Aust. J. Soil Res., 1996, 34, 789-802 Ammonia volatilisation from soil irrigated with urban sewage effluent C. J. SmithA, J. R. ~ r e n e and ~ ~ W. , J. BondA A Division of Soils, CSIRO, P O Box 639, Canberra, ACT 2601. Division of Plant Industry, CSIRO, P O Box 1600, Canberra, ACT 2601. Abstract Losses of ammonia (NH3) following sewage effluent irrigation of pasture were measured under different climatic conditions a t Wagga Wagga, New South Wales. Ammonia volatilisation was measured by the micrometeorological mass balance technique using 2 different passive samplers, and by an indirect technique based on the measurements of ammoniacal-N ( N H ~ S N H ~ ) concentration, pH, and temperature of the soil solution in the 0-3 mm soil layer, and wind speed a t 1a2 m above the soil surface. Maximal NH3 emission rates were measured directly following the effluent-irrigation. There was reasonable agreement between the 2 different passive gas samplers used to measure NH3 volatilisation. The NH3 volatilised was well related to the product of wind speed and the equilibrium ammonia concentration (calculated from the soil solution measurements) as was found in other studies. In addition, NH3 flux density was strongly related to evaporation; that is, when the water (effluent) evaporated NH3 was lost t o the atmosphere. Under high evaporative conditions, a maximum of 24% of the ammoniacal-N in the effluent was lost by volatilisation within 2 days of application. Additional keywords: nitrogen loss, micrometeorology, gas exchange. Introduction Ammonia (NH3) gas is emitted into the atmosphere following the application of alkaline-producing nitrogenous fertilisers (e.g. urea) or from surface-applied animal wastes (Hoff et al. 1981; Smith et al. 1988; Schilke-Gartley and Sims 1993; Gordon and Schuepp 1994; Sherlock et al. 1995). Volatilisation rates are affected , the by ( 2 ) the hydrolysis of the organic N compounds to ammonium ( N H ~ )(ii) exchange between N H in ~ solution and cation exchange sites in the soil, and ~ NH3 in the soil solution, and NH3 in the (iii) the equilibrium between N H and gaseous phase (Leuning et al. 1984; Freney et al. 1985; Sherlock and Goh 1985; Rachpal-Singh and Nye 1986; De Datta et al. 1989; Clay et al. 1990). Both the hydrolysis and equilibrium reactions are temperature-dependent. Models of NH3 volatilisation (Sherlock and Goh 1985; Rachpal-Singh and Nye 1986; Jayaweera and Mikkelsen 1990a, 1990b; Jayaweera et al. 1990) predict a diurnal cycle of volatilisation resulting from the diurnal changes in soil temperature. The highest rates predicted correspond to maximum soil temperatures. Similarly, wind speed has a major impact on NH3 volatilisation, with maximum emission corresponding to the period with the highest wind speed. Ammonia volatilisation from the surface application of wastes has resulted in losses ranging from 10 to 99% of the applied N, depending on the edaphic and environmental factors experienced following application (Beauchamp et al. 1982; Schilke-Gartley and Sims 1993). Volatilisation from urine or animal dung patches C. J. Smith et al. of grazing animals has long been recognised as an important pathway for N loss from the soil-plant ecosystem (Denmead et al. 1974; Ball et al. 1979; Sherlock and Goh 1985; Sherlock et al. 1989). Because of the alkaline characteristics of sewage effluent (Feigin e t al. 1991), NH3 volatilisation may be an important pathway for N loss when the material is applied to land surfaces. Volatilisation models (Sherlock and Goh 1985) predict considerable NH3 volatilisation following irrigation with sewage effluent, but few data are available to validate these predictions. This paper reports on the measurement of NH3 volatilisation following the irrigation of soil with urban sewage effluent. Ammonia volatilisation was measured with 2 different passive samplers, and an indirect method in which the flux was calculated from measurements of ammoniacal-N in the 0-3 mm soil layer, surface pH, temperature of the soil surface, and wind speed measured at 1 . 2 m above the soil surface. The results from the indirect method were compared with the micrometeorological method for measuring NH3 loss (Leuning e t al. 1985). Material and methods Field site and efluent chemistry The field experiment was conducted adjacent to the sewage treatment works for the Royal Australian Air Force a t Forest Hill, approximately 15 km east of Wagga Wagga, New South Wales. The soils a t the site are classified as a Red Chromosol (Isbell 1993), previously known as a red podzolic (Stace et al. 1968) or Rhodoxeralf (Soil Survey Staff 1992), a Red Kandosol (red earth or Ustorthent), and an intergrade between the 2 soils. Some properties of the surface soil (0-0.05 m) are pH(1: 5 soil :water) 7.3; pH(1:5 soil :0 . 1 M BaCl2) 5.3; cation exchange capacity (CEC) 10 cmol,/kg; total N 1.49 g/kg; and total C 22.8 g/kg. The area had been cultivated and sown to wheat (Triticum aestivum) from 1979 to 1981, followed by an improved pasture phase. The pasture was top-dressed with single superphosphate (150 kg/ha) in 1988 and with Calphos (100 kg/ha) in 1990. Secondary treated effluent was obtained from the sewage treatment works. Treatment included initial filtering to remove grit and processing in an oxidation pond in which oxygen, produced by surface aeration and algae through photosynthesis, is used by bacteria to decompose organic matter. Chemical properties of the effluent were pH 8.3; EC 1.26&0.04dS/m; ammoniacal N 1 1 . 8 3 f 0 . 3 mg/L; NO:-N, 1.24~0.07mg/L; Kjeldahl N, 19 mg/L. Ammonia volatilisation Ammonia volatilisation from a 25-m-radius circular area was measured in 2 experiments following the application of sewage effluent by sprinkler irrigation in December 1994 and January 1995. A total of 5 l f 7 mm of effluent was applied on 6 December 1994 and 41k5 mm was applied on 17 January 1995 between 0100 and 0700 hours. Measurements of NH3 volatilisation commenced immediately after irrigation and continued for 4 days. In January, the NH3 fluxes were low initially and became negligible following 5 mm of rainfall between 1800 and 0800 hours (overnight) on 18 January. On 18 January between 0900 and 1000 hours, urea was broadcast evenly by hand onto the circular area a t a rate equivalent to 80 kg N/ha to provide conditions likely to yield high NH3 fluxes. The vertical flux density of NH3 was determined by the procedure described in Smith et al. (1988) and Sherlock et al. (1995), using the ammonia sampler developed by Leuning et al. (1985). Samplers were placed on a mast at the centre of the circular area, 0.2, 0.4, 0.8, 1.2, 2.4, and 3.6 m above the soil surface, and changed 3 times daily. Emission was measured for the periods 0800-1300 hours, 1300-1800 hours, and 1800-0800 hours (overnight). Background measurements were made with samplers placed on a mast located a t the upwind side of the treated area. In addition, NH3 flux was determined using the passive samplers (Ferm tubes) described by Schjoerring et al. (1992) and manufactured by Mikrolab Aarhus A/S, Axel Kiers Vej 34, Ammonia volatilisation from effluent-irrigated soil DK-8270 Hoejdjerg, Denmark. The passive samplers were coated with oxalic acid (Schjoerring et al. 1992) and mounted at 0.2, 0.4, 0.8, 1.2, and 2 . 4 m above the soil surface on 4 masts placed at the corners of the largest square area that could be accommodated within the circular area. At each height, 2 passive samplers were mounted, one with the stainless steel disc facing towards the treated area, and the other with the disc facing away from the treated area (Schjoerring et al. 1992). Ammonia emitted from the circular area was collected through the open end of one sampler and through the stainless steel disc of the other sampler. The samplers were changed at 24-h intervals and returned to a mobile laboratory. High purity deionised water (3 mL) was added to each tube in order to dissolve the ammonium oxalate on the internal surface. The ammonium concentration of the resulting solution was determined by measuring the emerald-green colour (660 nm) formed by reaction of ammonia with sodium salicylate, sodium nitroprusside, and sodium hypochlorite at pH 12.8-13.0 (Technicon Traacs 800, Method No. 825-87T). The Technicon procedure was followed except the buffer was made by dissolving 58 g NaOH, 20 g ethylenediaminetetraacetic acid (disodium salt), 50 g sodium potassium tartrate, and 2 mL acetone in water. The solution was cooled to room temperature and diluted to 1 L. The flux density of NH3 was calculated using the equations given by Schjoerring et al. (1992). Indirect procedure for calculating NHaemission The driving forces for the volatilisation of NH3 are the difference between the NH3 concentration in equilibrium with the soil solution and that in the atmosphere, and wind speed (Freney et al. 1985; Sherlock et al. 1995). Therefore, the calculated vertical NH3 flux (F) is given by where k is an exchange coefficient, u, is the mean wind speed at the reference height (z), p, is the NH3 concentration a t height (z), and p, is the equilibrium NH3 concentration a t the soil surface. Denmead (1983) and Freney et al. (1985) have shown that, for an actively volatilising surface, p, is very much less than p,, thus p. can be set to zero in equation 1. The calculation of p, requires measurements of the solution ammoniacal-N concentration, pH, and temperature T ( O K ) and is obtained from the following equations (Leuning et al. 1984; Freney et al. 1985): Because of the difficulty of extracting the soil solution from the surface layer, we determined the surface soil pH with a flat surface electrode, surface soil temperature with thermocouples, and soil moisture and extractable NH;-N in the 0-3 mm layer by standard methods (Smith et al. 1988). Soil temperature was measured a t the surface and at 2.5, 5.0, 7.5, and 10 cm depths within the soil profile a t 2 sites within the treated area. The surface soil temperature sensors were installed by pushing a steel needle upwards into the vertical soil face of the small pit used for the installation of the thermocouples, at an angle of about 30' to the horizontal. 5 The probes were pushed into the preformed holes so that the tip of the probe was ~ 0 . mm below the soil surface. The other probes were installed horizontally into the vertical soil face of the installation pit. At the beginning and end of each NH3 sampling period, a flat-surface electrode and portable pH meter were used to measure the surface soil pH a t 8 locations upwind of the central NH3 sampling mast. These values were converted to [H+] concentrations to enable the calculation of the average pH for a particular sampling period. Two small soil cores (22 mm i.d.) were taken a t the 8 locations, and immediately separated into 0-3, 3-7, and 10-20 mm depth sections. In December, only the 0-3 mm depth section was taken. The samples were returned immediately to a field laboratory a t the site and C. J. Smith et al. extracted with 20 mL of 2 M KCl. The suspensions were filtered and the ammonium and nitrate concentrations of the filtrate were determined using a segmented flow analyser (Alpkem 1992). Soil moisture was determined on a second core taken a t each location by drying the samples a t 105OC. Mean wind speeds were measured in duplicate with cup anemometers positioned 1.2 m above the soil surface. - 3- 2z : n m -0 2- - - I" - z -: - Fig. 1. Cumulative NH3 loss measured with the samplers developed by Leuning et al. (1985) (e),and the samplers and procedures described by Schjoerring et al. (1992) (a). (a) Effluent applied in December, (b) effluent applied in January, and (c) urea applied in January. - 0 C - 1- m 3 5 1 I O O 17Jan95 18Jan95 I I 19Jan95 I I 20Jan95 Batch isotherms Batch exchange isotherms for N H were ~ determined in solutions having a constant positive charge concentration of 30 mmol,/L. Calcium chloride was used in the solution t o maintain the charge because Ca was the dominant exchangeable cation. A total of 24 different solutions with NH; concentrations ranging from 0 to 30 mmol,/L were used and measurements for each N H t concentration were carried out on duplicate soil samples. Each solution (20 mL) was equilibrated with 2 g of soil by shaking for 1 h on an end-over-end shaker. After equilibration, the suspension was centrifuged and the supernatant analysed for NH:. Soluble N H was ~ removed from the soil ~emainingin the centrifuge tube by shaking for 30 min with 20 mL of 70% ethanol (w/w), centrifuging at 2000 G for 10 min, and discarding the supernatant. The soil was then extracted twice by shaking for 1 h with 20 mL of 2 M KCl. Exchangeable N H ~ was determined on all the 2 M KC1 extracts and summed. The adequacy of the 1 h equilibration time was confirmed by shaking a series of tubes using the above procedure for 1, 2, and 3 h. Ammonia volatilisation from effluent-irrigated soil Evaporation Evaporation of water from the circular area was measured using PVC cylinders, 0.154 m i.d. by 0.285 m long, carefully pushed into the soil so that the tops of the cylinders were level with the surface (Leuning et al. 1994). The cylinders containing the soil (lysimeters) were removed and a plastic base was attached to the bottom. Each lysimeter was placed in a plastic bag that was sealed to the outside of the lysimeter with tape. An oversize sheet metal cylinder (NO. 17 m i.d.; 1 mm wall thickness) was inserted into each cavity, the soil was excavated from within the cylinder, and a plastic sheet was placed on the floor of the cylinder to prevent soil adhering to the lysimeter when it was returned to the field. Plants within the cylinders were sprayed with glyphosate a t the beginning of the measurement period in order t o minimise water loss by Paterson's curse (E. lycopsis L.). The lysimeters were weighed, t o a precision of 0 . 1 g, a t 0800, 1300, and 1800 hours each day. A new set of 2 lysimeters was extracted each day, or after rainfall, to minimise the effect of extraction of water by the plant roots in the undisturbed soil. Fig. 2. Ammonia flux density (histograms) and cumulative ammonia loss ( 0 )following the application of effluent and urea t o pasture in December and January. The ammonia flux density was measured using the sampler developed by Leuning et al. (1985). (a) Effluent applied in December, (b) effluent applied in January, and (c) urea applied in January. Results and discussion The exposure period chosen for the study with the Ferm tubes was 24 h because of the low flux density of NH3 and the small amount of NH3 collected by these C. J. Smith et al. tubes per hour (Schjoerring 1995). Although we were unable to measure the NH3 flux with the Ferm tubes at periods <24 h, there was good agreement between the rates of NH3 emission measured by the 2 micrometeorological methods (Fig. 1). Lower flux densities can be measured with the ammonia sampler developed by Leuning e t al. (1985), and thus, shorter exposure periods can be used. The longer the period of exposure, the greater the risk of wetting of the internal surface of the Ferm tubes during periods of heavy rainfall in combination with high winds (Schjoerring 1995). Furthermore, the need for the 24-h exposure period under conditions of low NH3 volatilisation precludes any study of the diurnal cycle. 10 6 Dec 94 10 1 7 Dec 94 8 Dec 94 9 Dec 94 I I I I 17 Jan 95 18Jan95 19Jan 95 20Jan95 Fig. 3. Surface soil temperatures a t the site during the experimental periods. In both experiments, NH3 was emitted at the maximum rate directly following irrigation. Rain (11 mm) fell between 1800 hours on 7 December and 1300 hours on 8 December and this was sufficient to reduce the NH3 flux to <0.2 pg N/m2.s (Fig. 2). The NH3 flux remained at this low level for the rest of the experiment. In both experiments, the NH3 fluxes showed the typical pattern of emission observed following application of urea or urine (Denmead et al. 1974; Hoff et al. 1981; Freney e t al. 1983; Ryden and McNeill 1984). The rate of NH3 emission was always greater during the day than at night. Ammonia fluxes were higher during the December experiment than during January (Fig. 2) and this is most likely due to the higher soil temperatures in December (Fig. 3). In December the soil temperature reached a maximum of about 38°C during the day, whereas in January the maximum temperature measured on the first few days after effluent irrigation was ~ 3 0 ° C(Fig. 3). Temperature directly affects the equilibrium between NH: and NH3 in the soil solution, and thus has a major influence on NH3 emission. Ammonia volatilisation from effluent-irrigated soil Following similar applications of NH:-N in December and January (6 and 4 . 8 kg N/ha), the loss of N through volatilisation was about 3 times higher in the December experiments (24%) than in January (8.5%). In the January effluent experiment, the NH3 fluxes were negligible after 5 mm of rain fell between 1800 and 0800 hours on 18 January. Urea was applied 1 day after effluent irrigation. The soil was considered to be sufficiently wet t o initiate the dissolution of the urea granules and begin hydrolysis of urea. Ammonia fluxes were larger following the application of urea than those measured after effluent irrigation (Fig. 2). Emissions increased with time to a maximum value of approximately 20 mg N/m2 . s measured 24 h after the urea application. The cumulative NH3 loss over a 48-h period after application amounted to 15 kg N/ha and corresponded to ~ 1 9 % of the urea-N applied. Rain started at about 0500 hours on 20 January with a total of 48 mm being measured at the experimental site. This amount of rainfall would be more than adequate to leach any undissolved urea and soluble ammoniacal-N from the surface soil (Khanna 1981). 14 - 12 - 10 - Dec94 % --5 16 14 + 12 - 10 - ' 94 I 2 - - Dec94 94 I I :.I:j::::: 4 2 0 - Fig. 4. Evaporation (0, B) and rainfall (arrows) a t the experimental site after the application of sewage effluent. r.5 - - - l l l I I l _ 17Jan9518Jan95 19Jan9520Jan95 Evaporation of water from the soil was significantly greater during December than in January (Fig. 4). Approximately 5.5 mm of water evaporated from the soil during the first 24 h in December, whereas only 2.2 mm was lost during the equivalent period in January. The greater evaporation measured in December than in January was associated with a larger amount of NH3 being lost in December. These results suggest that the rate of NH3 volatilisation is strongly influenced by the rate of water loss from the soil surface following irrigation. Previously, Denmead et al. (1974) and Freney et al. (1992) showed strong relationships between the amount of NH3 loss and the amount of evaporation. Freney et al. (1992) showed that dew which had accumulated on the sugar cane trash during C. J. Smith et al. the night controlled the hydrolysis of broadcast urea and thus the amount of NH3 present for the volatilisation process and that no ammonia was emitted until evaporation commenced. 100 10 7 1 6 Dec 94 7 Dec 04 8 Dec 94 9 Dec 94 Fig. 5. The pH (+) in the 0-3 mm soil layer, and extractable ammonium (0) and nitrate (0)in the 0-3, 3-10, and 10-20 mm layers after application of effluent and urea (80 kg N/ha). Since both the rates of evaporation of water from the soil surface and NH3 volatilisation are a function of the energy balance at the soil surface, there is a strong relationship between the vertical NH3 flux and the evaporation of water. Under effluent irrigation, the potential amount of NH3 present for volatilisation will be controlled by the ammoniacal-N concentration in the effluent and the surface soil pH, and temperature (equations 2 and 3). The pH of the soil surface was at its maximum value directly after irrigation and was similar to that of the effluent (Fig. 5). In the days following effluent irrigation, the pH declined to a value of 6 . 5 . A similar trend in pH was observed in the January experiment. Immediately after the addition of urea, the pH declined during the day, but increased during the night. The decline in pH may be attributed to the loss of NH3 from the soil solution and nitrification, whereas the increase in pH may be due to hydrolysis of the urea. Ammonia volatilisation from effluent-irrigated soil Maximal KC1-extractable ammoniacal-N concentrations in the surface 0-3 mm were measured directly after irrigation and decreased with time (Fig. 5). There was a corresponding increase in the KC1-extractable NO; concentrations in all soil layers for the January 1995 sampling, which showed that the ammoniacal-N applied in the effluent was rapidly oxidised. The rapid decrease in the NO; concentrations between 1800 and 1300 hours on December 8, and between 1800 and 0900 hours on January 20, was mainly due to NO; leaching following rainfalls of 10 and 15 mm, respectively. Fig. 6. Exchange isotherm for ammonium in the 0-50 mm layer of soil. The solid line is the best-fit line defined by equation 4. Data shown in ( b ) are for the low-concentration region of (a). NH,' concentration (rnmolc IL) The ammoniacal-N concentration in the soil solution was estimated from the values, using the N H ~ - Nabsorption isotherm shown KC1-extractable in Fig. 6. The conventional single-parameter isotherms did not fit the data, but a good fit to the data was obtained using the 2-parameter relationship of Rothmund-Kormfeld (Bond and Phillips 1990). The isotherm (solid line) is given by NHZ-N C. J. Smith et al. where S1 is N H sorbed ~ (mmol,/kg of soil)/CEC, and C' is ammoniacal-N in solution (C, mmol,/L)/total positive charge in solution (TC, 30 mmol,/L). The cation exchange capacity (CEC) of the 0-10 cm soil layer was 100 mmol,/kg. The fitted values for kl and n were 0.0790 (f0.0021) and 0.4786 (f0.006), respectively. Ammoniacal-N concentration in the soil solution was calculated from the 2 M KC1-extractable NH4+-N ([NH~$-N]~,~,~) using the equation where M,/M, is moisture content of the soil extracted. The above equation partitions the ammoniacal-N between the sorbed and solution phases when the 2 M KC1-extractable was less than the CEC of the soil. In this study, we restricted the use of the equation to NHZ-N values <30 mmol,/kg (equivalent to 420 mg N/kg). When the total NHZ-N values exceeded this value, we assumed that the amount sorbed was insignificant compared with that in solution, which is the case following the addition of urea-N. NHZ-N Fig. 7. Mean wind speeds a t the site during the experimental periods. The factors pH, temperature, and ammoniacal-N concentration in the soil solution were used to calculate the equilibrium NH3 concentration (po) in solution at the soil surface, using equations 2 and 3, which was multiplied by the mean windspeed for the exposure period (Fig. 7) to calculate the ammonia flux (equation 1). The relationship between these calculated flux values and the measured NH3 flux values is shown in Fig. 8, along with the regression lines for the relationships between ammonia flux density and u1.2 PO reported by Sherlock et al. (1995). In contrast to the results reported by Sherlock et al. (1995), poor linear relationships were found for our data sets. The high value for ul.apo, Ammonia volatilisation from effluent-irrigated soil marked 'A', associated with a low flux is most likely due to the inclusion of undissolved urea granules in the 0-3 mm soil sample. In this study, the urea granules were small (<1 mm diameter), and it was impossible to identify them after application t o the soil surface. Sherlock et al. (1995) reported a value for the exchange coefficient, k, of 6.9e - 05 following the application of urea to the soil surface, and 9.0e -05 following the application of synthetic urine, by using a linear regression forced through the origin. Regression analyses of our sewage effluent and urea data (excluding point A), with the intercept forced through zero, gave a k value of 2.74e - 05 (*4.4e - 06; P < 0.05; r2 = 0.65). When the linear regressions were fitted individually to the effluent data sets, the r2 values for the relationships were 0.54 for the December experiment, and 0.95 for January; the k values were 7. l l e - 04 (Jzl.77e - 04) and 8.03e - 05 (Jz7.le - 06) for December and January, respectively. These results confirm the findings of De Datta et al. (1989), that the exchange coefficient, k, is not constant for all times. It would therefore be necessary to determine k for each site and time, as was recommended for urea-fertilised upland crops, urine-affected pastures, and flooded soils (Sherlock et al. 1995; Freney et al. 1985; De Datta et al. 1989). Fig. 8. Relationship between measured NH3 flux, and the product of average wind speed a t 1 . 2 m above the soil surface and the calculated equilibrium NH3 gas concentration a t the soil surface (p,). Symbols represent sewage effluent, December experiment (a);sewage effluent, January experiment (m); and urea, January (A). C. J. Smith et al. Fig. 9. Relationship between measured NH3 flux density, and the water flux density following the application of effluent. Water flux density (m31m2.sec) A strong linear relationship between NH3 flux density and evaporation was observed for the effluent data sets (Fig. 9). The intercept of the linear regression was not significantly different from zero, and therefore a zero intercept model was fitted t o the data. The relationship obtained for the combined sets was where W is the evaporation of water (m3/m2. s). These data suggest that NH3 volatilisation from effluent-irrigated soil is controlled by the evaporation of 'free' effluent water at the soil surface. Ammoniacal-N in this fraction would not be accurately measured by the soil sampling techniques used, which may explain the poor relationship between NH3 flux and ul . 2 p o The slope of the regression (equation 6) represents the effective concentration of the ammoniacal-N in the effluent (pg N/m3 of solution) and is calculated to be 10.2 (f1.26) mg NIL. This value is consistent with the ammoniacal-N concentration ( ~ lmg l N/L) that was measured in the effluent. Thus, for the circumstances of our experiments, NH3 volatilisation during the first 24 h was controlled by the rate of evaporation of water and the ammoniacal-N concentration in the effluent. Conclusions The results show that there was reasonable agreement between 2 different passive gas samplers used t o measure NH3 volatilisation. However, we were unable to measure the NH3 flux with the Ferm tubes at periods of <24 h. In contrast, lower NH3 flux densities can be measured with the passive gas sampler developed by Leuning et al. (1985). Ammonia loss from sewage effluent could be calculated from the exchange coefficient, k, and measurements of surface soil ammoniacal-N, pH, and temperature, concurrently with wind speed at the reference height of 1a2 m. It is not possible to conclude that the magnitude of k would be constant for all sites and times, and as recommended by others (Freney et al. 1985; De Datta et al. 1989; Sherlock et al. 1995), the value needs to be determined for each site. A better relationship was observed between NH3 flux density and evaporation. This may be because Ammonia volatilisation from effluent-irrigated soil NH3 volatilisation predominantly occurs in the 24 h following effluent-irrigation when 'free' effluent water would be evaporating from soil and plant surfaces. In the absence of NH3 flux measurements, it would be possible to estimate the NH3 losses from effluent-irrigated sites from the effluent's ammoniacal-N together with the evaporation. The results show that NH3 losses can be important following effluent-irrigation. Losses of NH3 may be maximised by frequent applications of a small volume of effluent. Acknowledgments This study was supported by funds from the Land and Water Resources Research and Development Corporation, Murray Darling Basin Commission, New South Wales Public Works Department, and CSIRO Aust. National Priorities scheme. We also acknowledge the expert technical assistance provided by Evelyn A. Colvin. References Alpkem (1992). 'The Flow Solution.' (Alpkem Corporation: Wilsonville, OR.) Ball, P. 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