Water regime influence on trace gas emissions following spreading of waste V. Magliulo1, A.Goossens2, R. R. Sharpe3, L.A. Harper3 CNR – ISAFOM, Via Patacca, 85 - 80056 Ercolano (NA), Italy. Ph. +390817717325, fax +39062331095, V.Magliulo@ispaim.na.cnr.it 1 2 Ghent University, Faculty of Agricultural and Applied Biological Sciences, Laboratory of Applied Physical Chemistry, Coupure links 653, B-9000 Gent, Belgium 3 USDA-ARS, Southern Piedmont Conservation Research Center, 1420 Experiment Station Road, Watkinsville, GA 30677, USA Abstract: Waste products are valuable resources as fertilizers and suitable to be applied to crops and pastures. When concentrated into a small geographical area or applied in excessive amounts however, they can have detrimental environmental effects. Excess application, can result in enhanced CO 2, CH4, NH3 and N2O emissions to the atmosphere influencing global warming and destruction of the ozone layer. These gases have long atmospheric lifetimes, are consequently fairly well-mixed and therefore of global as well as local or regional importance. They represent a most serious treat to global climate in terms of greenhouse effect. NH4 emitted following waste applications can be transported in remote areas and contribute to acidification processes. Atmospheric impact of animal waste in the Mediterranean area was never assessed and few papers can be found in the literature. Reliable inventories of emissions cannot be carried out since emission factors were never assessed locally. In order to improve understanding of trace gas emissions as a function of agronomic techniques in this environment, a study was conducted to quantify emissions of ammonia, nitrous oxide, carbon dioxide, and methane from an alfalfa field in Southern Italy. Three 35 m circular plots were established in a two-year-old crop. Two plots were fertilized with chicken manure and one plot was irrigated. Ammonia fluxes were calculated using an Integrated Horizontal Flux mass balance technique. A Photo Acoustic Infrared Detector was used to measure N 2O, CO2, and CH4 fluxes from vented closed chambers. Ammonia volatilization peaked about 4.1 kg ha -1 d-1 and returned to background levels within 72 hours. Irrigation with 25 mm of water increased NH3 emission rates by about 67%. Emission rates of N2O, CO2, and CH4 were short-lived and returned to the same levels as the control plot within 7 days. Total gaseous N losses were about 19.1 and 15% of the applied N in the irrigated and non-irrigated plots, respectively. INTRODUCTION Ammonia (NH3) emissions to the atmosphere are a threat to the environment. Ammonia can combine with nitrate (NO3) and sulphate (SO4) to form particulate (Asman et al., 1998) which can cause haze and be hazardous to human health. The addition of NH3 to the soil can lead to acidification (van Bremen et al., 1982) and in low nutrient ecosystems can cause unwanted changes in plant species in natural environments (van Hove et al., 1987). Livestock farming is a major source of atmospheric NH3, contributing as much as 70% in areas of intensive farming (Jarvis and Pain, 1990) and it has been estimated that land application of manure contributes about 10% of the total NH3 emissions in Europe (Asman, 1992). Surface application of animal manures may lead to significant NH3 volatilisation. Knowledge of NH3 emission rates is necessary for the efficient crop utilization of manure N. Underestimation of NH3 loss can lead to N deficiency in the crop, while over estimation can result in over fertilization and N loss to the environment. Land application of manures can also increase nitrous oxide (N2O), methane (CH4), and carbon dioxide (CO2) emissions (Egginton and Smith, 1994; Mosier, 1998; Sharpe and Harper, 2002). Nitrous oxide is a radiatively active trace gas that contributes to global warming. The primary biogenic sources of N2O are nitrification denitrification of soil N (Knowles, 1982; Poth and Focht, 1985). Studies have shown that N2O emissions can be figure 1: Wind and temperature profiles and air pumping station increased by the addition of manures because of their high organic carbon (C) as well as N to stimulate Atti del Convegno CNR-ISAFOM, Portici (NA), 23-24 Settembre 2002 microbial activity (Beauchamp et al., 1996; Sharpe and Harper, 2002). Anthropogenic sources account for about 70% of the total annual CH4 emissions, with 16% coming from animal waste (IPCC, 1994). Little is known about the impact of animal waste in the Mediterranean area. The purpose of this study was to improve understanding of gas emissions associated with manure applications in a Mediterranean environment.. The research is a part of national project (CNR National Research Program on agro-industrial waste), aimed at improving the efficiency of use of animal waste, while minimizing environmental hazards (Magliulo, 2002a;.2002b; Magliulo et al, 2000; Goosens et al, 2000). MATERIALS AND METHODS The experiment was conducted in an alfalfa (Medicago sativa L) field in Southern Italy. Three circular plots were figure 2: Gas washing bottles for the determination of ammonia concentration profiles hours. Ammonia collected in the gas washing bottles was measured by a technique described by Weier et al. (1980). Windspeed was measured at the same heights using sensitive cup anemometers (fig. 1). The vertical NH 3 flux (F) was calculated as (Ryden and McNeill, 1984): Zp 1 F (UC UCb)dz X Z0 where X = radius of treated circle (m), U = windspeed (cm sec-1), C = atmospheric NH3 concentration (µg m-3) in the center of the circle, Cb = atmospheric NH3 concentration (µg m-3) in the check plot, Z = height of samplers (m). Fluxes of N2O, CH4, and CO2 were measured from vented closed chambers (inner diameter = 165 mm; height = 170 mm), placed on a collar permanently inserted in the soil (fig. 3). Fluxes were measured in four replicates in the N plot, 2 in the C plot, and 3 in the S plot. After closing the chamber, the concentrations in the headspace were measured every 3 minutes over a total period of 30 minutes, using a Photo Acoustic Infrared Detector, (Multi-Gas Monitor Type 1302, Bruel & Kjaer, Denmark) equipped with optical filters allowing the measure of N2O, CH4, and CO2, and water vapor. The fluxes were calculated through linear regression of the headspace concentration increases. Chambers of the different plots were measured at different times. Measurements started the day after the N plot was fertilized and irrigated for the second time. During the first two days after the fertilization/irrigation, fluxes were measured twice a day on the N plot (morning between 0930 and 1230, afternoon between 1430 and 1700). All fluxes were subjected to a parametric t-test to evaluate the effect of time and treatment. The significance of all tests was evaluated at the 0.05 level established in May, 1999. On June 2, the Northern (N) and Southern (S) plots were fertilized with 30 kg N ha -1 with chicken manure and the N plot was irrigated with 25 mm of water on June 3. The alfalfa was abut 83 cm tall when fertilized. The third plot (C) was the control plot and did not receive fertilization or irrigation. All plots were mowed on June 7. The N plot received on June 9 an additional 30 kg N ha-1 as chicken manure and was irrigated with about 30 mm of water. An Integrated Horizontal Flux (IHF) mass balance method was used to measure NH3 fluxes (fig. 1, 2). In this technique, the vertical NH3 flux is calculated from the differences in the amount of NH3 transported across the windward boundary and the center of the experimental plots. Ammonia concentrations were measured at five heights (75, 125, 175, and 225 cm) above the canopy at the center of the circular plot. Ammonia concentrations of the air samples were measured by drawing unfiltered air at a rate of 4 L min-1 through gas washing bottles (fig. 2) containing 80 mL of 0.1 M H 2SO4 for a period of 6 to 12 figure 3: Soil passive chambers and the photoacustic multigas detector Atti del Convegno CNR-ISAFOM, Portici (NA), 23-24 Settembre 2002 The crop was about 0.83 m tall when chicken manure was first applied. There was a larger and more rapid loss of NH3 from the irrigated (N) plot than the non-irrigated plot (S). In the N plot, NH3 volatilization peaked at about 4.1 kg ha-1 d-1 (fig. 4) and then rapidly decreased to background levels within 48 hr following application. Ammonia volatilization rates were lower in the S plot but did not return to background levels until 72 hr after application. Total N losses during the first three days following application were 7.7 and 4.6 kg ha-1 in the N and S plots, respectively. The larger loss with irrigated than non-irrigated is in contrast to other studies which have shown decreased volatilization with rain or irrigation (Klarenbeck and Bruing, 1991; Cabrera and Vervoort, 1998). The After the rapid NH3 volatilization associated with application, there was a small net uptake of NH3 in both the N and S plots. Uptake of atmospheric NH3 even in well fertilized soils has been reported in other studies (Hutchinson, et al., 1972; Sharpe and Harper, 2002). Net NH3 losses during the study were 9.2 and 5.3 kg ha -1 for the N and S fields, respectively. This was about 15 and 18 % of the total N applied to the N and S fields, respectively. The N2O emissions peaked the first day after fertilization 40 µg N2O-N m-2 min-1 RESULTS AND DISCUSSION N M S 10/6 a.m. 10/6 p.m. 15/6 30 20 10 0 -10 9/6 a.m. Total NH3 losses after the second manure/irrigation application were much smaller. Peak volatilization rate was about 1 kg N ha-1d-1 and total loss during the 48 hours following application was 1.4 kg N ha-1. The smaller loss after the second application was probably due to the movement of N into the soil. The alfalfa was cut on DOY 158. This allowed most of the manure to reach the soil surface and the irrigation leached the some of the N into the soil, reducing NH3 volatilization. and irrigation. Measured rates dropped rapidly on the second day and were about zero 7 days after fertilization (Fig. 5). The S plot which received the addition of chicken manure but did not receive irrigation, was not significantly different from the control plot. Two and 12 -1 N 10 -2 increased volatilization in this study may have been due to canopy interception and subsequent re-wetting of the dried manure. Chambers et al. (1997) reported that rewetting of dried manure increased NH3 losses due to increased hydration of uric acid to NH3 which can than be volatilized. Of the 30 kg N ha-1, 5 kg was inorganic N. As previously noted, N loss in the N plot was 7.7 kg ha-1 which indicates at least some of the organic N was rapidly hydrolyzed and subsequently lost as NH3. Assuming that all of the 4.6 kg N ha-1 lost from the S plot was inorganic N since the field was not irrigated, then as much as 92% of the inorganic N in the manure was lost within 72 hours of application. figure 4: N2 O average emission from the Northern, Middle(control) and Southern plot. Bars are standard error of the mean 8 mg CO2-C m min figure 4 : daily NH4 emission rates from the North and South plots, as a function of day of yea r(DOY). Irrigations are indicated by arrows 9/6 p.m. M S 6 4 2 0 9/6 a.m. 9/6 10/6 10/6 15/6 p.m. a.m. p.m. figure6: CO2 average emission from the Northern, Middle Atti del Convegno CNR-ISAFOM, Portici (NA), 23-24 Settembre(control) 2002 and Southern plot. Bars are standard error of the mean seven days after fertilization emission rates from the N plot were not significantly different from the control or S plot. Total N2O emissions over the measurement period (6.1 days) was 32.3 ± 5.3 mg N2O-N m-2, which represented about 1.1% of the applied N. Carbon dioxide emissions from the N plot followed a µg CH 4-C m-2 min-1 60 50 N M S authors (Coyne et al., 1995; Mosier et al., 1986; Sharpe and Harper, 2002). The addition of N and C in combination with water from irrigation, conditions favoring emissions, resulted in short-lived emissions of N2O, CO2, and CH4 which had returned to near zero within seven days. Irrigation after chicken manure application resulted in NH3 losses of about 67% greater than without irrigation. Total gaseous N losses (NH 3 plus N2O) was about 19.1 and 15% of the applied fertilizer N in the N and S plots, respectively REFERENCES 40 Asman, W.A.H. 1992. Ammonia emissions in Europe: Updated emission and emission variations. RIVM Bilthoven, The Netherlands. p. 88. 30 20 Asman, W.A.H., Sutton, M.A., Schjorring, J.K., 1998. Ammonia emission, atmospheric transport and deposition. New Phyt. 139, 27-48. 10 0 -10 9/6 9/6 10/6 10/6 15/6 a.m. p.m. a.m. p.m. figure 5: : CH4 average emission from the Northern, Middle (control) and Southern plot. Bars are standard error of the mean similar pattern as the N2O emissions (Fig. 6). The largest emissions were on the morning following fertilization with significantly lower emissions in the afternoon. Average emissions from the N plot on day 1 and 2 were not significantly different from each other or from emissions from the control or S plots. Total CO 2 emission at the N plot was 35.5 ± 7.1 g CO2-C m-2. Methane emissions (fig. 7) from the N plot also peaked the morning after fertilization and decreased during the afternoon. On day 2 emission rates showed a different trend with significantly greater emissions in the afternoon then the morning. The daily average fluxes, however, were not significantly different between day 1 and 2. After 7 days, the CH4 emissions had decreased to about zero. Two and seven days after fertilization the daily average CH4 emission from the N plot was no longer different from the emissions from the control or S plot. Total CH4 emission at the N plot was 61.9 ± 7.7 mg CH4C m-2. 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