Spatial and temporal variability in CH4 and N2O fluxes from a Scottish ombrotrophic peatland: Implications for modelling and up-scaling

Peatlands typically exhibit significant spatial heterogeneity which can lead to large uncertainties when catchment scale greenhouse gas fluxes are extrapolated from chamber measurements (generally <1 m²). Here we examined the underlying environmental and vegetation characteristics which led to within-site variability in both CH₄ and N₂O emissions and the importance of such variability in up-scaling. We also consider within-site variation in the controls of temporal dynamics. Net annual emissions (and coefficients of variation) for CH₄ and N₂O were 1.06 kg ha⁻¹ y⁻¹ (300%) and 0.02 kg ha⁻¹ y⁻¹ (410%), respectively. The riparian zone was a significant CH₄ hotspot contributing ∼12% of the total catchment emissions whilst covering only ∼0.5% of the catchment area. In contrast to many other studies we found smaller CH₄ emissions and greater uptake in chambers containing either sedges or rushes. We also found clear differences in the drivers of temporal CH₄ dynamics across the site, e.g. water table was important only in chambers which did not contain aerenchymous plants. We suggest that depending on the heterogeneity of the site, flux models could be improved by incorporating a number of spatially distinct sub-models, rather than a single model parameterized using whole-catchment averages.     

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.     

Accumulation of nitrous oxide and depletion of oxygen in seasonally frozen soils in northern Japan - Snow cover manipulation experiments

It has been suggested that soil-thawing and snow-melting are critical triggers for vigorous emissions of nitrous oxide (N₂O) from soils in cold regions. However, because soil freezing is affected by air temperature and snow cover, accurate predictions that estimate subsequent emissions of this important greenhouse gas are difficult to make. In this study, we measured in situ soil gas N₂O and oxygen (O₂) concentrations at two experimental sites in northern Japan over the period of a year, from November 2008 to October 2009, to clarify the factors stimulating N₂O production in soil at low temperatures. The sites were N-fertilized bare arable lands with different soil frost depths and snowmelt rates, according to the snow cover management imposed. Winter-to-spring net N₂O fluxes, ranging from −0.10 to 1.95 kg N₂O-N ha⁻¹, were positively correlated with the annual maximum soil frost depth (ranging from 0.03 to 0.41 m; r = 0.951***). In the plots with deeper maximum soil frost, winter-to-spring N₂O fluxes represented 58% to 85% of the annual values. Soil N₂O production was stimulated when the soil frost depth was greater than 0.15 m or the daily mean soil temperature at 0.05-m depth was below −2.0 °C. In the soil with the greatest frost depth, soil gas N₂O concentrations at the depth of 0.10 m peaked at 46 ppm when soil gas O₂ concentrations fell down to 0.12 m³ m⁻³ under soil temperature below 0.0 °C. Snowmelt acceleration had no stimulating effect on N₂O production in the soil during the winter-to-spring period.     

Microbial activity in soils frozen to below −39 °C

Recent research on life in extreme environments has shown that some microorganisms metabolize at extremely low temperatures in Arctic and Antarctic ice and permafrost. Here, we present kinetic data on CO₂ and ¹⁴CO₂ release from intact and ¹⁴C-glucose amended tundra soils (Barrow, Alaska) incubated for up to a year at 0 to −39°C. The rate of CO₂ production declined exponentially with temperature but it remained positive and measurable, e.g. 2-7 ng CO₂-C cm⁻³ soil d⁻¹, at −39 °C. The variation of CO₂ release rate (v) was adequately explained by the double exponential dependence on temperature (T) and unfrozen water content (W) (r²>0.98): v=A exp(λT+kW) and where A, λ and k are constants. The rate of ¹⁴CO₂ release from added glucose declined more steeply with cooling as compared with the release of total CO₂, indicating that (a) there could be some abiotic component in the measured flux of CO₂ or (b) endogenous respiration is more cold-resistant than substrate-induced respiration. The respiration activity was completely eliminated by soil sterilization (1 h, 121 °C), stimulated by the addition of oxidizable substrate (glucose, yeast extract), and reduced by the addition of acetate, which inhibits microbial processes in acidic soils (pH 3-5). The tundra soil from Barrow displayed higher below-zero activity than boreal soils from West Siberia and Sweden. The permafrost soils (20-30 cm) were more active than the samples from seasonally frozen topsoil (0-10 cm, Barrow). Finding measurable respiration to −39 °C is significant for determining, understanding, and predicting current and future CO₂ emission to the atmosphere and for understanding the low temperature limits of microbial activity on the Earth and on other planets.     

Fluxes of nitrous oxide and nitric oxide from experimental excreta patches in boreal agricultural soil

Nitric oxide (NO) and nitrous oxide (N₂O) emissions were measured from experimental dung and urine patches placed on boreal pasture soil during two growing seasons and one autumn period until soil freezing. N₂O emissions in situ were studied by a static chamber method. NO was measured with a dynamic chamber method using a NO analyser in situ. Mean emissions from the control plots were 47.6±4.5 μg N₂ON m⁻² h⁻¹ and 12.6±1.6 μg NON m⁻² h⁻¹. N₂O and NO emissions from urine plots (132±21.2 μg N₂ON m⁻² h⁻¹ and 51.9±7.6 μg NON m⁻² h⁻¹) were higher than those from dung plots (110.0±20.1 μg N₂ON m⁻² h⁻¹ and 14.7±2.1 μg NON m⁻² h⁻¹). There was a large temporal variation in N₂O and NO emissions. Maximum N₂O emissions were measured a few weeks after dung or urine application, whereas the maximum NO emissions were detected the following year. NO was responsible on average 14% (autumn) and 34% (summer) of total (NO+N₂O)N emissions from the pasture soil. NO emissions increased with increasing soil temperature and with decreasing soil moisture. N₂O emissions increased with increasing soil moisture, but did not correlate with soil temperature. Therefore we propose that N₂O and NO were produced mainly during different microbial processes, i.e., nitrification and denitrification, respectively. The results show that the overall conditions and mechanism especially for emissions of NO are still poorly understood but that there are differences in the mechanisms regulating N₂O and NO production.     

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.     

Do earthworms increase N2O emissions in ploughed grassland?

Earthworm activity has been reported to lead to increased production of the greenhouse gas nitrous oxide (N₂O). This is due to emissions from worms themselves, their casts and drilosphere, as well as to general changes in soil structure. However, it remains to be determined how important this effect is on N₂O fluxes from agricultural systems under realistic conditions in terms of earthworm density, soil moisture, tillage activity and residue loads. We quantified the effect of earthworm presence on N₂O emissions from a pasture after simulated ploughing of the sod (‘grassland renovation’) for different soil moisture contents during a 62-day mesocosm study. Sod (with associated soil) and topsoil were separately collected from a loamy Typic Fluvaquent. Treatments included low (L), medium (M) and high (H) moisture content, in combination with: only soil (S); soil+incorporated sod (SG); soil+incorporated sod+the anecic earthworm Aporrectodea longa (SGE). Nitrous oxide and carbon dioxide (CO₂) fluxes were measured for 62 d. At the end of the incubation period, we determined N₂O production under water-saturated conditions, potential denitrification and potential mineralization of the soil after removing the earthworms. Cumulative N₂O and CO₂ fluxes over 62 d from incorporated sod were highest for treatment HSGE (973 μg N₂O-N and 302 mg CO₂-C kg⁻¹ soil) and lowest for LSG (64 μg N₂O-N and 188 mg CO₂-C kg⁻¹ soil). Both cumulative fluxes were significantly different for soil moisture (p<0.001), but not for earthworm presence. However, we observed highly significant earthworm effects on N₂O fluxes that reversed over time for the H treatments. During the first phase (day 3-day 12), earthworm presence increased N₂O emissions with approximately 30%. After a transitional phase, earthworm presence resulted in consistently lower (approximately 50%) emissions from day 44 onwards. Emissions from earthworms themselves were negligible compared to overall soil fluxes. After 62 d, original soil moisture significantly affected potential denitrification, with highest fluxes from the L treatments, and no significant earthworm effect. We conclude that after grassland ploughing, anecic earthworm presence may ultimately lead to lower N₂O emissions after an initial phase of elevated emissions. However, the earthworm effect was both determined and exceeded by soil moisture conditions. The observed effects of earthworm activity on N₂O emissions were due to the effect of earthworms on soil structure rather than to emissions from the worms themselves.     

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.     

Microbial communities, biomass, and activities in soils as affected by freeze thaw cycles

Two Finnish agricultural soils (peat soil and loamy sand) were exposed to four freeze-thaw cycles (FTC), with a temperature change from −17.3±0.4 °C to +4.1±0.4 °C. Control cores from both soils were kept at constant temperature (+6.6±2.0 °C) without FTCs. Soil N₂O and CO₂ emissions were monitored during soil thawing, and the effects of FTCs on soil microbes were studied. N₂O emissions were extremely low in peat soil, possibly due to low soil water content. Loamy sand had high N₂O emission, with the highest emission after the second FTC. Soil freeze-thaw increased anaerobic respiration in both soil types during the first 3-4 FTCs, and this increase was higher in the peat soil. The microbial community structure and biomass analysed with lipid biomarkers (phospholipid fatty acids, 3- and 2- hydroxy fatty acids) were not affected by freezing-thawing cycles, nor was soil microbial biomass carbon (MIB-C). Molecular analysis of the microbial community structure with temperature gradient gel electrophoresis (TGGE) also showed no changes due the FTCs. These results show that freezing and thawing of boreal soils does not have a strong effect on microbial biomass or community structure.     

Earthworm activity as a determinant for N2O emission from crop residue

Earthworm activity may have an effect on nitrous oxide (N₂O) emissions from crop residue. However, the importance of this effect and its main controlling variables are largely unknown. The main objective of this study was to determine under which conditions and to what extent earthworm activity impacts N₂O emissions from grass residue. For this purpose we initiated a 90-day (experiment I) and a 50-day (experiment II) laboratory mesocosm experiment using a Typic Fluvaquent pasture soil with silt loam texture. In all treatments, residue was applied, and emissions of N₂O and carbon dioxide (CO₂) were measured. In experiment I the residue was applied on top of the soil surface and we tested (a) the effects of the anecic earthworm species Aporrectodea longa (Ude) vs. the epigeic species Lumbricus rubellus (Hoffmeister) and (b) interactions between earthworm activity and bulk density (1.06 vs. 1.61 g cm⁻³). In experiment II we tested the effect of L. rubellus after residue was artificially incorporated in the soil. In experiment I, N₂O emissions in the presence of earthworms significantly increased from 55.7 to 789.1 μg N₂O-N kg⁻¹ soil (L. rubellus; p<0.001) or to 227.2 μg N₂O-N kg⁻¹ soil (A. longa; p<0.05). This effect was not dependent on bulk density. However, if the residue was incorporated into the soil (experiment II) the earthworm effect disappeared and emissions were higher (1064.2 μg N₂O-N kg⁻¹ soil). At the end of the experiment and after removal of earthworms, a drying/wetting and freezing/thawing cycle resulted in significantly higher emissions of N₂O and CO₂ from soil with prior presence of L. rubellus. Soil with prior presence of L. rubellus also had higher potential denitrification. We conclude that the main effect of earthworm activity on N₂O emissions is through mixing residue into the soil, switching residue decomposition from an aerobic and low denitrification pathway to one with significant denitrification and N₂O production. Furthermore, A. longa activity resulted in more stable soil organic matter than L. rubellus.     

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.     

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.     

Dinitrogen and N2O emissions in arable soils: Effect of tillage, N source and soil moisture

A laboratory investigation was performed to compare the fluxes of dinitrogen (N₂), N₂O and carbon dioxide (CO₂) from no-till (NT) and conventional till (CT) soils under the same water, mineral nitrogen and temperature status. Intact soil cores (0-10 cm) were incubated for 2 weeks at 25 °C at either 75% or 60% water-filled pore space (WFPS) with ¹⁵N-labeled fertilizers (100 mg N kg⁻¹ soil). Gas and soil samples were collected at 1-4 day intervals during the incubation period. The N₂O and CO₂ fluxes were measured by a gas chromatography (GC) system while total N₂ and N₂O losses and their ¹⁵N mole fractions in the soil mineral N pool were determined by a mass spectrometer. The daily accumulative fluxes of N₂ and N₂O were significantly affected by tillage, N source and soil moisture. We observed higher (P<0.05) fluxes of N₂+N₂O, N₂O and CO₂ from the NT soils than from the CT soils. Compared with the addition of nitrate (NO₃⁻), the addition of ammonium (NH₄⁺) enhanced the emissions of these N and C gases in the CT and NT soils, but the effect of NH₄⁺ on the N₂ and/or N₂O fluxes was evident only at 60% WFPS, indicating that nitrification and subsequent denitrification contributed largely to the gaseous N losses and N₂O emission under the lower moisture condition. Total and fertilizer-induced emissions of N₂ and/or N₂O were higher (P<0.05) at 75% WFPS than with 60% WFPS, while CO₂ fluxes were not influenced by the two moisture levels. These laboratory results indicate that there is greater potential for N₂O loss from NT soils than CT soils. Avoiding wet soil conditions (>60% WFPS) and applying a NO₃⁻ form of N fertilizer would reduce potential N₂O emissions from arable soils.     

Spatial and temporal variation of nitrous oxide and methane flux between subtropical mangrove sediments and the atmosphere

We quantified spatial and temporal variations of the fluxes of nitrous oxide (N₂O) and methane (CH₄) and associated abiotic sediment parameters across a subtropical river estuary sediment dominated by grey mangrove (Avicennia marina). N₂O and CH₄ fluxes from sediment were measured adjacent to the river (“fringe”) and in the mangrove forest (“forest”) at 3-h intervals throughout the day during autumn, winter and summer. N₂O fluxes from sediment ranged from an average of −4 μg to 65 μg N₂O m⁻² h⁻¹ representing N₂O sink and emission. CH₄ emissions varied by several orders of magnitude from 3 μg to 17.4 mg CH₄ m⁻² h⁻¹. Fluxes of N₂O and CH₄ differed significantly between sampling seasons, as well as between fringe and forest positions. In addition, N₂O flux differed significantly between time of day of sampling. Higher bulk density and total carbon content in sediment were significant contributors towards decreasing N₂O emission; rates of N₂O emission increased with less negative sediment redox potential (E_h). Porewater profiles of nitrate plus nitrite (NO_x⁻) suggest that denitrification was the major process of nitrogen transformation in the sediment and possible contributor to N₂O production. A significant decrease in CH₄ emission was observed with increasing E_h, but higher sediment temperature was the most significant variable contributing to CH₄ emission. From April 2004 to July 2005, sediment levels of dissolved ammonium, nitrate, and total carbon content declined, most likely from decreased input of diffuse nutrient and carbon sources upstream from the study site; concomitantly average CH₄ emissions decreased significantly. On the basis of their global warming potentials, N₂O and CH₄ fluxes, expressed as CO₂-equivalent (CO₂-e) emissions, showed that CH₄ emissions dominated in summer and autumn seasons (82-98% CO₂-e emissions), whereas N₂O emissions dominated in winter (67-95% of CO₂-e emissions) when overall CO₂-e emissions were low. Our study highlights the importance of seasonal N₂O contributions, particularly when conditions driving CH₄ emissions may be less favourable. For the accurate upscaling of N₂O and CH₄ flux to annual rates, we need to assess relative contributions of individual trace gases to net CO₂-e emissions, and the influence of elevated nutrient inputs and mitigation options across a number of mangrove sites or across regional scales. This requires a careful sampling design at site-level that captures the potentially considerable temporal and spatial variation of N₂O and CH₄ emissions.     

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.     

Inhibition of denitrification and N2O emission by urine-derived benzoic and hippuric acid

Hippuric acid (HA) in cattle urine acts as a natural inhibitor of soil N₂O emissions. As HA concentration varies with diet, we determined critical HA levels. We also tested the hypothesis that the inhibition occurs because the HA breakdown product benzoic acid (BA) inhibits denitrification rates. During a 64-day incubation, we quantified emissions from artificial urine varying in HA, BA and glycine (Gly) concentrations, added to a sandy pasture soil. Increasing HA concentration from 0.4 to 5.6 mmol kg⁻¹ soil significantly decreased the average N₂O flux by 54%. At 3.9 mmol kg⁻¹ soil, denitrification levels were 50% reduced for BA as compared to Gly. We conclude that HA inhibits both denitrification and N₂O emission, at least partly through a BA mechanism.     

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.     

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.     

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.     

Seasonal variation and fire effects on CH4, N2O and CO2 exchange in savanna soils of northern Australia

Tropical savanna ecosystems are a major contributor to global CO₂, CH₄ and N₂O greenhouse gas exchange. Savanna fire events represent large, discrete C emissions but the importance of ongoing soil-atmosphere gas exchange is less well understood. Seasonal rainfall and fire events are likely to impact upon savanna soil microbial processes involved in N₂O and CH₄ exchange. We measured soil CO₂, CH₄ and N₂O fluxes in savanna woodland (Eucalyptus tetrodonta/Eucalyptus miniata trees above sorghum grass) at Howard Springs, Australia over a 16 month period from October 2007 to January 2009 using manual chambers and a field-based gas chromatograph connected to automated chambers. The effect of fire on soil gas exchange was investigated through two controlled burns and protected unburnt areas. Fire is a frequent natural and management action in these savanna (every 1-2 years). There was no seasonal change and no fire effect upon soil N₂O exchange. Soil N₂O fluxes were very low, generally between −1.0 and 1.0 μg N m⁻² h⁻¹, and often below the minimum detection limit. There was an increase in soil NH₄⁺ in the months after the 2008 fire event, but no change in soil NO₃⁻. There was considerable nitrification in the early wet season but minimal nitrification at all other times.Savanna soil was generally a net CH₄ sink that equated to between −2.0 and −1.6 kg CH₄ ha⁻¹ y⁻¹ with no clear seasonal pattern in response to changing soil moisture conditions. Irrigation in the dry season significantly reduced soil gas diffusion and as a consequence soil CH₄ uptake. There were short periods of soil CH₄ emission, up to 20 μg C m⁻² h⁻¹, likely to have been caused by termite activity in, or beneath, automated chambers. Soil CO₂ fluxes showed a strong bimodal seasonal pattern, increasing fivefold from the dry into the wet season. Soil moisture showed a weak relationship with soil CH₄ fluxes, but a much stronger relationship with soil CO₂ fluxes, explaining up to 70% of the variation in unburnt treatments. Australian savanna soils are a small N₂O source, and possibly even a sink. Annual soil CH₄ flux measurements suggest that the 1.9 million km² of Australian savanna soils may provide a C sink of between −7.7 and −9.4 Tg CO₂-e per year. This sink estimate would offset potentially 10% of Australian transport related CO₂-e emissions. This CH₄ sink estimate does not include concurrent CH₄ emissions from termite mounds or ephemeral wetlands in Australian savannas.