Short-term effects of single or combined application of mineral N fertilizer and cattle slurry on the fluxes of radiatively active trace gases from grassland soil

After implementation of legislative measures for the reduction of environmental hazards from nitrate leaching and ammonia volatilisation when using organic manures and fertilizers in Europe, much attention is now paid to the specific effects of these fertilizers on the dynamics of global warming-relevant trace gases in soil. Particularly nitrogen fertilizers and slurry from animal husbandry are known to play a key role for the CH₄ and N₂O fluxes from soils. Here we report on a short-term evaluation of trace gas fluxes in grassland as affected by single or combined application of mineral fertilizer and organic manure in early spring. Methane fluxes were characterised by a short methane emission event immediately after application of cattle slurry. Within the same day methane fluxes returned to negative, and on average over the 4-day period after slurry application, only a small but insignificant trend to reduced methane oxidation was found. Nitrous oxide emissions showed a pronounced effect of combined slurry and mineral fertilizer application. In particular fresh cattle slurry combined with calcium ammonium nitrate (CAN) mineral fertilizer induced an increase in mean N₂O flux during the first 4 days after application from 10 to 300 μg N₂O-N m⁻² h⁻¹. ¹⁵N analysis of emitted N₂O from ¹⁵N-labelled fertilizer or manure indicated that easily decomposable slurry C compounds induced a pronounced promotion of N₂O-N emission derived from mineral CAN fertilizer. Fluxes after application of either mineral fertilizer or slurry alone showed an increase of less than 5-fold. The NO_x sink strength of the soil was in the range of −6 to −10 μg NO_x-N m⁻² h⁻¹ and after fertilization it showed a tendency to be reduced by no more than 2 μg NO_x-N m⁻² h⁻¹, which was a result of both, increased NO emission and slightly increased NO₂ deposition. Associated determination of the N₂O:N₂ emission ratio revealed that after mineral N application (CAN) a large proportion (c. 50%) was emitted as N₂O, while after application of slurry with easily decomposable C and predominantly -N serving as N-source, the N₂O:N₂ emission ratio was 1:14, i.e. was changed in favour of N₂. Our work provides evidence that particularly the combination of slurry and nitrate-containing N fertilizers gives rise to considerable N₂O emissions from mineral fertilizer N pool.     

Emission of N2O, N2 and CO2 from soil fertilized with nitrate: effect of compaction, soil moisture and rewetting

Soil compaction and soil moisture are important factors influencing denitrification and N₂O emission from fertilized soils. We analyzed the combined effects of these factors on the emission of N₂O, N₂ and CO₂ from undisturbed soil cores fertilized with (150 kg N ha⁻¹) in a laboratory experiment. The soil cores were collected from differently compacted areas in a potato field, i.e. the ridges (ρ_D=1.03 g cm⁻³), the interrow area (ρ_D=1.24 g cm⁻³), and the tractor compacted interrow area (ρ_D=1.64 g cm⁻³), and adjusted to constant soil moisture levels between 40 and 98% water-filled pore space (WFPS).High N₂O emissions were a result of denitrification and occurred at a WFPS≥70% in all compaction treatments. N₂ production occurred only at the highest soil moisture level (≥90% WFPS) but it was considerably smaller than the N₂O-N emission in most cases. There was no soil moisture effect on CO₂ emission from the differently compacted soils with the exception of the highest soil moisture level (98% WFPS) of the tractor-compacted soil in which soil respiration was significantly reduced. The maximum N₂O emission rates from all treatments occurred after rewetting of dry soil. This rewetting effect increased with the amount of water added. The results show the importance of increased carbon availability and associated respiratory O₂ consumption induced by soil drying and rewetting for the emissions of N₂O.     

Effect of management, climate and soil conditions on N2O and NO emissions from an arable crop rotation using high temporal resolution measurements

Quantifying the nitrous oxide (N₂O) and nitric oxide (NO) fluxes emitted from croplands remains a major challenge. Field measurements in different climates, soil and agricultural conditions are still scarce and emissions are generally assessed from a small number of measurements. In this study, we report continuously measured N₂O and NO fluxes with a high temporal resolution over a 2-year crop sequence of barley and maize in northern France. Measurements were carried out using 6 automatic chambers at a rate of 16 mean flux measurements per day. Additional laboratory measurements on soil cores were conducted to study the response of NO and N₂O emissions to environmental conditions.The detection limit of the chamber setup was found to be 3 ng N m⁻² s⁻¹ for N₂O and 0.1 ng N m⁻² s⁻¹ for NO. Nitrous oxide fluxes were higher than the threshold 37% of the time, while they were 72% of the time for NO fluxes.The cumulated annual NO and N₂O emissions were 1.7 kg N₂O-N ha⁻¹ and 0.5 kg NO-N ha⁻¹ in 2007, but 2.9 kg N₂O-N ha⁻¹ and 0.7 kg NO-N ha⁻¹ in 2008. These inter-annual differences were largely related to crop types and to their respective management practices. The forms, amounts and timing of nitrogen applications and the mineralization of organic matter by incorporation of crop residues were found to be the main factor controlling the emissions peaks. The inter-annual variability was also due to different weather conditions encountered in 2007 and 2008. In 2007, the fractioned N inputs applied on barley (54 kg ha⁻¹ in March and in April) did not generate N₂O emissions peaks because of the low rainfall during the spring. However, the significant rainfall observed in the summer and fall of 2007, promoted rapid decomposition of barley residues which caused high levels of N₂O emissions. In 2008, the application of dairy cattle slurry and mineral fertilizer before the emergence of maize (107 kg N_min ha⁻¹ or 130 kg N_tot ha⁻¹ in all) coincided with large rainfalls promoting both NO and N₂O emissions, which remained high until early summer.Laboratory measurements corroborated the field observations: NO fluxes were maximum at a water-filled pore space (WFPS) of around 27% while N₂O fluxes were optimal at 68% WFPS, with a maximum potentially 14 times larger than for NO.     

Sources and rates of nitrous oxide emissions from grazed grassland after application of N-labelled mineral fertilizer and slurry

Nitrogen (N) fertilizer application and grazing are known to induce nitrous oxide (N₂O) emissions from grassland soils. In a field study, general information on rates of N₂O emission, the effect of cattle grazing and the type (mineral fertilizer, cattle slurry) and amount of N supply on the flux of N₂O from a sandy soil were investigated. N₂O emissions from permanent grassland managed as a mixed system (two cuts followed by two grazing cycles) were monitored over 11 months during 2001-2002 in northern Germany using the closed chamber method. The field experiment consisted of four regionally relevant fertilizer combinations, i.e. two mineral N application rates (0 and 100 kg N ha⁻¹ yr⁻¹) and two slurry levels (0 and 74 kg N ha⁻¹ yr⁻¹).Mean cumulative N₂O-N loss was 3.0 kg ha⁻¹ yr⁻¹, and the cumulative ¹⁵N-labelled N₂O emissions varied from 0.03% to 0.19% of the ¹⁵N applied. ¹⁵N labelling indicated that more N₂O was emitted from mineral N than from slurry treated plots, and in all treatments the soil N pool was always clearly the major source of N₂O. Regarding the total cumulative N₂O losses, differences among treatments were not significant, which was caused by: (i) a high variance in emissions during and after cattle grazing due to the random distribution of excrements and by (ii) high N₂ fixation of white clover in the 0 kg N ha⁻¹ treatments, which resulted in similar N status of all treatments. However before grazing started, treatments showed significant differences. After cattle grazing in summer, N₂O emission rates were higher than around the time of spring fertilizer application, or in winter. Grazing resulted in N₂O flux rates up to 489 μg N₂O-N m⁻² h⁻¹ and the grazing period contributed 31-57% to the cumulative N₂O emission. During freeze-thaw cycles in winter (December-February) N₂O emission rates of up to 147 μg N₂O-N m⁻² h⁻¹ were measured, which contributed up to 26% to the annual N₂O flux. The results suggest that N fertilizer application and grazing caused only short-term increases of N₂O flux rates whereas the major share of annual N₂O emission emitted from the soil N pool. The significantly increased N₂O fluxes during freeze-thaw cycles show the importance of emission events in winter which need to be covered by measurements for obtaining reliable estimates of annual N₂O emissions.     

Elevated CO2 concentration and nitrogen fertilisation effects on N2O and CH4 fluxes and biomass production of Phleum pratense on farmed peat soil

The effects of elevated CO₂ supply on N₂O and CH₄ fluxes and biomass production of Phleum pratense were studied in a greenhouse experiment. Three sets of 12 farmed peat soil mesocosms (10 cm dia, 47 cm long) sown with P. pratense and equally distributed in four thermo-controlled greenhouses were fertilised with a commercial fertiliser in order to add 2, 6 or 10 g N m⁻². In two of the greenhouses, CO₂ concentration was kept at atmospheric concentration (360 μmol mol⁻¹) and in the other two at doubled concentration (720 μmol mol⁻¹). Soil temperature was kept at 15 °C and air temperature at 20 °C. Natural lighting was supported by artificial light and deionized water was used to regulate soil moisture. Forage was harvested and the plants fertilised three times during the basic experiment, followed by an extra fertilisations and harvests. At the end of the experiment CH₄ production and CH₄ oxidation potentials were determined; roots were collected and the biomass was determined. From the three first harvests the amount of total N in the aboveground biomass was determined. N₂O and CH₄ exchange was monitored using a closed chamber technique and a gas chromatograph. The highest N₂O fluxes (on average, 255 μg N₂O m⁻² h⁻¹ during period IV) occurred just after fertilisation at high water contents, and especially at the beginning of the growing season (on average, 490 μg N₂O m⁻² h⁻¹ during period I) when the competition of vegetation for N was low. CH₄ fluxes were negligible throughout the experiment, and for all treatments the production and oxidation potentials of CH₄ were inconsequential. Especially at the highest rates of fertilisation, the elevated supply of CO₂ increased above- and below-ground biomass production, but both at the highest and lowest rates of fertilisation, decreased the total amount of N in the aboveground dry biomass. N₂O fluxes tended to be higher under doubled CO₂ concentrations, indicating that increasing atmospheric CO₂ concentration may affect N and C dynamics in farmed peat soil.     

N2O emissions and product ratios of nitrification and denitrification as affected by freezing and thawing

Agricultural soils contribute significantly to atmospheric nitrous oxide (N₂O). A considerable part of the annual N₂O emission may occur during the cold season, possibly supported by high product ratios in denitrification (N₂O/(N₂+N₂O)) and nitrification (N₂O-N/(NO₃⁻-N+NO₂⁻-N)) at low temperatures and/or in response to freeze-thaw perturbation. Water-soluble organic materials released from frost-sensitive catch crops and green manure may further increase winter emissions. We conducted short-term laboratory incubations under standardized moisture and oxygen (O₂) conditions, using nitrogen (N) tracers (¹⁵N) to determine process rates and sources of emitted N₂O after freeze-thaw treatment of soil or after addition of freeze-thaw extract from clover. Soil respiration and N₂O production was stimulated by freeze-thaw or addition of plant extract. The N₂O emission response was inversely related to O₂ concentration, indicating denitrification as the quantitatively prevailing process. Denitrification product ratios in the two studied soils (pH 4.5 and 7.0) remained largely unaltered by freeze-thaw or freeze-thaw-released plant material, refuting the hypothesis that high winter emissions are due to frost damage of N₂O reductase activity. Nitrification rates estimated by nitrate (NO₃⁻) pool enrichment were 1.5-1.8 μg NO₃-N g⁻¹ dw soil d⁻¹ in freeze-thaw-treated soil when incubated at O₂ concentrations above 2.3 vol% and one order of magnitude lower at 0.8 vol% O₂. Thus, the experiments captured a situation with severely O₂-limited nitrification. As expected, the O₂ stress at 0.8 vol% resulted in a high nitrification product ratio (0.3 g g⁻¹). Despite this high product ratio, only 4.4% of the measured N₂O accumulation originated from nitrification, reaffirming that denitrification was the main N₂O source at the various tested O₂ concentrations in freeze-thaw-affected soil. N₂O emission response to both freeze-thaw and plant extract addition appeared strongly linked to stimulation of carbon (C) respiration, suggesting that freeze-thaw-induced release of decomposable organic C was the major driving force for N₂O emissions in our soils, both by fuelling denitrifiers and by depleting O₂. The soluble C (applied as plant extract) necessary to induce a CO₂ and N₂O production rate comparable with that of freeze-thaw was 20-30 μg C g⁻¹ soil dw. This is in the range of estimates for over-winter soluble C loss from catch crops and green manure plots reported in the literature. Thus, freeze-thaw-released organic C from plants may play a significant role in freeze-thaw-related N₂O emissions.     

CH4 oxidation and N2O emissions at varied soil water-filled pore spaces and headspace CH4 concentrations

Emission of N₂O and CH₄ oxidation rates were measured from soils of contrasting (30-75%) water-filled pore space (WFPS). Oxidation rates of ¹³C-CH₄ were determined after application of 10 μl ¹³C-CH₄ l⁻¹ (10 at. % excess ¹³C) to soil headspace and comparisons made with estimates from changes in net CH₄ emission in these treatments and under ambient CH₄ where no ¹³C-CH₄ had been applied. We found a significant effect of soil WFPS on ¹³C-CH₄ oxidation rates and evidence for oxidation of 2.2 μg ¹³C-CH₄ d⁻¹ occurring in the 75% WFPS soil, which may have been either aerobic oxidation occurring in aerobic microsites in this soil or anaerobic CH₄ oxidation. The lowest ¹³C-CH₄ oxidation rate was measured in the 30% WFPS soil and was attributed to inhibition of methanotroph activity in this dry soil. However, oxidation was lowest in the wetter soils when estimated from changes in concentration of ¹²⁺¹³C-CH₄. Thus, both methanogenesis and CH₄ oxidation may have been occurring simultaneously in these wet soils, indicating the advantage of using a stable isotope approach to determine oxidation rates. Application of ¹³C-CH₄ at 10 μl ¹³C-CH₄ l⁻¹ resulted in more rapid oxidation than under ambient CH₄ conditions, suggesting CH₄ oxidation in this soil was substrate limited, particularly in the wetter soils. Application of and (80 mg N kg soil⁻¹; 9.9 at.% excess ¹⁵N) to different replicates enabled determination of the respective contributions of nitrification and denitrification to N₂O emissions. The highest N₂O emission (119 μg ¹⁴⁺¹⁵N-N₂O kg soil⁻¹ over 72 h) was measured from the 75% WFPS soil and was mostly produced during denitrification (18.1 μg ¹⁵N-N₂O kg soil⁻¹; 90% of ¹⁵N-N₂O from this treatment). Strong negative correlations between ¹⁴⁺¹⁵N-N₂O emissions, denitrified ¹⁵N-N₂O emissions and ¹³C-CH₄ concentrations (r=−0.93 to −0.95, N₂O; r=−0.87 to −0.95, denitrified ¹⁵N-N₂O; P<0.05) suggest a close relationship between CH₄ oxidation and denitrification in our soil, the nature of which requires further investigation.     

Denitrification in grass swards is increased under elevated atmospheric CO2

Emissions of N₂O and N₂ were measured from Lolium perenne L. swards under ambient (36 Pa) and elevated (60 Pa) atmospheric CO₂ at the Swiss free air carbon dioxide enrichment experiment following application of 11.2 g N m⁻² as ¹⁵NH₄¹⁵NO₃ or ¹⁴NH₄¹⁵NO₃ (1 at.% excess ¹⁵N). Total denitrification (N₂O+N₂) was increased under elevated pCO₂ with emissions of 6.2 and 19.5 mg ¹⁵N m⁻² measured over 22 d from ambient and elevated pCO₂ swards, respectively, supporting the hypothesis that increased belowground C allocation under elevated pCO₂ provides the energy for denitrification. Nitrification was the predominant N₂O producing process under ambient pCO₂ whereas denitrification was predominant under elevated pCO₂. The N₂-to-N₂O ratio was often higher under elevated pCO₂ suggesting that previous estimates of gaseous N losses based only on N₂O emissions have greatly underestimated the loss of N by denitrification.     

Carbon dioxide, nitrous oxide and methane dynamics in boreal organic agricultural soils with different soil characteristics

The annual carbon dioxide (CO₂), nitrous oxide (N₂O) and methane (CH₄) dynamics were measured with static chambers on two organic agricultural soils with different soil characteristics. Site 1 had a peat layer of 30 cm, with an organic matter (OM) content of 74% in the top 20 cm. Site 2 had a peat layer of 70 cm but an OM content of only 40% in the top 20 cm. On both sites there were plots under barley and grass and also plots where the vegetation was removed. All soils were net sources of CO₂ and N₂O, but they consumed atmospheric CH₄. Soils under barley had higher net CO₂ emissions (830 g CO₂-C m⁻² yr⁻¹) and N₂O emissions (848 mg N₂O-N m⁻² yr⁻¹) than those under grass (395 g CO₂-C m⁻³ yr⁻¹ and 275 mg N₂O-N m⁻² yr⁻¹). Bare soils had the highest N₂O emissions, mean 2350 mg N₂O-N m⁻² yr⁻¹. The mean CH₄ uptake rate from vegetated soils was 100 mg CH₄-C m⁻³ yr⁻¹ and from bare soils 55 mg CH₄-C m⁻² yr⁻¹. The net CO₂ emissions were higher from Site 2, which had a high peat bulk density and a low OM content derived from the addition of mineral soil to the peat during the cultivation history of that site. Despite the differences in soil characteristics, the mean N₂O emissions were similar from vegetated peat soils from both sites. However, bare soils from Site 2 with mineral soil addition had N₂O emissions of 2-9 times greater than those from Site 1. Site 1 consumed atmospheric CH₄ at a higher rate than Site 2 with additional mineral soil. N₂O emissions during winter were an important component of the N₂O budget even though they varied greatly, ranging from 2 to 99% (mean 26%) of the annual emission.     

CH4 oxidation and emissions of CH4 and N2O from Lolium perenne swards under elevated atmospheric CO2

Emissions of N₂O and CH₄ and CH₄ oxidation rates were measured from Lolium perenne swards in a short-term study under ambient (36 Pa) and elevated (60 Pa) atmospheric CO₂ at the Free Air Carbon dioxide Enrichment experiment, Eschikon, Switzerland. Elevated pCO₂ increased (P<0.05) N₂O emissions from high N fertilised (11.2 g N m⁻²) swards by 69%, but had no significant effect on net emissions of CH₄. Application of ¹³C-CH₄ (11 μl l⁻¹; 11 at.% excess ¹³C) to closed chamber headspaces in microplots enabled determination of rates of ¹³C-CH₄ oxidation even when net CH₄ fluxes from main plots were positive. We found a significant interaction between fertiliser application rate and atmospheric pCO₂ on ¹³C-CH₄ oxidation rates that was attributed to differences in gross nitrification rates and C and N availability. CH₄ oxidation was slower and thought to be temporarily inhibited in the high N ambient pCO₂ sward. The most rapid CH₄ oxidation of 14.6 μg ¹³C-CH₄ m⁻² h⁻¹ was measured in the high fertilised elevated pCO₂ sward, and we concluded that either elevated pCO₂ had a stimulatory effect on CH₄ oxidation or inhibition of oxidation following fertiliser application was lowered under elevated pCO₂. Application of ¹⁴NH₄¹⁵NO₃ and ¹⁵NH₄¹⁵NO₃ (10 at.% excess ¹⁵N) to different replicates enabled determination of the respective contributions of nitrification and denitrification to N₂O emissions. Inhibition of CH₄ oxidation in the high fertilised ambient pCO₂ sward, due to competition between NH₃ and CH₄ for methane monooxygenase enzymes or toxic effects of NH₂OH or NO₂⁻ produced during nitrification, was hypothesised to increase gross nitrification (12.0 mg N kg dry soil⁻¹) and N₂O emissions during nitrification (327 mg ¹⁵N-N₂O m⁻² over 11 d). Our results indicate that increasing atmospheric concentrations of CO₂ may increase emissions of N₂O by denitrification, lower nitrification rates and either increase or decrease the ability of soil to act as a sink for atmospheric CH₄ depending on fertiliser management.     

Nitrogen oxides emission from soils bearing a potato crop as influenced by fertilization with treated pig slurries and composts

Nitrous oxide, nitric oxide and denitrification losses from an irrigated soil amended with organic fertilizers with different soluble organic carbon fractions and ammonium contents were studied in a field study covering the growing season of potato (Solanum tuberosum). Untreated pig slurry (IPS) with and without the nitrification inhibitor dicyandiamide (DCD), digested thin fraction of pig slurry (DTP), composted solid fraction of pig slurry (CP) and composted municipal solid waste (MSW) mixed with urea were applied at a rate of 175 kg available N ha⁻¹, and emissions were compared with those from urea (U) and a control treatment without any added N fertilizer (Control). The cumulative denitrification losses correlated significantly with the soluble carbohydrates, dissolved N and total C added. Added dissolved organic C (DOC) and dissolved N affected the N₂O/N₂ ratio, and a lower ratio was observed for organic fertilizers than from urea or unfertilized controls. The proportion of N₂O produced from nitrification was higher from urea than from organic fertilizers. Accumulated N₂O losses during the crop season ranged from 3.69 to 7.31 kg N₂O-N ha⁻¹ for control and urea, respectively, whereas NO losses ranged from 0.005 to 0.24 kg NO-N ha⁻¹, respectively. Digested thin fraction of pig slurry compared to IPS mitigated the total N₂O emission by 48% and the denitrification rate by 33%, but did not influence NO emissions. Composted pig slurry compared to untreated pig slurry increased the N₂O emission by 40% and NO emission by 55%, but reduced the denitrification losses (34%). DCD partially inhibited nitrification rates and reduced N₂O and NO emissions from pig slurry by at least 83% and 77%, respectively. MSW+U, with a C:N ratio higher than that of the composted pig slurry, produced the largest denitrification losses (33.3 kg N ha⁻¹), although N₂O and NO emissions were lower than for the U and CP treatments.This work has shown that for an irrigated clay loam soil additions of treated organic fertilizers can mitigate the emissions of the atmospheric pollutants NO and N₂O in comparison with urea.     

Nitrous oxide emissions from boreal organic soil under different land-use

Nitrous oxide emissions were studied with a static chamber technique during 2 years from a drained organic soil in eastern Finland. After drainage, the soil was forested with birch (Betula pendula Roth) and 22 years later, part of the forest was felled and then used for cultivation of barley (Hordeum vulgare L.) and grass. The annual N₂O emissions from the cultivated soil (from 8.3 to 11.0 kg N₂O-N ha⁻¹ year⁻¹) were ca. twice the annual emission from the adjacent forest site (4.2 kg N₂O-N ha⁻¹ year⁻¹). The N₂O emissions from the soils without plants (kept bare by regular cutting or tilling) were also lower (from 6.5 to 7.1 kg N₂O-N ha⁻¹ year⁻¹) than those from the cultivated soil. There was a high seasonal variation in the fluxes with a maximum in spring and early summer. The N₂O fluxes during the winter period accounted for 15-60% of the total annual emissions. N₂O fluxes during the snow-free periods were related to the water table (WT) level, water-filled pore space, carbon mineralisation and the soil temperature. A linear regression model with CO₂ production, WT and soil temperature at the depth of 5 cm as independent variables explained 54% of the variation in the weekly mean N₂O fluxes during the snow-free periods. N₂O fluxes were associated with in situ net nitrification, which alone explained 58% of the variation in the mean N₂O fluxes during the snow-free period. The N₂O-N emissions were from 1.5 to 5% of net nitrification. The acetylene blockage technique indicated that most of the N₂O emitted in the snow-free period originated from denitrification.     

The influence of winter soil cover on spring nitrous oxide emissions from an agricultural soil

In temperate regions, a majority of N₂O is emitted during spring soil thawing. We examined the influence of two winter field covers, snow and winter rye, on soil temperature and subsequent spring N₂O emissions from a New York corn field over two years. The first season (2006-07) was a cold winter (2309 h below 0 °C at 8 cm soil depth), historically typical for the region. The snow removal treatment resulted in colder soils and higher N₂O fluxes (73.3 vs. 57.9 ng N₂O-N cm⁻² h⁻¹). The rye cover had no effect on N₂O emissions. The second season (2007-08) was a much milder winter (1271 h below freezing at 8 cm soil depth), with lower N₂O fluxes overall. The winter rye cover resulted in lower N₂O fluxes (5.9 vs. 33.7 ng N₂O-N cm⁻² h⁻¹), but snow removal had no effect. Climate scenarios predict warmer temperature and less snow cover in the region. Under these conditions, spring N₂O emissions can be expected to decrease and could be further reduced by winter rye crops.     

Land use effects on gross nitrogen mineralization, nitrification, and N2O emissions in ephemeral wetlands

Stable ¹⁵N isotope dilution and tracer techniques were used in cultivated (C) and uncultivated (U) ephemeral wetlands in central Saskatchewan, Canada to: (1) quantify gross mineralization and nitrification rates and (2) estimate the relative proportion of N₂O emissions from these wetlands that could be attributed to denitrification versus nitrification-related processes. In-field incubation experiments were repeated in early May, mid-June and late July. Mean gross mineralization and nitrification rates (10.3 and 3.1 mg kg⁻¹ d⁻¹, respectively) did not differ between C and U wetlands on any given date. Despite these similarities, the mean NH₄⁺ pool size in the U wetlands (17.2 mg kg⁻¹) was two to three times that of the C wetlands (6.7 mg kg⁻¹) whereas the mean NO₃⁻ pool size in U wetlands (2.2 mg kg⁻¹) was less than half that of C wetlands (5.8 mg kg⁻¹). Mean N₂O emissions from the C wetlands decreased from 112.8 to 17.0 ng N₂O m² s⁻¹ from May to July, whereas mean U-wetland N₂O emissions ranged only from 31.8 to 51.1 ng N₂O m² s⁻¹ over the same period. This trend is correlated to water-filled pore space in C wetlands, demonstrating a soil moisture influence on emissions. Denitrification is generally considered the dominant emitter of N₂O under anaerobic conditions, but in the C wetlands, only 49% of the May emissions could be directly attributed to denitrification, decreasing to 29% in July. In contrast, more than 75% of the N₂O emissions from the U wetlands arose from denitrification of the soil NO₃⁻ pool throughout the season. These land use differences in emission sources and rates should be taken into consideration when planning management strategies for greenhouse gas mitigation.     

Nitrous oxide emissions from agricultural soils at low temperatures: a laboratory microcosm study

We studied in laboratory microcosms (intact soil cores) N₂O and CO₂ emissions from four different agricultural soil types (organic soil, clay, silt and loam) at low temperatures with or without freezing-thawing events. When the temperature of the frozen soil cores was increased stepwise from −8 °C the N₂O emissions began to increase at −0.5 °C, and peaked at −0.1 °C in the organic, clay and silt soils, and at +1.6 °C in the loam soils. However, a stepwise decrease in soil temperature from +15 °C also induced an increase in the N₂O emissions close to the 0 °C. These emissions peaked between −0.4 and +2.5 °C depending on the soil type and water content. However, the emission maxima were from 2 to 14.3% of those encountered in the experiments where frozen soils were thawed. Our results show that in addition to the well-documented thawing peak, soils also can have a maximum in their N₂O emission near 0 °C when soil temperature decrease. These emissions, however, are less than those emitted from thawing soils. The correlations between the N₂O and CO₂ emissions were weak. Our results suggest that N₂O is produced in soils down to a temperature of −6 °C.     

Emissions and spatial variability of N2O, N2 and nitrous oxide mole fraction at the field scale, revealed with N isotopic techniques

The accurate measurement of nitrous oxide (N₂O) and dinitrogen (N₂) during the denitrification process in soils is a challenge which will help to estimate the contribution of soil N₂O emissions to global warming. Oxygen concentration, nitrate concentration and carbon availability are generally the main factors that control soil denitrification rate and the amount of N₂O or N₂ emitted. The aim of this paper is to present a database of the N₂O mole fraction measured at the field scale, and to test hypotheses concerning its regulation. A ¹⁵N-nitrate tracer solution was added to 36 undisturbed soil cores on a 20 m×20 m cultivated field plot. Fluxes of CO₂, N₂O and N₂ from the soil surface were monitored for 24 h. Soil moisture, bulk density, carbon, nitrogen and mineral nitrogen concentration were also measured to investigate possible spatial relationships between their variations and those of N₂O, N₂ and nitrous oxide mole fraction. Under high water content, nitrous oxide and N₂ emissions were highly variable with variation coefficients of 70-140%. N₂O emission rates were about twice as high as those of N₂, with a total denitrification rate ranging from 269 to 3843 g N ha⁻¹ d⁻¹. After 24 h of incubation, the values of nitrous oxide mole fraction ranged from 0.15 to 0.94 and no significant decline during incubation time was observed. Spatial variability of N₂O, N₂ and nitrous oxide mole fraction was high and no spatial dependence was observed at the scale of the experimental plot. Only tenuous relationships between gaseous nitrogen emissions and soil properties (mainly nitrate concentration and moisture content) were found. Meanwhile, a positive correlation was observed between N₂ and CO₂ emissions. This result supports the hypothesis that an increase in soil available organic carbon leads to N₂ emissions as the end product of denitrification.     

Boreal pine forest floor biogenic volatile organic compound emissions peak in early summer and autumn

In boreal forests, canopy-scale emissions of biogenic volatile organic compounds (BVOCs) are rather well characterised, but knowledge of ecosystem-scale BVOC emissions is still inadequate. We used adsorbent tubes to measure BVOCs from a boreal Scots pine (Pinus sylvestris L.) forest floor in southern Finland and analysed the compounds with a gas chromatograph-mass spectrometer. The most abundant compound group was the monoterpenes (averaging 5.04 μg m⁻² h⁻¹), in which α-pinene, Δ³-carene and camphene contributed over 90% of the emissions. Emissions of other terpenoids (isoprene and sesquiterpenes) were low (averaging 0.05 and 0.04 μg m⁻² h⁻¹, respectively). BVOC emissions from the forest floor varied seasonally, peaking in early summer and autumn, with most of the compounds following similar patterns. The emission pattern was sustained throughout the measurement period, suggesting that the main sources of the emissions remained more or less stable. We compared the BVOC fluxes with environmental parameters such as temperature, precipitation and PAR, and with fluxes of other trace gases (CO₂, CH₄, N₂O), as well as with ground vegetation photosynthesis and with litter input. Several of these parameters were correlated with the presence of BVOCs. The sources of soil BVOC emissions are very poorly understood, but our results suggest, that changes in litter quantity and quality, soil microbial activity and the physiological stages of plants are linked with changes in BVOC fluxes.     

Nitrous oxide emissions from cattle-impacted pasture soil amended with nitrate and glucose

There is little information concerning N₂O fluxes in the pasture soil that has received large amounts of nutrients, such as urine and dung, for several years. The aims of this study were to (1) experimentally quantify the relationship between mineral N input and N₂O emissions from denitrification, (2) describe the time course of N₂O fluxes resulting in N inputs, and (3) find whether there exists an upper limit of the amount of nitrogen escaping the soil in the form of N₂O. The study site was a grassland used as a cattle overwintering area. It was amended with KNO₃ and glucose corresponding to 10–1,500 kg N and C per hectare, covering the range of nutrient inputs occurring in real field conditions. Using manual permanent chambers, N₂O fluxes from the soil were monitored for several days after the amendments. The peak N₂O emissions were up to 94 mg N₂O–N m⁻² h⁻¹, 5–8 h after amendment. No upper limit of N₂O emissions was detected as the emissions were directly related to the dose of nutrients in the whole range of amendments used, but the fluxes reflected the soil and environmental conditions, too. Thus, in three different experiments performed during the season, the total cumulative losses of N₂O–N ranged from 0.2 to 5.6% of the applied 500kg ha⁻¹. Splitting of high nutrient doses lowered the rate of N₂O fluxes after the first amendment, but the effect of splitting on the total amount of N₂O–N released from the soil was insignificant, as the initial lower values of emissions in the split variants were compensated for by a longer duration of gas fluxes. The results suggest that the cattle-impacted soil has the potential to metabolize large inputs of mineral nitrogen over short periods (∼days). Also, the emission factors for did not exceed values reported in literature.     

Rapid shift from denitrification to nitrification in soil after biogas residue application as indicated by nitrous oxide isotopomers

Nitrous oxide (N₂O) is one of the major greenhouse gases emitted from soils, where it is mainly produced by nitrification and denitrification. It is well known that rates of N₂O release from soils are mainly determined by the availability of substrates and oxygen, but N₂O source apportioning, highly needed to advance N₂O mitigation strategies, still remains challenging. In this study, using an automated soil incubation system, the N₂O site preference, i.e. the intramolecular ¹⁵N distribution, was analyzed to evaluate the progression in N₂O source processes following organic soil amendment. Biogas fermentation residue (BGR; originating from food waste fermentation) was applied to repacked grassland soil cores and compared to ammonium sulfate (AS) application, both at rates equivalent to 160 kg NH₄⁺-N ha⁻¹, and to unamended soil (control). The soil cores were incubated in a helium-oxygen atmosphere with 20 kPa O₂ for 43 days at 80% water-filled pore space. 43-day cumulative N₂O emissions were highest with BGR treated soil accounting for about 1.68 kg N₂O-N ha⁻¹ while application of AS caused much lower fluxes of c. 0.23 kg N₂O-N ha⁻¹. Also, after BGR application, carbon dioxide (CO₂) fluxes showed a pronounced initial peak with steep decline until day 21 whereas with ammonium addition they remained at the background level. N₂O dual isotope and isotopomer analysis of gas samples collected from BGR treated soil indicated bacterial denitrification to be the main N₂O generating process during the first three weeks when high CO₂ fluxes signified high carbon availability. In contrast, in the second half after all added labile carbon substrates had been consumed, nitrification, i.e. the generation of N₂O via oxidation of hydroxylamine, gained in importance reaching roughly the same N₂O production rate compared to bacterial denitrification as indicated by N₂O SP. Overall in this study, bacterial denitrification seemed to be the main N₂O forming process after application of biogas residues and fluxes were mainly driven by available organic carbon.     

Modelling variability in N2O emissions from fertilized agricultural fields

Estimates of long-term landscape-scale N₂O emissions for greenhouse gas inventories are complicated by large temporal and spatial variability. Much of this variability is likely caused by topographic effects on surface and subsurface water flows. We hypothesized that this variability could be explained as degassing events during anaerobic soil conditions and during transitions from anaerobic to aerobic soil conditions as controlled by precipitation and subsequent water redistribution in complex landscapes. We simulated degassing events in the ecosystem model ecosys run in three-dimensional mode to simulate a fertilized agricultural field with topographic variation derived from a digital terrain map. N₂O emissions modelled from two areas within the field that had received 15.5 and 9.9 g N m⁻² as urea in May 1998 were compared with those measured by micrometeorological flux towers during June and July 1998. Modelled N₂O emissions during 1998 accounted for 2.3 and 2.0% of urea N applied at 15.5 and 9.9 g N m⁻², respectively. Degassing events in the model coincided with a key N₂O emission event measured in the field during several days after a rainfall in mid-June. During this event, modelled and measured surface fluxes rose rapidly to exceed 1 mg N m⁻² h⁻¹ for 2-3 d before declining. Emissions modelled concurrently at different topographic positions within the landscape during the emission event had coefficients of variation that varied over time between 30 and 180%. Much of the spatial variability in modelled emissions was attributed to temporal differences in the progression of emission events at different landscape positions caused by lateral water movement. The magnitude of temporal and spatial variability in N₂O emissions suggests that aggregation of flux measurements to regional scales should be based upon sub-daily measurements at representative landscape positions, rather than upon less frequent measurements at individual sites as currently done. The use of three-dimensional ecosystem models with input from digital terrain maps may provide a means for such aggregation to be conducted.