Determinants of nitrous oxide emission from agricultural drainage waters

Emissions of the powerful greenhouse gas nitrous oxide (N₂O) from agricultural drainage waters are poorly quantified and its determinants are not fully understood. Nitrous oxide formation in agricultural soils is known to increase in response to N fertiliser application, but the response of N₂O in field drainage waters is unknown. This investigation combined an intensive study of the direct flux of N₂O from the surface of a fertilised barley field with measurement of dissolved N₂O and nitrate (NO₃) concentrations in the same field’s drainage waters. Dissolved N₂O in drainage waters showed a clear response to field N fertilisation, following an identical pattern to direct N₂O flux from the field surface. The range in N₂O concentrations between individual field drains sampled on the same day was large, indicating considerable spatial variability exists at the farm scale. A consistent pattern of very rapid outgassing of the dissolved N₂O in open drainage ditches was accentuated at a weir, where increased turbulence led to a clear drop in dissolved N₂O concentration. This study underlines the need for carefully planned sampling campaigns wherever whole farm or catchment N₂O emission budgets are attempted. It adds weight to the argument for the downward revision of the IPCC emission factor (EF₅-g) for NO₃ in drainage waters.     

Nitrous Oxide in Agricultural Drainage Waters Following Field Fertilisation

Dissolved nitrous oxide (N₂O), nitrate (NO₃ ^-), and ammonium (NH₄ ⁺) concentrations in an agricultural field drain were intensively measured over the period of field nitrogen (N) fertilisation and for several weeks thereafter. Supersaturations of dissolved N₂O were observed in field drain waters throughout the study. On entry to an open drainage ditch, concentrations of dissolved N₂O rapidly decreased and a total N₂O-N emission via this pathway of 13.2 g over the period of study (45 days) was calculated. This compared with a predicted emission of the order of 300 g, based on measured losses of NO₃ ^- and NH₄ ⁺ in the field drainage water, and the default IPCC emission factor of 0.01 kg N₂O-N per kg Nentering rivers and estuaries. In contrast to widespread evidence of a clear relationship between the amount of N applied to agricultural land and subsequent direct N₂O emission from the soil surface, the relationship between the amount of N₂O in soil drainage waters and the amount of N applied was poor. We conclude that the complexity, both spatially and temporally, of the processes ultimately responsible for the amount of N₂O in agricultural drainage waters make a straightforward relationship between N₂O concentration and N application rate unlikely in all but the simplest of systems.     

Nitrous Oxide Emissions from Two Riparian Ecosystems: Key Controlling Variables

Nitrous oxide (N₂O) emissions were measured weekly to fortnightly between April 2001 and March 2002 from two riparian ecosystems drainingdifferent agricultural fields. The fields differed in the nature of the crop grown and the amount of fertiliser applied. Soil water content and soil temperature were very important controls of N₂O emission rates, with a ‘threshold’ response at 24% moisture content (by volume) and 8 °C, below which N₂O emission was very low.N₂O fluxes were higher at the site that had receivedthe most fertiliser N, but NO₃ ^- was not a limiting factor at either site. There was also a ‘threshold’ effect of rainfall, in which major rainfall events (≥10 mm) triggered a pulse of high N₂O emission if none of the other environmental factors were limiting. These results suggest the existence of multiple controls on N₂O emissions operating at a range of spatial and temporal scales and that non-linear relationships, perhaps with a hierarchical structure, are needed to model these emissions from riparian ecosystems.     

Winter and Spring Thaw Measurements of N2O,NO and NOx Fluxes using a Micrometeorological Method

The impact of nitrogen fertilizers on gaseous emissions duringwinter and spring-thaw is not well understood and was the objective of this research. Using a micrometeorological method,N₂O, NO and NO_x fluxes from ryegrass were measured from November 1997 to March 1998. Three different mineralfertilizers were applied in November: urea (U), slow-release urea(SRU) and ammonium nitrate (AN). N₂O emissions during the winter were small, increasing significantly in March. Total losses of N₂O-N were significantly higher from SRU and U plots, with winter N₂O emissions accounting for 50% of annual losses. Nitric oxide fluxes from all plots weresmall during the measurement period (<0.9 ng N m^-2 s^-1). The NO fluxes from U and AN fertilized plots were significantly higher than from SRU and control plots. NO₂ fluxes were always negative (–6 ng N m^-2 s^-1)indicating deposition, but decreased to –2 ng N m^-2s^-1 when snow was present on the soil surface. Our resultsindicate that the form of inorganic N applied has an effect on NO+ N₂O emissions but not on NO₂ fluxes.Sponsored by CAPES – Brasília, Brazil     

Field scale N2O flux measurements from grassland using eddy covariance

In order to assess nitrous oxide (N₂O) emissions from typical intensively managed grassland in northern Britain fluxes were measured by eddy covariance using tuneable diode laser absorption spectroscopy from June 2002 to June 2003 for a total period of 4000 h. With micrometeorological techniques it is possible to obtain a very detailed picture of the fluxes of N₂O at field scale (10³–10⁴ m²), which are valuable for extrapolation to regional scales. In this paper three of the four fertilizer applications were investigated in detail. N₂O emissions did not always show a clear response. Hourly fluxes were very large immediately after the June 2002 nitrogen fertilizer application, peaking at 2.5 mg N₂O–N m^?2 s^?1. Daily fluxes were averaging about 300 ng N₂O m^?2 s^?1 over the 4 days following fertilizer application. The response of N₂O emissions was less evident after the August fertilization, although 2 days after fertilizer application an hourly maximum flux of 554 ng N₂O–N m^?2 s^?1 was registered. For the rest of August the flux was undetectable. The differences between fertilization events can be explained by different environmental conditions, such as soil temperature and rainfall. A fertiliser-induced N₂O emission was not observed after fertilizer application in March 2003, due to lack of rainfall. The total N₂O flux from June 2002 to June 2003 was 5.5 kg N₂O–N ha^?1y^?1, which is 2.8% of the total annual N fertilizer input.     

The release of nitrous oxide from the intertidal zones of two European estuaries in response to increased ammonium and nitrate loading

Nitrous oxide (N₂O) release and denitrification rates were investigated from the intertidal saltmarsh and mudflats of two European river estuaries, the Couesnon in Normandy, France and the Torridge in Devon, UK. Sediment cores and water were collected from each study site and incubated for 72 h in tidal simulation chambers. Gas samples were collected at 6 and 12 h intervals from the chambers during incubation. From these N₂O emission rates were calculated. The greatest rates for both N₂O production and denitrification were measured from saltmarsh cores. These were 1032 mol N₂O m^–2 day^–1 and 2518 mol N₂ m^–2 day^–1, respectively, from the Couesnon and 109 mol N₂O m^–2 day^–1 and 303 mol N₂ m^–2 day^–1 from the Torridge. A strong positive correlation was apparent with N₂O emission rates and ammonium concentration in the sediment, nitrate concentration in floodwater and sediment aerobicity.     

Field scale N2O flux measurements from grassland using eddy covariance

In order to assess nitrous oxide (N₂O) emissions from typical intensively managed grassland in northern Britain fluxes were measured by eddy covariance using tuneable diode laser absorption spectroscopy from June 2002 to June 2003 for a total period of 4000 h. With micrometeorological techniques it is possible to obtain a very detailed picture of the fluxes of N₂O at field scale (10³–10⁴ m²), which are valuable for extrapolation to regional scales. In this paper three of the four fertilizer applications were investigated in detail. N₂O emissions did not always show a clear response. Hourly fluxes were very large immediately after the June 2002 nitrogen fertilizer application, peaking at 2.5 mg N₂O–N m^–2 s^–1. Daily fluxes were averaging about 300 ng N₂O m^–2 s^–1 over the 4 days following fertilizer application. The response of N₂O emissions was less evident after the August fertilization, although 2 days after fertilizer application an hourly maximum flux of 554 ng N₂O–N m^–2 s^–1 was registered. For the rest of August the flux was undetectable. The differences between fertilization events can be explained by different environmental conditions, such as soil temperature and rainfall. A fertiliser-induced N₂O emission was not observed after fertilizer application in March 2003, due to lack of rainfall. The total N₂O flux from June 2002 to June 2003 was 5.5 kg N₂O–N ha^–1y^–1, which is 2.8% of the total annual N fertilizer input.     

Whole-year-round Observation of N<Subscript>2</Subscript>O Profiles in Soil: A Lysimeter Study

Despite many studies of the N₂O emission, there is a lack of knowledge on the role of subsoil for N₂O emission, particularly in sandy soils. To obtain insight into the entrapment, diffusion, convection and ebullition of N₂O in the soil, the N₂O concentration in the soil atmosphere was measured over a period of 1 year in 4 lysimeters (agricultural soil monoliths of 1 m2 × 2 m) at 30, 50, 80, 155, and 190 cm depth with altogether 86 gas probes. Additionally the N₂O emission into the atmosphere was measured in 20 closed chambers at the soil surface. Concurrently the soil temperature and soil water content were recorded in order to quantify their effects on the fate of N₂O in the soil. Results of the continuous measurements between January and December 2006 were: N₂O concentrations were highest in the deeper soil; maximum concentration was found at a depth of 80 cm, where the water content was high and the gas transport reduced. The highest N₂O concentration was recorded after ‘special events’ like snowmelt, heavy rain, fertilization, and grubbing. The combination of fertilization and heavy rain led to an increase of up to 2,700 ppb in the subsoil.     

N2O emission from a combined ex-situ nitrification and in-situ denitrification bioreactor landfill

A combined process comprised of ex-situ nitrification in an aged refuse bioreactor (designated as A bioreactor) and in-situ denitrification in a fresh refuse bioreactor (designated as F bioreactor) was constructed for investigating N₂O emission during the stabilization of municipal solid waste (MSW). The results showed that N₂O concentration in the F bioreactor varied from undetectable to about 130 ppm, while it was much higher in the A bioreactor with the concentration varying from undetectable to about 900 ppm. The greatly differences of continuous monitoring of N₂O emission after leachate cross recirculation in each period were primarily attributed to the stabilization degree of MSW. Moreover, the variation of N₂O concentration was closely related to the leachate quality in both bioreactors and it was mainly affected by the COD and COD/TN ratio of leachate from the F bioreactor, as well as the DO, ORP, and NO₃^?-N of leachate from the A bioreactor.     

Study of nitrogen oxide absorption in the calcium sulfite slurry

Experiments were conducted using a bubbling reactor to investigate nitrogen oxide absorption in the calcium sulfite slurry. The effects of CaSO₃ concentration, NO₂/NO mole ratio and O₂ concentrations on NO₂ and SO₂ absorption efficiencies were investigated. Five types of additives, including MgSO₄, Na₂SO₄, FeSO₄, MgSO₄/Na₂SO₄ and FeSO₄/Na₂SO₄, had been evaluated for enhancing NO₂ absorption in CaSO₃ slurry. Results showed that CaSO₃ concentration had significant impact on NO₂ and SO₂ absorption efficiencies, and the highest absorption efficiencies of SO₂ and NO₂ could reach about 99.5 and 75.0 %, respectively. Furthermore, the NO₂ absorption was closely related to the NO₂/NO mole ratio, and the existence of NO₂ in flue gas may promote NO absorption. The presence of O₂ in simulated flue gas was disadvantage for NO _x removal because it can oxidize sulfite to sulfate. It was worth pointing out that FeSO₄/Na₂SO₄ was the best additive among those investigated additives, as the NO₂ removal efficiency was significantly increased from 74.8 to 95.0 %. IC and in situ FTIR results suggest that the main products were NO₃ ^? and NO₂ ^? in liquid phase and N₂O, N₂O₅ and HNO₃ in gas phase during the CaSO₃ absorption process.     

The influence of atmospheric n deposition on nitrous oxide and nitric oxide fluxes and soil ammonium and nitrate concentrations

The deposition of atmospheric N to soils provides sources of available N to the nitrifying and denitrifying microbial community and subsequently influences the rate of NO and N₂O emissions from soil. We have investigated the influence of three different sources of enhanced N deposition on NO and N₂O emissions 1) elevated NH₃ deposition to woodlands downwind of poultry and pig farms, 2) increased wet cloud and occult N deposition to upland forest and moorland and 3) enhanced N deposition to trees as NO^? ₃ and NH⁺ ₄ aerosol. Flux measurements of NO and N₂O were made using static chambers in the field or intact and repacked soil cores in the laboratory and determination of N₂O by gas chromatography and of NO by chemiluminescence analysis. Rates of N deposition to our study sites were derived from modelled estimates of N deposition, NH₃ concentrations measured by passive diffusion and inference from measurements of the ²¹⁰Pb inventory of soils under tree canopies compared with open grassland. NO and N₂O emissions and KCl-extractable soil NH⁺ ₄ and NO^? ₃ concentrations all increased with increasing N deposition rate. The extent of increase did not appear to be influenced by the chemical form of the N deposited. Systems dominated by dry-deposited NH₃ downwind of intensive livestock farms or wet-deposited NH⁺ ₄and NO^? ₃ in the upland regions of Britain resulted in approximately the same linear response. Emissions of NO and N₂O from these soils increased with both N deposition and KCl extractable NH⁺ ₄, but the relationship between NH⁺ ₄ and N deposition (ln NH⁺ ₄ = 0.62 ln N_deposition+0.21, r ² = 0.33, n = 43) was more robust than the relationship between N deposition and soil NO and N₂O fluxes.     

The release of nitrous oxide from the intertidal zones of two European estuaries in response to increased ammonium and nitrate loading

Nitrous oxide (N₂O) release and denitrification rates were investigated from the intertidal saltmarsh and mudflats of two European river estuaries, the Couesnon in Normandy, France and the Torridge in Devon, UK. Sediment cores and water were collected from each study site and incubated for 72 h in tidal simulation chambers. Gas samples were collected at 6 and 12 h intervals from the chambers during incubation. From these N₂O emission rates were calculated. The greatest rates for both N₂O production and denitrification were measured from saltmarsh cores. These were 1032 μmol N₂O m^?2 day^?1 and 2518 μmol N₂ m^?2 day^?1, respectively, from the Couesnon and 109 μmol N₂O m^?2 day^?1 and 303 μmol N₂ m^?2 day^?1 from the Torridge. A strong positive correlation was apparent with N₂O emission rates and ammonium concentration in the sediment, nitrate concentration in floodwater and sediment aerobicity.     

Analysis of the St. Petersburg Traffic Data using the OSPM Model

Since October 1998 two DOAS instruments were installed at the level of the first floor and at the top of a building located in St. Petersburg at Pestelya Street. The collected datacovers the time period of December 1998–March 2001, and include concentrations of benzene, toluene, NO and NO₂, ozone and SO₂. There is also an additional information about the traffic intensity and meteorological conditions. The results of the analysis of this data set, using the OSPM model, are presented here with the goal to understand the features of the air pollution dispersion in this street canyon and to analyse the information about the emission factors of the vehicles. In particular, the model results are used for the solution of the inverse problem of reconstructing the emission factors from measured concentrations. The results obtained indicate that most of the concentrations are well inside the Russian standards with the only exception of NO₂ (mean and 98-th percentile are equal to 57.8 and 119.2 g m^-3 for the street level). The same values for benzene are 18.5 and 62.6, respectively. Emission estimates show that there is a possibility that the NO_x and benzene basic emission factors recommended by the Russian national guidelines could result in overestimating the traffic emissions. These considerations are supplemented with the model sensitivity tests carried out in connection with the problem of predictability of NO₂ concentrations in the street canyon. Tests indicate that NO₂ concentrations are not very sensitive to NO_x emissions because of the usually low urban background ozone levels.     

The estimation of N2O emissions from municipal solid waste incineration facilities: The Korea case

The greenhouse gases (GHGs) generated in municipal solid waste (MSW) incineration are carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O). In South Korea case, the total of GHGs from the waste incineration facilities has been increasing at an annual rate 10%. In these view, waste incineration facilities should consider to reduce GHG emissions.This study is designed to estimate the N₂O emission factors from MSW incineration plants, and calculate the N₂O emissions based on these factors. The three MSW incinerators examined in this study were either stoker or both stoker and rotary kiln facilities. The N₂O concentrations from the MSW incinerators were measured using gas chromatography-electron capture detection (GC-ECD) equipment.The average of the N₂O emission factors for the M01 plant, M02 plant, and M03 plant are 71, 75, and 153 g-N₂O/ton-waste, respectively. These results showed a significant difference from the default values of the intergovernmental panel on climate change (IPCC), while approaching those values derived in Japan and Germany. Furthermore, comparing the results of this study to the Korea Energy Economics Institute (KEEI) (2007) data on waste incineration, N₂O emissions from MSW incineration comprised 19% of the total N₂O emissions.     

Variability of nitrous oxide and carbon dioxide emissions continuously measured in solid waste incinerators

Nitrous oxide and carbon dioxide were continuously measured and variability of emission factors (EFs) was evaluated in five municipal waste incinerators (MWIs) and four industrial waste incinerators (IWIs) from 24 to 86 days between 2008 and 2011. N₂O EFs were calculated by Monte Carlo simulation and mean N₂O EFs were 7.1, 107, 127, 219 g N₂O/ton waste combusted in MWIs with selective catalytic reduction (SCR) for NOx control, MWIs with selective non-catalytic reduction (SNCR), IWIs with SNCR, and a MWI using fluidized bed with SNCR, respectively. Climate-relevant CO₂ EFs ranged from 0.45 to 0.72 ton CO₂/ton waste combusted in MWIs. Maximum values of upper limit for 95% confidence intervals (CIs) of N₂O EFs estimated in each MWIs with SCR, MWIs with SNCR, IWIs with SNCR were 185, 94, 101% of mean N₂O EFs, respectively. Meanwhile, maximum values of upper limit for 95% CIs of CO₂ EFs were much lower as between 18 and 36% in those facilities. 84% CIs of mean N₂O EFs in MWIs with SNCR and IWIs with SNCR were overlapped indicating those values are not significantly different.     

A conceptual model of spatially heterogeneous nitrogen leaching from a welsh moorland catchment

Soil- and stream-water data from the Plynlimon research area, mid-Wales, have been used to develop a conceptual model of spatial variations in nitrogen (N) leaching within moorland catchments. Extensive peats, in both hilltop and valley locations, are considered near-complete sinks for inorganic N, but leach the most dissolved organic nitrogen (DON). Peaty mineral soils on hillslopes also retain inorganic N within upper organic horizons, but a proportion percolates into mineral horizons as nitrate (NO^? ₃), either through incomplete immobilisation in the organic layer, or in water bypassing the organic soil matrix via macropores. This NO^? ₃ reaches the stream where mineral soilwaters discharge (via matrix throughflow or pipeflow) directly to the drainage network, or via small N-enriched flush wetlands. NO^? ₃ in hillslope waters discharging into larger valley wetlands will be removed before reaching the stream. A concept of catchment ‘nitrate leaching zones’ is proposed, whereby most stream NO^? ₃ derives from localised areas of mineral soil hillslope draining directly to the stream; the extent of these zones within a catchment may thus determine its overall susceptibility to elevated surface water NO^? ₃ concentrations.     

Kinetic and Mechanistic Studies of NO X Selective Catalytic Reduction Over In/Al2O3 and N2O Decomposition Over Ru/Al2O3

Detailed kinetic studies are presented for two reactions: the nitric oxide (NO) selective catalytic reduction (SCR) by propene over indium/alumina (In/Al₂O₃) and the nitrous oxide (N₂O) reduction over ruthenium/alumina (Ru/Al₂O₃). Both reactions were studied in the presence of excess oxygen (O₂) to simulate the composition of flue gases. Apparent activation energies and apparent orders of reaction were calculated in experiments performed under differential reaction conditions. We used our experimental results to propose the reaction mechanism that leads to nitrogen formation over the two catalysts. The NO reduction proceeds through the initial formation of C _X H _Y O _Z N, a reaction intermediate that reacts with activated nitrogen oxides (NO _X ). Nitrous oxide is catalytically decomposed to nitrogen (N₂) over Ru/Al₂O₃.     

Quantification of multiple methane emission sources at landfills using a double tracer technique

A double tracer technique was used successfully to quantify whole-site methane (CH₄) emissions from Fakse Landfill. Emissions from different sections of the landfill were quantified by using two different tracers. A scaled-down version of the tracer technique measuring close-by to localized sources having limited areal extent was also used to quantify emissions from on-site sources at the landfill facility, including a composting area and a sewage sludge storage pit. Three field campaigns were performed. At all three field campaigns an overall leak search showed that the CH₄ emissions from the old landfill section were localized to the leachate collection wells and slope areas. The average CH₄ emissions from the old landfill section were quantified to be 32.6 ± 7.4 kg CH₄ h⁻¹, whereas the source at the new section was quantified to be 10.3 ± 5.3 kg CH₄ h⁻¹. The CH₄ emission from the compost area was 0.5 ± 0.25 kg CH₄ h⁻¹, whereas the carbon dioxide (CO₂) and nitrous oxide (N₂O) flux was quantified to be in the order of 332 ± 166 kg CO₂ h⁻¹ and 0.06 ± 0.03 kg N₂O h⁻¹, respectively. The sludge pit located west of the compost material was quantified to have an emission of 2.4 ± 0.63 kg h⁻¹ CH₄, and 0.03 ± 0.01 kg h⁻¹ N₂O.     

Spatially Disaggregated Inventories of Soil NO and N2O Emissions for Great Britain

Estimates of soil N₂O and NOemissions at regional and country scales arehighly uncertain, because the most widely usedmethodologies are based on few data, they do notinclude all sources and do not account forspatial and seasonal variability. To improveunderstanding of the spatial distribution of soilNO and N₂O emissions we have developedsimple multi-linear regression models based onpublished field studies from temperate climates.The models were applied to create spatialinventories at the 5 km² scale of soil NOand N₂O emissions for Great Britain. The N₂O regression model described soilN₂O emissions as a function of soil N input,soil water content, soil temperature and land useand provided an annual N₂O emission of 128 kt N₂O-N yr^-1. Emission rates largerthan 12 kg N₂O-N ha^-1 yr^-1 werecalculated for the high rainfall grassland areasin the west of Great Britain.Soil NO emissions were calculated using tworegression models, which described NO emissionsas a function of soil N input with and without afunction for the water filled pore space. Thetotal annual emissions from both methods, 66 and7 kt NO-N yr^-1, respectively, span the rangeof previous estimates for Great Britain.     

Temporal Trends in Water Chemistry in the Turkey Lakes Watershed Ontario,Canada, 1982-1999

The Turkey Lakes Watershed (TLW) was established in 1980 as asite for study of the ecosystem effects of acidic deposition, andsince then there has been 40% reduction in North AmericanSO₂ emissions. Monitoring records for bulk deposition,shallow and deep ground water, two headwater streams and two lakeoutflows have been tested to identify statistically significantmonotonic trends. The TLW appears to be responding to decliningacidifying emissions because the most prevalent chemical trendacross sample types/stations was decreasing SO₄ ^2-. Increasing pH was detected in four of the seven data sets, butonly the H⁺ decrease in bulk deposition was of a magnitudeto be an important ionic compensation for the SO₄ ^2-decline. There is little evidence of acidification recovery inTLW waters however. Increasing alkalinity was found only in theoutflow of the penultimate lake of the basin, and in fact, deepground water and the other lake outflow had decreasing alkalinitytrends (i.e., continuing acidification). For the surface waterstations, the greater part of the ionic compensation fordeclining SO₄ ^2- was decreasing base cations, and as aresult, these waters are probably becoming more dilute with time,although only the headwater streams exhibited decliningconductivity. Five of seven data sets had increasing dissolvedorganic carbon concentrations. Increasing NO₃ ^- wasimportant in ground waters. Drought has strongly influencedtrends and delayed recovery by mobilizing S stored in catchmentwetlands and/or soils.