Contribution of nitrification and denitrification to N2O emissions from urine patches

Urine deposition by grazing livestock causes an immediate increase in nitrous oxide (N₂O) emissions, but the responsible mechanisms are not well understood. A nitrogen-15 (¹⁵N) labelling study was conducted in an organic grass-clover sward to examine the initial effect of urine on the rates and N₂O loss ratio of nitrification (i.e. moles of N₂O-N produced per moles of nitrate produced) and denitrification (i.e. moles of N₂O produced per moles of N₂O+N₂ produced). The effect of artificial urine (52.9 g N m⁻²) and ammonium solution (52.9 g N m⁻²) was examined in separate experiments at 45% and 35% water-filled pore space (WFPS), respectively, and in each experiment a water control was included. The N₂O loss derived from nitrification or denitrification was determined in the field immediately after application of ¹⁵N-labelled solutions. During the next 24 h, gross nitrification rates were measured in the field, whereas the denitrification rates were measured in soil cores in the laboratory. Compared with the water control, urine application increased the N₂O emission from 3.9 to 42.3 μg N₂O-N m⁻² h⁻¹, whereas application of ammonium increased the emission from 0.9 to 6.1 μg N₂O-N m⁻² h⁻¹. In the urine-affected soil, nitrification and denitrification contributed equally to the N₂O emission, and the increased N₂O loss resulted from a combination of higher rates and higher N₂O loss ratios of the processes. In the present study, an enhanced nitrification rate seemed to be the most important factor explaining the high initial N₂O emission from urine patches deposited on well-aerated soils.     

Nitrous oxide production by nitrification and denitrification in soil aggregates as affected by O2 concentration

Nitrous oxide emitted by soils can be produced either by denitrification in anoxic conditions or by nitrification in presence of O₂. The relative importance of the two processes, particularly under varied partial pressures of O₂, is not always known. This paper focuses on the influence of O₂ concentration on N₂O production by nitrification and denitrification in an arable Orthic Luvisol. Soil aggregates (2-3 mm size), water unsaturated, received 116 mg N kg⁻¹ as ammonium sulphate labelled with ¹⁵N and were incubated during 14 days at different O₂ partial pressures: 0, 0.35, 0.76, 1.5, 4.3 and 20.4 kPa. A ¹⁵N tracing technique was used to quantify nitrification and denitrification rates. ¹⁵N₂O and ¹⁵N₂ were measured. Oxygen pressure appeared to strongly influence both nitrification and denitrification rates and also N₂O emissions. Nitrification rates were reduced by a factor of 6-9 when O₂ decreased from 20.4 to 0.35 kPa. They were highly correlated with O₂ consumption rates. Denitrification mainly occurred in complete anoxic conditions. The proportion of N₂O emitted by denitrification was estimated by two independent methods: one based on ¹⁵N tracing using isotope composition of NH₄, NO₃ and N₂O, the other based on the measurement of the ¹⁵N₂O:¹⁵N₂ ratio. The two methods gave close results. The highest N₂O emissions were obtained under complete anoxic conditions and were due to denitrification. However, N₂O emissions almost as important were obtained at day 14 with 1.5 kPa O₂ pressure, and they were due to nitrification. Nitrification was the main source of N₂O at O₂ concentrations greater than 0.35 kPa. The amounts of N₂O-N emitted by nitrification were linearly related to the amounts of N nitrified, but the slope of the regression was highly dependent on O₂ concentration: it varied from 0.16 to 1.48% when O₂ concentration was reduced from 20.4 to 0.76 kPa. Emissions of N₂O by nitrification may then be quite significant if nitrification occurs at a reduced O₂ concentration.     

The N2O product ratio of nitrification and its dependence on long-term changes in soil pH

The contribution of nitrification to the emission of nitrous oxide (N₂O) from soils may be large, but its regulation is not well understood. The soil pH appears to play a central role for controlling N₂O emissions from soil, partly by affecting the N₂O product ratios of both denitrification (N₂O/(N₂+N₂O)) and nitrification (N₂O/(NO₂⁻+NO₃⁻). Mechanisms responsible for apparently high N₂O product ratios of nitrification in acid soils are uncertain. We have investigated the pH regulation of the N₂O product ratio of nitrification in a series of experiments with slurries of soils from long-term liming experiments, spanning a pH range from 4.1 to 7.8. ¹⁵N labelled nitrate (NO₃⁻) was added to assess nitrification rates by pool dilution and to distinguish between N₂O from NO₃⁻ reduction and NH₃ oxidation. Sterilized soil slurries were used to determine the rates of chemodenitrification (i.e. the production of nitric oxide (NO) and N₂O from the chemical decomposition of nitrite (NO₂⁻)) as a function of NO₂⁻ concentrations. Additions of NO₂⁻ to aerobic soil slurries (with ¹⁵N labelled NO₃⁻ added) were used to assess its potential for inducing denitrification at aerobic conditions. For soils with pH?5, we found that the N₂O product ratios for nitrification were low (0.2-0.9‰) and comparable to values found in pure cultures of ammonia-oxidizing bacteria. In mineral soils we found only a minor increase in the N₂O product ratio with increasing soil pH, but the effect was so weak that it justifies a constant N₂O product ratio of nitrification for N₂O emission models. For the soils with pH 4.1 and 4.2, the apparent N₂O product ratio of nitrification was 2 orders of magnitude higher than above pH 5 (76‰ and 14‰). This could partly be accounted for by the rates of chemodenitrification of NO₂⁻. We further found convincing evidence for NO₂⁻-induction of aerobic denitrification in acid soils. The study underlines the role of NO₂⁻, both for regulating denitrification and for the apparent nitrifier-derived N₂O emission.     

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.     

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.     

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.     

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.     

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.     

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.     

Community composition and activities of denitrifying bacteria from adjacent agricultural soil, riparian soil, and creek sediment in Oregon, USA

We examined denitrifying bacteria from wet soils and creek sediment in an agroecosystem in Oregon, USA that received inputs of nitrogen (N) fertilizer. Our objective was to determine the variation in denitrifying community composition and activities across three adjacent habitats: a fertilized agricultural field planted to perennial ryegrass, a naturally vegetated riparian area, and creek sediment. Using C₂H₂ inhibition, denitrifying enzyme and N₂O-reductase activities were determined in short-term incubations of anaerobic slurries. A key gene in the denitrification pathway, N₂O reductase (nosZ), served as a marker for denitrifiers. Mean denitrifying enzyme activity (DEA) was similar among habitats, ranging from 0.5 to 1.8 μg N g⁻¹ dry soil h⁻¹. However, the ratio of N₂O production, without C₂H₂, to DEA was substantially higher in riparian soil (0.64±0.02; mean±standard error, n=12) than in agricultural soil (0.19±0.02) or creek sediment (0.32±0.03). Mean N₂O-reductase activity ranged from 0.5 to 3.2 μg N g⁻¹ dry soil h⁻¹, with greater activity in agricultural soil than in riparian soil. Denitrifying community composition differed significantly among habitats based on nosZ terminal-restriction fragment length polymorphisms. The creek sediment community was unique. Communities in the agricultural and riparian soil were more closely related but distinct. A number of unique nosZ genotypes were detected in creek sediment. Sequences of nosZ obtained from riparian soil were closely related to nosZ from Bradyrhizobium japonicum. Although nosZ distribution and N₂O-reductase activity differed among habitats, relationships between activity and community composition appeared uncoupled across the agroecosystem.     

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.     

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.     

Denitrification enzyme activity and potential of subsoils under grazed grasslands assayed by membrane inlet mass spectrometer

The importance of subsoil denitrification on the fate of agriculturally derived nitrate (NO₃) leached to groundwater is crucial for budgeting N in an ecosystem and for identifying areas where the risk of excess NO₃ is reduced. However, the high atmospheric background of di-nitrogen (N₂) causes difficulties in assessing denitrification enzyme activity (DEA) and denitrification potential (DP) in soils directly. Here, we apply Membrane Inlet Mass Spectrometry (MIMS) technique to investigate indirectly DEA and DP in soils by measuring N₂/Ar ratio changes in headspace water over soil. Soils were collected from 0-10, 15-25 and 60-70 cm depths of a grazed ryegrass and grass-clover. The samples were amended with helium-flushed deionized water containing ranges of NO₃ and carbon (glucose-C) and were incubated for six hours in the dark at 21 °C. The peaks for N₂/Ar ratio, declined with increasing soil depth, indicating a reduced substrate requirements to initiate DEA en-masse (15-30 mg NO₃-N alone or with 60-120 mg glucose-C, kg⁻¹ soil). The dissolved N₂O concentrations were very small (0.004-0.269 μg N kg⁻¹ soil) but responded well to the added N and C, showing a reduction in DEA with soil depth. In three separate studies, only subsoils were incubated for 3 days at 12 °C with 20-30 mg NO₃-N ± 40-60 mg glucose-C, kg⁻¹ soil. Denitrification capacity (DC, NO₃ only treatment) was not statistically different to the control (no amendment) within a land use (0.03-0.05 vs. 0.07-0.22 mg N kg⁻¹ soil d⁻¹), the highest being in ryegrass subsoils receiving groundwater. The DP was significantly (P < 0.0001) higher in subsoils under ryegrass than under grass-clover (0.50-0.71 vs. 1.15 mg N kg⁻¹ soil d⁻¹). The rates of DP (NO₃ + glucose-C) increased significantly (P < 0.0001) in unsaturated and saturated subsoils (0.92 and 2.19 mg N kg⁻¹ soil d⁻¹, respectively) of grass-clover, due to the higher reductive state resulting from the 10 day pre-incubation. Available C accelerated denitrification in soils and superseded the temporary elevation in oxidative state due to NO₃ addition. The substrates load differences between the land uses regulated the degree of denitrification rates. Results suggest that both dissolved N₂O measured by gas chromatography and N₂/Ar ratio measured by MIMS to indirectly determine DEA, and the latter to quantify total DC/DP in soils can be used. However, interference of oxygen in the MIMS system should be considered if available C is added or is naturally elevated in soil or groundwater.     

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.     

Gaseous and leaching nitrogen losses from no-tillage and conventional tillage systems following surface application of cattle manure

Previous studies have demonstrated inconsistent results on the impact of tillage systems on nitrogen (N) losses from field-applied manure. This study assessed the impact of no-tillage (NT) and conventional tillage (CT) systems on gaseous N losses, N₂O:N₂O + N₂ ratios and NO₃⁻-N leaching following surface application of cattle manure. The study was undertaken during the 2003/2004 and 2004/2005 seasons at two field sites in Nova Scotia namely, Streets Ridge (SR) in Cumberland County and the Bio-environmental Engineering Centre (BEEC) in Truro. Results showed that the NT system had higher (p < 0.05) NH₃ losses than CT. Over the two seasons, manure incorporation in CT reduced NH₃ losses on average by 86% at SR and 78% at BEEC relative to NT. At both sites and during both seasons, denitrification rates and N₂O fluxes in NT were generally higher than in CT plots, presumably due to higher soil water and organic matter content in NT. Over the two seasons, mean denitrification rates at SR were 239 and 119 g N ha⁻¹ d⁻¹, while N₂O fluxes were 120 and 64 g N ha⁻¹ d⁻¹ under NT and CT, respectively. At BEEC mean denitrification rates were 114 and 71 g N ha⁻¹ d⁻¹, while N₂O fluxes were 52 and 27 g N ha⁻¹ d⁻¹ under NT and CT, respectively. Conversely, N₂O:N₂O + N₂ ratios were lower in NT than CT suggesting more complete reduction of N₂O to N₂ under NT. When averaged across all soil depths, NO₃⁻-N was higher (p < 0.05) in CT than NT. Nitrate-N decreased with depth at both sites regardless of tillage. In most cases, NO₃⁻-N was higher under CT than NT at all soil depths. Similarly, flow-weighted average NO₃⁻-N concentrations in drainage water were generally higher under CT. This may be partly attributed to higher denitrification rates under NT. Therefore, NT may be a viable strategy to remove NO₃⁻-N from the soil, and thus, reduce NO₃⁻-N contamination of groundwater. However, it should be noted that while the use of NT reduces NO₃⁻-N leaching it may come with unintended environmental tradeoffs, including increased NH₃ and N₂O emissions.     

Heterotrophic and autotrophic nitrification in two acid pasture soils

Laboratory incubation experiments, using ¹⁵N-labeling techniques and simple analytical models, were conducted to measure heterotrophic and autotrophic nitrification rates in two acid soils (pH 4.8-5.3; 1/5 in H₂O) with high organic carbon contents (6.2-6.8% in top 5 cm soil). The soils were from pastures located near Maindample and Ruffy in the Northeast Victoria, Australia. Gross rates of N mineralization, nitrification and immobilization were measured. The gross rates of autotrophic nitrification were 0.157 and 0.119 μg N g⁻¹ h⁻¹ and heterotrophic nitrification rates were 0.036 and 0.009 μg N g⁻¹ h⁻¹ for the Maindample and Ruffy soils, respectively. Heterotrophic nitrification accounted for 19% and 7% of the total nitrification in the Maindample and Ruffy soils, respectively. The heterotrophic nitrifiers used organic N compounds and no as the substrate for nitrification.     

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.     

Nitrate leaching in soil: Tracing the NO3 sources with the help of stable N and O isotopes

Legumes increase the plant-available N pool in soil, but might also increase NO₃⁻ leaching to groundwater. To minimize NO₃⁻ leaching, N-release processes and the contribution of legumes to NO₃⁻ concentrations in soil must be known. Our objectives were (1) to quantify NO₃⁻-N export to >0.3 m soil depth from three legume monocultures (Medicago x varia Martyn, Onobrychis viciifolia Scop., Lathyrus pratensis L.) and from three bare ground plots. Furthermore, we (2) tested if it is possible to apply a mixing model for NO₃⁻ in soil solution based on its dual isotope signals, and (3) estimated the contribution of legume mineralization to NO₃⁻ concentrations in soil solution under field conditions. We collected rainfall and soil solution at 0.3 m soil depth during 1 year, and determined NO₃⁻ concentrations and δ¹⁵N and δ¹⁸O of NO₃⁻ for >11.5 mg NO₃⁻-N l⁻¹. We incubated soil samples to assess potential N release by mineralization and determined δ¹⁵N and δ¹⁸O signals of NO₃⁻ derived from mineralization of non-leguminous and leguminous organic matter.Mean annual N export to >0.3 m soil depth was highest in bare ground plots (9.7 g NO₃⁻-N m⁻²; the SD reflects the spatial variation) followed by Medicago x varia monoculture (6.0 g NO₃⁻-N m⁻²). The O. viciifolia and L. pratensis monocultures had a much lower mean annual N export (0.5 and 0.3 g NO₃⁻-N m⁻²). The averaged NO₃⁻-N leaching during 70 days was not significantly different between field estimates and incubation for the Medicago x varia Martyn monoculture.The δ¹⁵N and δ¹⁸O values in NO₃⁻ of rainfall (δ¹⁵N: 3.3±0.8‰; δ¹⁸O: 30.8±4.7‰), mineralization of non-leguminous SOM (9.3±0.9‰; 6.7±0.8‰), and mineralization of leguminous SOM (1.5±0.6‰; 5.1±0.9‰) were markedly different. Applying a linear mixing model based on these three sources to δ¹⁵N and δ¹⁸O values in NO₃⁻ of soil solution during winter 2003, we calculated 18-41% to originate from rainfall, 38-57% from mineralization of non-leguminous SOM, and 18-40% from mineralization of leguminous SOM.Our results demonstrate that (1) even under legumes NO₃⁻-N leaching was reduced compared to bare ground, (2) the application of a three-end-member mixing model for NO₃⁻ based on its dual isotope signals produced plausible results and suggests that under particular circumstances such models can be used to estimate the contributions of different NO₃⁻ sources in soil solution, and (3) in the 2nd year after establishment of legumes, they contributed approximately one-fourth to NO₃⁻-N loss.     

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.