200 cm Corn-100 cm Corn-200 CEL_ —( cm)-— (ppm) 0- 15 14. 25.8 27.9 27.7 15- 30 16. 19.0 26.1 37.5 30- 60 12. 12.8 18.4 29.0 60- 90 10. 11.4 15.0 19.6 90-120 13. 9.8 12.9 18.2 120-150 11. 8.4 11.5 18.5 150-210 10. 7.8 11.4 16.6 210-270 11. 9.7 12.3 17.7 Tile drains (120 cm) 3. 5.4 6.6 8.5 79 Table 7. Influence of fertilization and irrigation rate on the nutrient concentration of grass in two cuttings, 1977. Nutrients Treatment N P K . Ca Tfig I - __ First cutting (percent of dry weight) Check 1.81 .49 1.77 .64 .24 N 2.28 .55 2.29 .72 .34 K 1.73 .43 1.70 .62 .23 NK 2.43 .52 2.16 .69 .31 LSD (0.05) (.47) (.07) (.31) (NS) (NS) 100 cm 2.02 .47 1.65 .58 .20 200 cm 2.11 .53 2.70 .76 .36 LSD (0.05) (NS) (NS) (NS) (NS) (NS) Second cutting Check 1.97 .67 1.54 .72 .16 N 2.06 .64 1.52 .70 .16 K 1.95 .65 1.64 .76 .18 NK 2.10 .64 1.56 .70 .16 LSD (0.05) (NS) (NS) (NS) (NS) (NS) 100 cm 1.86 .60 1.48 .64 .16 200 cm 2.17 .70 1.05 .80 .17 LSD (0.05) (.19) (NS) (NS) (.05) (NS) 80 ' Table 8. Influence of fertilization and irrigation rate on the nutrient concentration of grass in two cuttings, 1978 Nutrients Treatment N P K Ca ’Mg (percent of dry weight) First cutting Check 1.26 .27 2.16 .30 .12 N 1.25 .27 2.10 .29 .10 K 1.23 .26 2.20 .29 .11 NK 1.33 .26 2.13 .28 .10 LSD (0.05) (NS) (NS) (NS) (NS) (NS) 100 cm 1.26 .27 2.15 .28 .10 200 cm 1.28 .26 2.15 .30 .11 LSD (0.05) (NS) (NS) (NS) (.02) (NS) Second cutting *Check 1.26 .42 2.38 .54 .19 N 1.25 .40 2.44 .67 .26 K 1.23 .43 2.13 .56 .20 NK 1.33 .39 2.32 .61 .22 LSD (0.05) (0.07) (.02) (0.28) (0.07) (.07) 100 cm 1.26 .41 2.45 .57 .23 200 cm 1.28 .41 2.18 .62 .21 LSD (0.05) (NS) (NS) (0.20) (0.05) (NS) 81 As shown in Table 9, additional fertilizer had only one effect upon nutrient concentration in corn. Nitrogen fertilization increased N concentration in the crop. Phosphorus concentration was higher in corn grown in plots receiving the higher irrigation rate. The dry matter yield of bromegrass was increased by additional irrigation and fertilizations. Table 10 shows that only the combination of N and K fertilization consistently increased dry matter production. Irrigation rate did not have a significant effect on dry matter production or grain yield of corn, as shown in Table 11. Of the two corn varieties grown in the experiment, Pioneer 3780 yielded more silage and grain than did Funks 4444. Nitrogen fertili- zation, but not additional K, increased grain and silage production. The major determinant of nutrient removal was dry matter yield of the crop. Corn took up more N, P and K than did bromegrass (Table 12). Increased irrigation rate stimulated removal of N, P and K by bromegrass and increased the removal of P by corn (Table 13). Phosphorus removal was unaffected by additional fertilization. Of the two corn varieties, Pioneer 3780 removed more of the nutrients than did Funks 4444. More N was added to the crops as fertilizer than was removed by the induced increase in production. The increase in N uptake by corn in subplots receiving additional N fertilization was a 40.9 kg/ha, the increase in subplots receiving both N and K was 52.9 kg/ha. In subplots cropped in bromegrass the increases in N removal for these treatments were 30.5 and 65.2 kg/ha 82 Table 9 . Influence of fertilization and irrigation rate on nutrient concentration of corn silage in 1977 and 1978. Nutrients Treatment N P K . Ca Mg 1977 -percent of dry weight Check .96 . .48 1.15 .31 .20 N 1.08 .43 1.14 .29 .19 K .94 .43 1.11 i .28 .20 NK 1.08 .39 1.13 .27 .18 L50 (0.05) (.05) (.05) (NS) (NS) (NS) 100 cm 1.00 .40 1.14 .27 .20 200 cm 1.03 .47 1.12 .30 .19 LSD (0.05) (NS) (.07) (NS) (NS) (NS) 1978 (Check 1.08 .33 1.22 .34 .24 N 1.09 .32 1.11 .32 .25 K 1.03 .33 1.21 .33 .24 NK 1.12 .34 1.23 .36 .25 LSD (0.05) (0.07) (NS) (NS) (NS) (NS) 100 cm 1.02 .27 1.11 .28 .21 200 cm 1.14 .38 1.27 .39 .27 LSD (0.05) (0.05) (.05) (.14) (.05) (.03) 83' Table'H). Influence of fertilization and irrigation rate on dry matter yield of bromegrass in 1977 and 1978. 1977 1978 First Second First Second Treatment cutting cutting, Total cutting cutting Total (metric tons/ha) 100 cm Check 2.69 1.40 4.09 4.95 2.32 7.27 N 4.52 1.77 6.29 5.31 3.66 8.98 K 2.63 1.22 3.85 4.64 2.69 7.33 NK 7 4.68 1.59 6.17 5.68 4.15 9.83 LSD (0.05) (1.59) (NS) (NS) (NS) 200 cm Check 5.50 1.59 7.08 5.80 4.34 10.14 N 5.68 1.34 7.02 5.37 4.40 9.77 K 4.34 1.65 5.98 5.86 4.82 10.69 NK 8.06 1.53 9.59 5.74 5.19 10.93 LSD (0.05) (1.59) (NS) (NS) (NS) Fert. Treat. Av. Check 4.09 1.47 5.56 3.60 5.07 8.67 N 5.07 1.53 6.59 4.52 4.88 9.40 K 3.48 1.22 4.70 3.66 5.31 8.97 NK ; 6.29 1.59 7.88 4.88 5.50 10.38 LSD (0.05) (1.10) (NS) (0.55) (0.55) Water Treat. Av. 100 cm 3.60 1.53 5.13 5.13 3.18 8.30 200 cm 5.86 1.40 7.27 5.68 4.70 10.38 LSD (0.05) (1.59) (NS) (0.55) (0.55) Table 11. Yield of corn, as silage and grain in 1977 and 1978, as affected by fertilization, effluent application rate and corn hybrid. Silage Yield+ Grain Yield Treatment 1977 1978 1977 1978 —(metric ton/ha)- ——-(quintal/ha)——-— Fertilization Check 14.9 13.4 85 58 N 17.3 16.7 107 97 K 15.7 13.8 85 59 LSD (0.05) (1.3) (1.4) ( 8) (4) Water rate 100 cm 17.0 15.3 99 75 200 cm 16.3 15.4 95 8O LSD (0.05) (NS) (NS) (NS) (NS) Corn variety Pioneer 3780 17.6 16.4 107 86 Funks 4444 15.7 14.2 86 7O LSD (0.05) (1.3) (1.0) (3) (5) +Dry weight. 85 Table 12. Effect of crop and corn variety on uptake of N, P and K in 1977 and 1978. Nutrient Uptake Treatment N P - K (kg/ha) Crop (1977) Bromegrass 121.0 31.6 113.2 Corn 170.8 71.2 185.9 LSD (0.05) (27.1) (5.8) (18.3) Variety (1977) Pioneer 3780 178.8 68.4 172.6 Funks 4444 162.8 74.1 199.1 LSD (0.05) (17.4) (6.7) (15.4) Variety (1978) Pioneer 3780 179.0 54.7 195.7 Funks 4444 154.6 46.3 169.9 LSD (0.05) (20.5) (7.4) (23.9) 86 Table 13. Effect of irrigation rate and additional fertilization on uptake of N, P and K by corn and bromegrass in 1977 and 1978. Crop Uptake Corn ‘ Brome rass Treatment N P K N E K 1977 (kg/ha) Irr. Rate 100 cm 169.3 67.1 178.0 93.4 24.3 76.5 200 cm 172.2 75.4 193.7 144.0 37.8 143.7 LSD (0.05) (NS) (6.4) (NS) (38.2) (7.3) (29.2) Fertilization Check 144.8 70.5 169.2 102.2 31.1 99.7 N 188.4 74.4 196.5 132.7 34.9 129.8 K 149.5 67.3 169.2 80.5 22.8 79.3 NK 200.6 72.8 208.6 167.4 38.3 144.3 LSD (0.05) (15.1) (NS) (17.6) (47.8) (5.3) (52.7) 1978 Irr. Rate 100 cm 157.9 41.6 169.3 200 cm 175.7 59.4 196.3 LSD (0.05) (NS) (5.7) (23.8) Fertilization Check 145.3 44.4 165.2 N 183.4 52.8 183.2 K 143.3 45.6 168.0 NK 195.3 59.2 214.8 LSD (0.05) (24.5) (10.0) (32.1) 87 respectively. Since both crops received 112.1 kg/ha N as additional fertilizer 50% or less of the additional N was not taken up by the crops. The efficacy of additional N fertilization must be judged by two factors: (1) the load of fertilizer N finding its way to the groundwater and (2) the economic benefit from the increased crop production. As will be shown in the next section, much of the added N not removed by the crop did not find its way to the ground- water. This disparity was most pronounced under grass. The danger of N pollution may be less than indicated by incomplete N removal by the crop. Changes in the Soil During the 1977 and 1978 seasons, the chemical components measured *2 and Ca+2 and soluble 01’) (extractable P, exchangeable Na+, K+, Mg changed little. Table 14 presents the concentration of these ions in Fall 1978. The distribution of extractable P in the soil profile, shown in Table 15, varied greatly from time to time but no real trend was discernible in 1977 and 1978. Comparing the concentrations of extractable P in 1977 and 1978 with those in spring 1973, it is clear that considerable amounts of P had accumulated in the soil profile since the beginning of the experiment. The only obvious change in the profile distribution between 1977 and 1978 was a small increase in the P concentration in the lower depths. Calcium and Mg+2 concentrations varied greatly from sample to sample but showed no tendency for accumulation or loss. Potassium, on the other hand, had a higher concentration in the soil profile 88 Tablelll. Concentrations of extractable P and exchangeable K, Ca, Mg and Na in soil samples at given depths (Fall, 1978). Depth (cm) P K Ca Mg Na {09/9 soil) 0 - 15 126 72 1655 242 140 15 - 30 36 69 1351 234 135 30 - 60 14 71 1596 291 147 60 - 9o 7 62 2410 314 175 90 - 120 3 49 3092 279 129 120 - 150 2 31 3072 201 96 150 - 210 1 30 3164 194 95 210 - 270 1 35 4200 193 89 89 Table 15 , Extractable phosphorus concentrations in the soil (profile ' for Spring of 1973 and Spring and Fall of 1977 and 1978. Depth (cm) 4-73 4-18-77 11-11-77 4-18-78 11-22-78 (Hg P/g soil) 0 - 15 9 107 98 109 126 15 - 30 8 77 44 65 36 30 - 60 5 7 10 13 14 60 - 90 3 4 4 6 7 9O - 120 3 2 3 5 ' 3 120 - 150 2 1 3 3 2 150 - 210 2 1 2 2 1 210- 270 2 1 2 2 1 90 each spring than the subsequent fall. The concentration of K+ in the soil in spring 1978 were greater than those in fall 1977. Sodium behaved the opposite of K+. The concentration was higher in fall than spring. This is consistent with a build-up of Na+ during the irrigation season fellowed by leaching during the winter and spring snow melt. Surface samples taken in each subplot showed little real variation. Each year, the subplots received the same fertilizer treatment so any effects which were additive would have been able to accumulate. The irrigation rate affected K+ accumulation in samples taken in 1978. The K+ concentration was less in the plots a+2 and irrigated at 200 cm/year. In 1978, the concentration of K+, C Mg+2 were lower in the corn plots. Consistently, the K+ concentration was greater in soil from subplots receiving additional K fertilizer. The Depressive Effect of Grasses Upon the Concentration of N05 As the data presented in Table 2 show, the concentration of NO} in tiles under grass was less than that under corn. These mean values, while statistically significant, do not tell the whole story. As can be seen from Figures 6 and 7, the concentration of N03 in tiles under corn was much more variable than that under grass. The concentration of N03 under grass was fairly constant throughout the growing season, whereas the concentration of the ion under corn was typically quite high in the spring and fall and only approached the concentration found in the tiles under grass during the middle of the season, when the growth of corn was greatest. The mean concentrations of N03 in wells under grass and corn point out the disparity between the .Kemp ea mapaa cave leave»? 03» pm maoeu oz» cone: Lopez mmmcwmcu mp?» mg» cm Zimoz mo cowpmcpcmucou .o acumen Dam gem omm omm DEWITY _oap cup om, om_ d u d - - - a - \‘IIIIIIIII'II'I’ l-IIIIII.II.III-Ill\“'llll.lullllll|l \\ (III-II 1 llllmm