Nitrous Oxide Concentrations in the Soil of a Mown Grassland: Comparison of Model Results with Soil Profile Measurements

Nitrous oxide (N₂O) concentrations in the soilprofile of a fertilized grassland on the Swiss plateauwere measured at irregular intervals during one year.Air samples were taken from air-permeable tubesinstalled at depths between 2 and 100 cm belowthe surface. Highest concentrations in thetopsoil were observed following precipitationafter fertilization. In the subsoil,concentrations were highest when the soil watercontent fell below about 92% after a wet periodand mineral nitrogen was available from priorfertilization. N₂O concentrations in thetopsoil were simulated with the process-basedgrassland ecosystem model PaSim 2.5 (PastureSimulation Model) and compared with measured soilN₂O concentrations. The model simulated wellthe concentration peaks after fertilizeradditions and the concentrations in winter. Butthe simulated baseline concentrations during thegrowing season were overestimated. Possiblecauses for this discrepancy are discussed andsuggestions are made to improve the model.     

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.     

Ammonia volatilization,N2O and CO2 emissions from landfill leachate-irrigated soils

Effects of leachate addition on ammonia volatilization and N₂O and CO₂ emissions from two different soils were investigated using the 10-day laboratory incubation method at two levels of moisture content. Ammonia volatilization was dominated by soil pH and only occurred in alkaline clay soil, where 0.26–0.32% of soil ammonia could be lost. The N₂O emission from the alkaline clay soil was one order of magnitude greater than that from the acidic sandy soil, when either water or leachate was irrigated. Increasing the moisture content from 46% water-filled pore space (WFPS) to 70% WFPS in the alkaline clay soil or the acidic sandy soil by either water or leachate irrigation increased the N₂O emission by over twofold. The CO₂ emission from each soil sample at the two WFPSs was almost the same. The CO₂ emission from the alkaline clay soil with leachate addition was 72% lower than that from the acidic sandy soil with leachate addition, and 6.7 times higher than that from the alkaline clay soil with distilled water addition. Ammonia volatilization and N₂O emission under leachate irrigation could be minimized by avoiding the excessively wet condition and by selecting the acidic sandy soil with low organic carbon and total nitrogen content.     

Influence of H<Subscript>2</Subscript> on the decomposition of halides by nonthermal plasma incorporated with in situ alkaline absorption

To control the emission of halides into the environment, an experiment on the nonthermal plasma decomposition of the halides CF₄, CHF₃, C₂HCl₃, and CHClF₂ was conducted in a wire-in-tube corona reactor. It was found that the decomposition of C₂HCl₃ and CHClF₂ was easy compared with the decomposition of CF₄ and CHF₃. With the addition of H₂ in N₂ gas, the decomposition ratio of CF₄, C₂HCl₃, and CHClF₂ increased. In contrast, the decomposition ratio of CHF₃ in a hydrogen-rich atmosphere was lower than that in an N₂ atmosphere. It was demonstrated that the yields of HF and/or HCl formed during halide decomposition clearly increased in the presence of H₂ in N₂ gas. Furthermore, in order to prevent the production of unwanted products from halide decomposition, a combination of plasma decomposition and in situ alkaline absorption was devised by coating a layer of Ca(OH)₂ onto the surface of the grounding electrode. It was demonstrated that the Ca(OH)₂ sorbent played an effective role as a scavenger, participating in halide decomposition by capturing reaction products such as HCl and HF, therefore resulting in increased halide decomposition.     

Simulation of Exterior Conditions in Permanently Closed Soil Chambers by Controlling Air Flow,Soil Water Content,and Temperature

Volatile substances and gases resulting e.g. from degradation processes of chemicals in soils emit into the atmosphere and no chemical mass balance is complete without considering this path. Closed soil chambers allow the evaluation of this transfer to the atmosphere. This study deals with the influence of soil chambers with a glass plate cover on physical soil conditions in the chambers and the possibility to simulate the exterior conditions within the chambers. The water content immediately at the soil surface is an important factor for the microbial activity and the transfer of gaseous compounds to the atmosphere as well. It is monitored by specially designed water content sensors in 1 cm depth in the chamber and as control outside. Funnels with a cross section equal to the soil surface area of the chamber collect the rain water and channel it into the soil chamber. This results in soil water content in the chambers very similar to that outside. For the purpose of analysing ¹⁴CO₂ and volatile ¹⁴C-compounds, air is permanently pumped through the chamber. In order to simulate natural conditions, the wind speed is measured 1 cm above the soil surface outside the chambers. A control circuit adjusts the air flow through the chamber to a value corresponding to the wind speed outside. Temperature measurements in 1 cm depth verify that there is no significant difference between the soil chamber and the control outside.     

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.     

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.     

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.     

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.     

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.     

Reductive decomposition of waste gypsum with SiO<Subscript>2</Subscript>, Al<Subscript>2</Subscript>O<Subscript>3</Subscript>, and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> additives

From the point of view of a sustainable and environment-friendly society based on the recycling of material resources, it is preferable to utilize waste gypsum as a substitute for lime, which is currently produced by the calcination of limestone. In the present work, the reductive decomposition of CaSO₄ was investigated under an atmosphere of CO: 2 vol%, CO₂: 30 vol%, with N₂ as a carrier gas without and with the addition of SiO₂, Al₂O₃, or Fe₂O₃. It was found that the decomposition temperature of CaSO₄ was significantly reduced from 1673 K to 1223 K when only 5 wt% Fe₂O₃ was added to CaSO₄. In the case of the addition of SiO₂ or Al₂O₃ to CaSO₄, the decomposition temperature was reduced from 1673 K to 1623 K. This was due to the formation of composite oxides (calcium ferrite, calcium silicate, or calcium aluminate) during the reaction of CaSO₄ with the additives at a lower temperature. In addition, the formation of unfavorable product CaS was inhibited in the presence of 5 wt% Fe₂O₃, and this inhibition effect further increased as the addition of Fe₂O₃ was increased. In contrast, no significant effect on the inhibition of CaS formation was observed on the addition of SiO₂ or Al₂O₃.     

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.     

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.     

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 ₄ ⁺ and 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.     

Effect of fresh green waste and green waste compost on mineral nitrogen, nitrous oxide and carbon dioxide from a Vertisol

Incorporation of organic waste amendments to a horticultural soil, prior to expected risk periods, could immobilise mineral N, ultimately reducing nitrogen (N) losses as nitrous oxide (N₂O) and leaching. Two organic waste amendments were selected, a fresh green waste (FGW) and green waste compost (GWC) as they had suitable biochemical attributes to initiate N immobilisation into the microbial biomass and organic N forms. These characteristics include a high C:N ratio (FGW 44:1, GWC 35:1), low total N (<1%), and high lignin content (>14%). Both products were applied at 3 t C/ha to a high N (plus N fertiliser) or low N (no fertiliser addition) Vertisol soil in PVC columns. Cumulative N₂O production over the 28 day incubation from the control soil was 1.5 mg/N₂O/m², and 11 mg/N₂O/m² from the control + N. The N₂O emission decreased with GWC addition (P < 0.05) for the high N soil, reducing cumulative N₂O emissions by 38% by the conclusion of the incubation. Analysis of mineral N concentrations at 7, 14 and 28 days identified that both FGW and GWC induced microbial immobilisation of N in the first 7 days of incubation regardless of whether the soil environment was initially high or low in N; with the FGW immobilising up to 30% of available N. It is likely that the reduced mineral N due to N immobilisation led to a reduced substrate for N₂O production during the first week of the trial, when soil N₂O emissions peaked. An additional finding was that FGW + N did not decrease cumulative N₂O emissions compared to the control + N, potentially due to the fact that it stimulated microbial respiration resulting in anaerobic micro sites in the soil and ultimately N₂O production via denitrification. Therefore, both materials could be used as post harvest amendments in horticulture to minimise N loss through nitrate-N leaching in the risk periods between crop rotations. The mature GWC has potential to reduce N₂O, an important greenhouse gas.     

Transformations of nitrogen at the interface between the topsoil and an impervious clay subsoil

Much work has been done on gaseous emissions and leaching of nitrogenous compounds from whole soil profiles and also from soil surface measurements which are assumed to be mainly due to topsoil activity. In soils with an impervious clay subsoil, the boundary between the topsoil and subsoil may provide an interface for microbial activity, including N transformations. In this study, we investigated movement and transformations of two reactive N species (nitrate and urea) at the subsoil interface using a series of replicate, intact soil blocks, under two contrasting watering regimes. We measured fluxes in both liquid and gaseous phases and demonstrated that nitrate reaching the subsoil interface does not necessarily leach into water systems, but may denitrify immediately and could, therefore, add to atmospheric pollution through N₂O production. On the other hand, ammonium reaching the subsoil interface either directly, or after mineralization, appears to be more mobile than expected and has the potential to pollute watercourses.     

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 fields 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.     

Transformations of nitrogen at the interface between the topsoil and an impervious clay subsoil

Much work has been done on gaseous emissions and leaching of nitrogenous compounds from whole soil profiles and also from soil surface measurements which are assumed to be mainly due to topsoil activity. In soils with an impervious clay subsoil, the boundary between the topsoil and subsoil may provide an interface for microbial activity, including N transformations. In this study, we investigated movement and transformations of two reactive N species (nitrate and urea) at the subsoil interface using a series of replicate, intact soil blocks, under two contrasting watering regimes. We measured fluxes in both liquid and gaseous phases and demonstrated that nitrate reaching the subsoil interface does not necessarily leach into water systems, but may denitrify immediately and could, therefore, add to atmospheric pollution through N₂O production. On the other hand, ammonium reaching the subsoil interface either directly, or after mineralization, appears to be more mobile than expected and has the potential to pollute watercourses.     

Effect of ZnCl<Subscript>2</Subscript> impregnation ratio on pore structure of activated carbons prepared from cattle manure compost: application of N<Subscript>2</Subscript> adsorption-desorption isotherms

Activated carbons were prepared from cattle manure compost (CMC) by ZnCl₂ activation with various ZnCl₂/CMC mass ratios. Based on the N₂ adsorption-desorption isotherms, mathematical models including the Dubinin-Radushkevich (DR) equation, the α_s plot, and the Horvath-Kawazoe method were used to analyze the pore structural characteristics of the prepared activated carbons. It was found that for carbons possessing both micro-and mesopores, the DR method provided a more accurate estimation than the α_s method for the extent of microporosity. The effect of the ZnCl₂ impregnation ratio on the pore structure was discussed using the DR method. The results revealed that pore evolution involved three distinct regions with increases in the amount of impregnated ZnCl₂: raising the ZnCl₂/CMC mass ratio from 0.00 to 0.50 resulted in a 19-fold increase in micropore volume (V_me ^D) but caused no change in the mesopore volume (V_me ^D); increasing the ZnCl₂/CMC mass ratio from 0.50 to 1.00 led to an increment in V_mi ^D of about 50% and in V_me ^D of 170%; while raising the ratio from 1.50 to 2.50 caused a slight decrease in V_mi ^D but a 200% increment in the value of V_me ^D.     

National Greenhouse Gas Inventories: Understanding Uncertainties versus Potential for Improving Reliability

We investigated the Austrian national greenhouse gas emission inventory to review the reliability and usability of such inventories. The overall uncertainty of the inventory (95% confidence interval) is just over 10% of total emissions, with nitrous oxide (N₂O) from soils clearly providing the largest impact. Trend uncertainty – the difference between 2 years – is only about five percentage points, as important sources like soil N₂O are not expected to show different behavior between the years and thus exhibit a high covariance. The result is very typical for industrialized countries – subjective decisions by individuals during uncertainty assessment are responsible for most of the discrepancies among countries. Thus, uncertainty assessment cannot help to evaluate whether emission targets have been met. Instead, a more rigid emission accounting system that allows little individual flexibility is proposed to provide harmonized evaluation uninfluenced by the respective targets. Such an accounting system may increase uncertainty in terms of greenhouse gas fluxes to the atmosphere. More importantly, however, it will decrease uncertainty in intercountry comparisons and thus allow for fair burden sharing. Setting of post-Kyoto emission targets will require the independent evaluation of achievements. This can partly be achieved by the validation of emission inventories and thorough uncertainty assessment.