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Effect of fertilization history on shortterm emission of CO2 and N2O after the application of different N fertilizers a laboratory study
Nadine Jger , Andreas Duffner , Bernard Ludwig & Heiner Flessa
a a c a b b

Soil Science of Temperate and Boreal Ecosystems, BsgenInstitute, University of Gttingen , Gttingen , Germany
b

Department of Environmental Chemistry , University of Kassel , Witzenhausen , Germany


c

Institute of Agricultural Climate Research, Johann Heinrich von Thnen-Institut , Braunschweig , Germany Published online: 18 Jan 2012.

To cite this article: Nadine Jger , Andreas Duffner , Bernard Ludwig & Heiner Flessa (2013) Effect of fertilization history on short-term emission of CO2 and N2O after the application of different N fertilizers a laboratory study, Archives of Agronomy and Soil Science, 59:2, 161-171, DOI: 10.1080/03650340.2011.621420 To link to this article: http://dx.doi.org/10.1080/03650340.2011.621420

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Archives of Agronomy and Soil Science Vol. 59, No. 2, February 2013, 161171

Eect of fertilization history on short-term emission of CO2 and N2O after the application of dierent N fertilizers a laboratory study
Nadine Ja gera*, Andreas Dunerb, Bernard Ludwigb and Heiner Flessaa,c
a

Soil Science of Temperate and Boreal Ecosystems, Busgen-Institute, University of Gottingen, Gottingen, Germany; bDepartment of Environmental Chemistry, University of Kassel, Witzenhausen, Germany; cInstitute of Agricultural Climate Research, Johann Heinrich von Thunen-Institut, Braunschweig, Germany (Received 19 May 2011; nal version received 26 August 2011) Increasing organic carbon (OC) stocks in soils reduce atmospheric CO2, but may also cause enhanced N2O emissions. The objective of this study was to determine whether there are any dierences in N2O and CO2 emissions from sandy arable soils with dierent soil OC and total nitrogen stocks due to the annual application of either farmyard manure (S-FYM) or mineral fertilizer (S-MIN) over 27 years. A laboratory incubation was performed to test the short-term eects of the application of dierent fertilizers [farmyard manure (FYM), KNO3 (MIN) and biogas waste (BW)] on N2O and CO2 emissions. The CO2 emission rates indicated that OC availability in the soil was higher after BW application than after FYM application. N2O emission for 53 days following fertilizer application amounted to 0.01% (MIN), 0.21% (FYM) and 24% (BW) of the total amount of N applied. The high emissions induced by BW were attributed to the combination of a high availability of OC and ammonium in the fermented waste. Fertilization history, which caused higher soil OC stocks in S-FYM, did not inuence N2O emissions. The results suggest that characterization of C and N pools in organic fertilizers is required to assess their impact on N2O emissions. Keywords: biogas waste; nitrous oxide; soil organic matter; carbon dioxide; fertilization

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Introduction Soils can act as a source but also as a sink of the greenhouse gases carbon dioxide (CO2) and nitrous oxide (N2O) (Mosier et al. 1998; Smith et al. 2003). Worldwide, organic carbon (OC) stocks in soils at a depths of 0200 cm are approximately three gy times greater than the quantity of CO2-C in the atmosphere (Batjes 1996; Jobba and Jackson 2000), and N2O emissions from agricultural soils account for *60% of the current increase in atmospheric N2O (IPCC 2007). Results from fertilization experiments show that OC and total nitrogen (Nt) stocks in cultivated soils can be increased by the long-term application of organic fertilizers (Powlson et al. 1998; Raun et al. 1998; Blair et al. 2006). Thus, the implementation of fertilization strategies, which are based on organic fertilizers, and the associated transient increase in soil C stocks, might result in a transient reduction

*Corresponding author. Email: njaeger@gwdg.de


ISSN 0365-0340 print/ISSN 1476-3567 online 2013 Taylor & Francis http://dx.doi.org/10.1080/03650340.2011.621420 http://www.tandfonline.com

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in the net greenhouse gas emission from crop production. However, increased contents of OC and Nt in arable upland soils may also promote emission of the greenhouse gas N2O (Lal 2004), which is *298 times more eective in terms of radiative forcing than CO2 (based on a time horizon of 100 years; IPCC 2007). Thus, from the perspective of global warming, it is crucial to assess the impacts of C sequestration strategies not only for CO2, but also for other greenhouse gases (Qiu et al. 2009). Little is known about the long-term eects of dierent fertilization strategies and the associated changes in soil organic carbon (SOC) and Nt contents on the emission of N2O. Model results suggest that N2O emissions probably increase with increasing stocks of OC in soils (Li et al. 2005; Qiu et al. 2009). In particular, easily available organic matter fractions were found to trigger N2O emissions because they can promote the formation of anoxic microsites in soils (Parkin 1987; Flessa and Beese 1995) and because they can provide substrates for nitrication and denitrication (Chang et al. 1998; Velthof et al. 2003). Several authors have reported increased N2O emissions directly after the application of organic fertilizers (Chang et al. 1998; Petersen 1999; Flessa and Beese 2000; Van Groenigen et al. 2004). However, the signicance of the long-term eects of C accumulation in agricultural soils on N2O emission is less clear. The few experimental results on the long-term eects of increased organic matter stocks do not provide a consistent picture (Chang et al. 1998; Kilian et al. 1998; De Wever et al. 2002; Meng et al. 2005), even though it is often assumed that increased C stocks result in increased N2O emissions. Chang et al. (1998) determined N2O emissions from soils with an annual solid manure application over 21 years. They found increasing N2O emissions with increasing manuring rate and suggested that repeated manure application may promote N2O losses by the accumulation of OC and nitrate in soil. We hypothesize that the long-term application of farmyard manure and the associated increase in OC and Nt stocks increase N2O emission following fertilizer application. In addition, we hypothesize that the long-term impact of dierent fertilization strategies (application of mineral N or organic manures) on N2O emission is low compared with the eects induced by the direct application of dierent fertilizers. The objective of this study was to determine the eects of dierent long-term fertilization with either mineral fertilizer (S-MIN) or farmyard manure (S-FYM), which resulted in dierent soil OC and Nt stocks, on the emission of N2O and CO2 following the application of fertilizers with dierent contents of bioavailable OC and mineral N [FYM, KNO3, biogas waste (BW) from fermented maize silage]. Material and methods Study site and soil sampling Soil samples were taken from a long-term fertilization experiment at the Institute for Biodynamic Research (IBDF) in Darmstadt, Germany (49850 N, 88340 E, 100 m.a.s.l., mean precipitation of 590 mm yr71). Since 1980, composted dairy cattle manure (SFYM) and calcium ammonium nitrate (S-MIN) have been applied each year in a split-block design with four replicates. The crop rotation consisted of red clover (Trifolium pratense L.), spring wheat (Triticum aestivum L.), potato (Solanum tuberosum L.) and winter rye (Secale cereale L.). The fertilization rate for crops was 140 kg N ha71 yr71 in both fertilization treatments. The farmyard manure from cattle was composted in piles for about nine months before application and the last

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manure application took place 29 months before the soil samples were taken. After harvest, straw remained on the S-MIN eld; it was rst removed and then recycled with composted farmyard manure on the S-FYM eld. The mean annual C input by straw incorporation in the S-MIN treatment was 0.93 t C ha71 yr71, whereas the input by manure application in the S-FYM treatment was 1.3 t C ha71 yr71 (Heinze et al. 2010). The soil type is a Cambisol with 86% sand, 9% silt und 5% clay in the Ap horizon. The main chemical properties of the soil are summarized in Table 1. After almost 30 years of dierent fertilization history, OC and Nt contents were signicantly higher in the S-FYM treatment than in the S-MIN treatment. In February 2007, soil samples were taken from the topsoil (010 cm) of both fertilization treatments (n 4). The eld-moist soil samples were sieved (52 mm). After drying and grinding the samples, OC and N contents were determined using an automated C and N analyzer (Heraeus Elementar Vario EL, Hanau, Germany). Soil pH was measured in a 1072 M CaCl2 solution with a soil/solution ratio 1:2.5. To determine the eective cation-exchange capacity (CEC), soil samples were leached with 100 mL of a 1 M ammonium chloride (NH4Cl) solution for 4 h, as described by Ko nig and Fortmann (1996). Cations in the extract were measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES) (Spectro, Kleve), and exchangeable protons were calculated from the pH of the NH4Cl solution before and after percolation (Table 1). Experimental design and analyses During the incubation experiment, the eect of the application of dierent fertilizer types on the emission dynamics of N2O and CO2 from two soils with dierent fertilization history (S-MIN and S-FYM) was determined. One hundred and twenty grams of eld-moist, sieved (52 mm) soil were put into incubation vessels with a volume of 0.36 L (Sartorius, Go ttingen) and compacted to a soil bulk density of 1.4 g cm73. All samples were adjusted to a soil moisture content of 40% of the waterholding capacity and preincubated for 12 days. After this period, four replicates of each treatment were adjusted to a constant soil moisture content equal to 60% water-lled pore space (WFPS) and the following fertilization treatments were established: (1) control without fertilizer application (control), (2) application of farmyard manure (FYM), (3) application of KNO3 (MIN), and (4) application of BW. All fertilizers were applied at a rate of 31 mg Nt per incubation vessel, which is equal to a surface related N input of 60 kg ha71. The composition of the applied fertilizers is summarized in Table 2. The farmyard manure from cattle was stored for

Table 1. Chemical properties (mean with standard deviation in parentheses, n 4) of soils (0710 cm) with dierent fertilization histories. OC Treatment S-FYM S-MIN (g kg 9.95a 7.88b
71

Nt ) (g kg 0.95a 0.72b
71

pH (CaCl2) 6.1 5.6

CEC (mmolc kg71) 44.64a 45.69a (5.61) (4.43)

(0.25) (0.17)

(0.03) (0.02)

Note: Soils were fertilized with composted farmyard manure (S-FYM) or calcium ammonium nitrate (SMIN) for 27 years. Dierent letters indicate signicant dierences between the dierently fertilized soils (Students t-test). OC, organic carbon; Nt, total nitrogen; CEC, cation exchange capacity.

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Table 2. Composition of the fertilizers used in the incubation study and application rates of total N (Nt) and organic C (OC). Fertilizer FYM MIN BW Dry matter (%) 21.94 7.56 OC (g kg71) 91.38 34.68 Nt (g kg71) 5.55 14.00 1.65 NH4-N (g kg71) 0.06 1.22 C/N 16.5 21.5 Applied OC (mg kg71) 4249.2 5427.4 Applied N (mg kg71) 258 258 258

Note: FYM, farmyard manure from cattle; MIN, KNO3; BW, biogas waste.

two months in piles before application. The BW originated from fermentation of maize silage. The fresh organic manures, which had a dry matter content of 22% (FYM) and 8% (BW) (Table 2), were mixed with the soil and KNO3 (MIN) was dissolved before application. The water content of the applied manures was taken into consideration when adjusting the soil moisture to 60% WFPS. The samples were incubated at 208C in the dark for 53 days. Soil moisture was determined gravimetrically and readjusted if necessary. Emissions of CO2 and N2O were determined at 3-day intervals by closing the lid of the incubation vessels for 1 h. In the case of very high ux rates (necessary only for the treatment with BW), the incubation vessels were put into larger gas accumulation jars (volume of 2.16 L) and the closing period was reduced to 10 min. Gas samples (8 mL) were taken with a gastight syringe via a sampling port in the lid of the incubation vessels directly before the lid was closed and at the end of the gas accumulation period. CO2 and N2O analyses were performed by manual injection of these gas samples in a gas chromatographic system with an electron capture detector (described by Lofteld et al. 1997). Emission rates were calculated from the increase in gas concentration within the headspace of the incubation vessel using incubation time and headspace volume. Extractable ammonium (NH4) and nitrate were determined at the beginning of incubation and 26, 41 and 53 days after the beginning of the experiment using parallel incubated soil samples. The soil/solution ratio during extraction was 1:2. Photometric analysis of mineral N was carried out using a continuous ow analyzer (S/A 20/40 Skalar Analytical, Erkelenz). Total N in the organic manures was determined by the DUMAS-combustion method (FP 2000, Fa. Leco Instruments, Mo nchengladbach). The OC content was determined with an elemental analyser (Elementar Vario Max, Hanau). Statistical analyses Dierences between the two soils with dierent fertilization history (S-MIN, SFYM) with regard to the content of OC, Nt, pH, CEC were tested with Students ttest (p  0.05). The same procedure was used to test the dierences between the two soils (S-MIN, S-FYM) with respect to the cumulative CO2 and N2O emission following the addition of dierent fertilizers. Dierences in cumulative emissions from the dierent fertilization treatments, which were established during the incubation experiment (control, MIN, FYM, BW), were tested with a one-way analysis of variance (ANOVA) followed by Fishers Least Signicant Dierence (LSD) test.

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The emission rates of CO2 from the control and MIN treatments were similar with a mean ux rate of *160 mg CO2-C kg71 h71 (Figure 1). The cumulative CO2 uxes of the control treatments indicate that 2.1% (S-MIN) and 2.0% (S-FYM) of the soil OC was mineralized during the incubation period of 53 days. The CO2 emission rates were higher after the FYM treatment and even higher after the BW treatment throughout the entire incubation period (Figures 1 and 2). Maximum CO2 emission rates of *1000 mg CO2-C kg71 h71 (FYM) and *5000 mg CO2-C kg71 h71 (BW) were measured during the second week after fertilization. In the experiment, fertilizer application was standardized with respect to the total quantity of N applied. Thus, the amount of OC added was 21.7% greater for the BW treatment than for the FYM treatment (Table 2). Cumulative CO2 emission was

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Figure 1. Emission rates of (a) CO2, (b) N2O and (c) soil nitrate (mean+SD, n 4) for soils with dierent fertilization histories (S-FYM, soil with long-term application of farmyard manure; S-MIN, soil with long-term application of mineral fertilizers) after the application of KNO3 (MIN) and farmyard manure (FYM) at day 3 (black arrow) and without fertilizer application (control).

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Figure 2. Emission rates of (a) CO2, (b) N2O and (c) soil nitrate (means+SD, n 4) for soils with dierent fertilization histories (S-FYM, soil with long-term application of farmyard manure; S-MIN, soil with long-term application of mineral fertilizers) after the application biogas waste (BW) at day 3 (black arrow). The maximum emission rates of N2O during the third week after BW application were not recorded by our analytical system.

*2.7 times higher for the BW treatment than for the FYM treatment (Table 3). The cumulative CO2 ux indicated that 38% (in S-FYM) and 28% (in S-MIN) of the BW-carbon and 13% (both treatments) of the FYM-carbon were mineralized during the experiment (Table 3). There was no clear eect of the fertilization history (SMIN, S-FYM) on the CO2 emission dynamics following the application of the dierent fertilizers (Figures 1 and 2). However, the cumulative CO2 emission following BW application was higher for S-FYM than for S-MIN, indicating a slightly higher mineralization of OC in the S-FYM soil after BW application. Application of FYM and BW resulted in increased N2O emission rates throughout the entire incubation period (Figures 1 and 2), and these emission rates were considerably higher than those following the application of KNO3. The highest N2O emission rates by far occurred after application of BW, and both soils treated with this fertilizer exhibited distinct N2O emission dynamics: a rapid increase during the second week after the addition of BW, a high level of N2O emission for about

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Table 3. Cumulative N2O and CO2 emissions (means and standard deviation) for 53 days following the application of dierent fertilizers to soil samples with dierent fertilization histories (S-FYM and S-MIN). CO2-C Cumulative uxes Soil S-FYM S-MIN S-FYM S-MIN S-FYM S-MIN S-FYM S-MIN Fertilizer control control MIN MIN FYM FYM BW BW (mg kg71) 201.6 164.3 136.1 146.5 738.8 700.5 2259.3 1692.2
Aa Ba Aa Aa Ab Ab Ac Bc

N2O-N Emission factor (%) Cumulative uxes (mg kg71) 50.01 0.03 0.02 0.05 0.50 0.71 63.87 61.43
Aa Aa Aa Aa Aa Aa Ab Ab

SD (25.9) (31.8) (20.3) (31.1) (60.1) (38.9) (212.8) (210.4)

(SD) (0.03) (0.07) (0.05) (0.06) (0.13) (0.28) (7.53) (14.70)

Emission factor (%)

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12.6 12.6 37.9 28.2

0.01 0.01 0.20 0.27 24.74 23.78

Note: Control, without fertilizer; MIN, KNO3; FYM, farmyard manure; BW, biogas waste. Emissiom factors were calculated from the amount of organic carbon (OC) and total nitrogen (Nt) added in relation to the dierence between the total emission from the fertilized soil and from the control. Flux rates with dierent upper case letters indicate signicant dierences between the two soils S-FYM and S-MIN (Students t-test, p 5 0.05). Flux rates with dierent lower case letters indicate signicant dierences between the fertilizer types and the control (ANOVA with Fishers LSD test, p  0.05).

two to three weeks followed by a decline to 25 mg N2O-N kg71 h71 until day 53 (Figure 2). These relatively low, nal N2O ux rates were even higher than the maximum N2O emission rates observed for the soils fertilized with FYM (maximum emissions 1.4 and 1.1 mg N2O-N kg71 h71 for S-FYM and S-MIN, respectively). The cumulative N2O emission for the entire incubation period of 53 days increased in the order control 5MIN 5 FYM 5 5 BW (Table 3), and the total emissions were 24% of the applied N for BW, 0.21% for FYM and 0.01% for MIN. The estimated emission of 24% of applied N for BW is actually a conservative estimate: we failed to record the maximum emission rate during the third week after BW application because our system was not congured to register such unexpectedly high emission rates (Figure 2). Discussion CO2 emission from the control treatments was higher for S-FYM than S-MIN (Table 3). The results show that the increase of OC content in S-FYM resulted in increased microbial respiration and O2 consumption. However, the specic mineralization rate (CO2-C emission related to the SOC content) was similar for both soils (S-MIN and S-FYM). This observation indicates a relatively high stabilization or recalcitrance of the additional SOC in S-FYM. The results are in line with the observation that long-term application of farmyard manure favors the accumulation of aliphatic compounds in soil organic matter (S mon 2005), which are considered to represent a particularly recalcitrant form of soil C (Baldock et al. 1997). Our results also agree with model results published by Heitkamp et al. (2009), who suggested that the labile SOC fractions of the analyzed soils were not inuenced by the type of fertilizer applied. The higher SOC content of the S-FYM treatment was explained by an increase in the SOC pool with intermediate stability.

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The emission dynamics of CO2 following application of FYM and BW reect the bioavailability and mineralization of the added organic matter. Our results show that mineralization rates were considerably higher for the BW treatments than for the FYM treatments. The dierence could not be explained by the addition of 1.3 times more organic matter to the BW treatments since the increase of the cumulative CO2 emissions induced by the addition of BW was 3.8 times (S-FYM) and 2.8 times (SMIN) higher than for the respective FYM treatments. The specic mineralization rate was 2.2 (S-MIN) to 3.0 (S-FYM) times higher for BW than for FYM. The dierent substrates of these fertilizers, i.e. cattle excrement with straw for FYM and maize silage for BW, probably contributed to these dierences. Both processes, composting and anaerobic digestion of the original material, reduce the content of easily available OC and result in a biological stabilization process, which is reected by decreasing C mineralization rates (FYM) mez and decreasing CH4 production rates (BW), respectively (Bernal et al. 1998; Go et al. 2007; Li et al. 2009). However, the composition of the organic remains and their stability in aerated soils are dierent. Composting of cattle manure results in a more advanced stage of organic matter oxidation and a greater enrichment in mez et al. 2007). The latter aromatic compounds than the digestion process (Go allows the accumulation of short-chain fatty acids, which can be rapidly mineralized under aerated conditions (Kirchmann and Lundvall 1993). Kirchmann (1991) analyzed the mineralization of aerobically and anaerobically treated animal manures in soil. He found a consistent pattern for all manures tested. The emission of CO2 following manure application was higher for anaerobic manures than aerobic manures. Senbayram et al. (2009) also determined CO2 emissions from an arable soil after the application of biogas waste from fermented maize plants. Their results agree with our observation that the biogas waste contains an easily available OC pool, which is mineralized within the rst weeks after application. N2O emission from the MIN treatments was at the same low level as emissions from the unfertilized soils, even if the amount of available nitrate was highest in these treatments. This indicates that denitrication was restricted by adequate aeration of the sandy soil at 60% WFPS. The application of organic manures signicantly increased N2O emission rates even if the amount of available nitrate was lower. This suggests that the increase in OC availability was the rate-determining factor for N2O emission from the studied soils. Available C can trigger denitrication and N2O emission by dierent processes: it is a substrate for denitrifying bacteria (Dendooven et al. 1996), and it increases metabolic activity and O2 consumption, which can result in the formation of anaerobic microenvironments (Flessa and Beese 1995; Clemens and Huschka 2001). In addition to these direct eects of available C, mineralization of organic compounds with high N contents can also stimulate N release and provide mineral N for nitrication and denitrication (Dendooven et al. 1996). Our results are in line with several other studies, which provided evidence for higher N2O emissions from arable soils receiving organic manures than synthetic mineral N (Petersen 1999; van Groenigen et al. 2004; Dambreville et al. 2006; Rochette et al. 2008). Our results show that N2O emissions were 86127 times higher from the BW treatments produced by anaerobic digestion of maize silage than from the FYM treatments. This clear dierence can be explained by the availability of OC and mineral N in these organic manures. The anaerobic digestion and aerobic composting resulted in contrasting chemical characteristics of the organic material

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applied to the soils as BW or FYM treatment, respectively. Both procedures reduced the initial content of readily available OC in organic substances. However, composting results in C and N stabilization in FYM, whereas anaerobic digestion results in the accumulation of considerable quantities of NH4 and biodegradable organic compounds in BW. Dierences in N availability were evident from the ratio NH4-N to Nt, which was 0.01 for FYM and 0.74 for BW. The combination of increased availability of OC and mineral N results in a greater potential for BW than for FYM to stimulate nitrication, denitrication and N2O emission. The high net-nitrication rates induced by BW application are reected in the increasing nitrate concentrations in these treatments. Several studies have shown that anaerobic digestion reduced N2O eld emissions induced by slurry application (Petersen 1999; Clemens and Huschka 2001; Amon et al. 2006). This was explained by a reduction of readily available OC during fermentation. However, our results suggest that C availability in BW is still considerably greater than in composted FYM. In summary, the presented results indicate that the characterization of C and N pools in organic manures is required to assess their impact on soil N2O emission. Another factor that has probably contributed to the dierent N2O emission from the applied FYM and BW is the water content of these organic fertilizers. The high moisture content of the applied BW (92%) may have favored the formation of anoxic areas and denitrication. Overall, our results show that the hypothesis that organic matter accumulation in soils promotes N2O emission is not valid for the sandy soils of the Darmstadt longterm experiment site if WFPS of these soils would not be higher than 60%. Meng et al. (2005) analyzed N2O emissions from dierently fertilized soils in China (mean annual precipitation of 615 mm during the experimental period, sandy loam texture, alluvial Inceptisol). In agreement with our results, they reported that OC and N contents were higher in a sandy loam soil with long-term application of manure than with application of mineral fertilizer, but there were no signicant dierences of N2O emission. Soil moisture content at their sites (WFPS of 14 to 56%) was even lower than in our incubation study. Kilian et al. (1998) measured N2O emission rates from eld plots established on loess-derived soils with dierent fertilization history in Southern Germany. They concluded that the C and N enrichment of these arable soils by long-term organic fertilization resulted in a detectable increase in N2O emission. However, this eect was small compared to the direct eects of the quantity and timing of fertilizer application. This observation is in line with the results of our study Conclusion We found no evidence from our incubation study that increased OC and Nt stocks, which originated from long-term application of composted farmyard manure, promoted emissions of N2O from a sandy soil at 60% WFPS. The missing eect of soil OC and N accumulation on N2O emission appeared to be inuenced by the general good soil aeration, which restricts N2O production by denitrication. Longterm application of composted farmyard manure resulted in enhanced soil respiration. Increased N2O emissions occurred directly following the application of organic manures, and highest emissions were induced by the application of biogas waste. The amount of easily available OC, mineral N and water was much higher in biogas waste than composted farmyard manure. Our results suggest that these

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factors favored N2O emission by denitrication. We found no eect of the fertilization history on N2O emission induced by the application of dierent fertilizers. The results indicate that N2O emissions from the application of biogas waste can be large and that they, thus, have to be considered when determining the net eect of biogas production on mitigating greenhouse gas emission. References
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