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In this paper we discuss three topics concerning N₂O emissions from agricultural systems. First, we present an appraisal of N₂O emissions from agricultural soils (Assessment). Secondly, we discuss some recent efforts to improve N₂O flux estimates in agricultural fields (Measurement), and finally, we relate recent studies which use nitrification inhibitors to decrease N₂O emissions from N-fertilized fields (Mitigation). To assess the global emission of N₂O from agricultural soils, the total flux should represent N₂O from all possible sources; native soil N, N from recent atmospheric deposition, past years fertilization, N from crop residues, N₂O from subsurface aquifers below the study area, and current N fertilization. Of these N sources only synthetic fertilizer and animal manures and the area of fields cropped with legumes have sufficient global data to estimate their input for N₂O production. The assessment of direct and indirect N₂O emissions we present was made by multiplying the amount of fertilizer N applied to agricultural lands by 2% and the area of land cropped to legumes by 4 kg N₂O-N ha⁻¹. No regard to method of N application, type of N, crop, climate or soil was given in these calculations, because the data are not available to include these variables in large scale assessments. Improved assessments should include these variables and should be used to drive process models for field, area, region and global scales. Several N₂O flux measurement techniques have been used in recent field studies which utilize small and ultralarge chambers and micrometeorological along with new analytical techniques to measure N₂O fluxes. These studies reveal that it is not the measurement technique that is providing much of the uncertainty in N₂O flux values found in the literature but rather the diverse combinations of physical and biological factors which control gas fluxes. A careful comparison of published literature narrows the range of observed fluxes as noted in the section on assessment. An array of careful field studies which compare a series of crops, fertilizer sources, and management techniques in controlled parallel experiments throughout the calendar year are needed to improve flux estimates and decrease uncertainty in prediction capability. There are a variety of management techniques which should conserve N and decrease the amount of N application needed to grow crops and to limit N₂O emissions. Using nitrification inhibitors is an option for decreasing fertilizer N use and additionally directly mitigating N₂O emissions. Case studies are presented which demonstrate the potential for using nitrification inhibitors to limit N₂O emissions from agricultural soils. Inhibitors may be selected for climatic conditions and type of cropping system as well as the type of nitrogen (solid mineral N, mineral N in solution, or organic waste materials) and applied with the fertilizers.

Laboratory experiments were carried out to study the effect of various factors that affect the efficacy of the nitrification inhibitors, benzotriazole, o-nitrophenol, m-nitroaniline and dicyandiamide. In a Paleustalf, increasing concentrations of the inhibitors from 0 to 15 mg/kg soil prolonged the nitrification up to 60 days. Increase in temperature from 10 to 30°C decreased the efficacy of all four nitrification inhibitors (by 6–62% at 30 days). Benzotriazole was equally effective in soil moisture conditions ranging from 40 to 80% of the maximum water holding capacity of the soil (WHC). o-Nitrophenol and m-nitroaniline were more effective at 60% WHC, while the efficacy of DCD was more at 40% WHC. Addition of 1000 mg/kg soil of fresh organic matter reduced the efficacies of o-nitrophenol, m-nitroaniline and benzotriazole by 55, 65 and 22%, respectively while the reduction in the efficacy of dicyandiamide was non-significant. Liming an acidic soil (Kandiustalf) to change the pH from 5.4 to 8.3 decreased the efficacies of the nitrification inhibitors and decreased the ammonium content in the soil at 30 days from 55 to 9 mg/kg in case of o-nitrophenol and m-nitroaniline and from 53 to 35 mg/kg in case of benzotriazole and dicyandiamide.

A ¹⁵N labelling technique was used to measure N₂O and N₂ emissions from an undisturbed grassland soil treated with cow urine and held at 30 cm water tension and 20 ° C in a laboratory. Large emissions of dinitrogen were detected immediately following urine application to pasture. These coincided with a rapid and large increase in soil water-soluble carbon levels, some of this increase being attributed to solubilization of soil organic matter by high pH and ammonia concentrations. Emissions of nitrous oxide generally increased with time in contrast to dinitrogen fluxes which decreased as time progressed. Estimated losses of N₂O and N₂ over a 30 day period were between 1 to 5% and 30 to 65% of the urine N applied plus N mineralized from soil organic matter, respectively. Most of the N₂ and N₂O originated from denitrification with nitrification - denitrification being of minor significance as a source of N₂O. Comparisons of the ¹⁵N enrichments in the soil mineral N pools and the evolved N₂O suggested that much of the N₂O was produced in the 5-8 cm zone of the soil. It is concluded that established grassland soils contain large amounts of readily-oxidizable organic carbon which may be used by soil denitrifying organisms when nitrate is non-limiting and soil redox potential is lowered due to high rates of biological activity and high soil moisture contents.

One approach to reduce NO3 movement to groundwater is increasing the proportion of N supplied to the crop as NH4–N. Nitrification inhibitors (NI's) can be used to enhance NH4–N supply, but most studies have focused on yield response, with little attention given to environmental impacts. To determine the effect of enhanced NH4 sources on corn grain yield, N uptake and NO3 movement to groundwater, three sidedress materials were compared during three different growing seasons. Application of anhydrous ammonia (AA) and addition of the NI, dicyandiamide (DCD) to urea-ammonium nitrate (UAN) both reduced NO3 leaching losses relative to that incurred with UAN. With AA and UAN + DCD (as compared with UAN) subsoil solution NO3 concentrations were reduced by an average of: 1.1 mg NO3–N kg-1 soil following (fall 1993) a dry growing season; 2.4 mg NO3–N kg-1 soil during (spring and summer 1994) and 1.4 mg NO3–N kg-1 soil after (fall 1994) a wet growing season; and 0.5 mg NO3–N kg-1 soil following (fall 1995) a growing season with intermediate rainfall. Based on average solution NO3 concentrations and approximate drainage after harvest, estimated N losses between harvest and freeze-up were 43, 22 and 19 kg N ha-1 with UAN, UAN + DCD and AA, respectively (average of 3 years). Grain yields and aboveground N uptake were greater with AA and UAN + DCD than with UAN, and residual fertilizer N (applied N less aboveground N uptake) was 18, 6 and -2 kg N ha-1 with UAN, UAN + DCD and AA, respectively (average of 3 years). As is often observed, the trend for greater yield with addition of the NI was not large or consistent enough to meet registration criteria. Data demonstrating reduced NO3 leaching are also relevant, and positive environmental impacts should be a criterion for registration. For growers who are reluctant to use AA, this would provide an alternative source to maximize yield while minimizing NO3 movement to groundwater.

Nitrification rates (n) in the floodwater of an alkaline clay were measured in the absence or presence of rice plants by inhibition of ammonium oxidation and 15N-dilution techniques. Floodwater nitrate concentrations in control treatments showed a marked diurnal variation, and were higher than in the inhibitor treatments after the first day. Ammonium concentrations in floodwater declined exponentially in all treatments, being markedly affected by diffusion and NH3 volatilization but little affected by nitrification and plant uptake. Nitrification rates in floodwater estimated by 15N-dilution were generally higher than the rates estimated by the inhibitor method. Estimates of n were generally higher during daylight hours than at night, and did not differ significantly between planted and unplanted pots. Microbial immobilisation of labelled ammonium and gross N immobilisation were not affected by addition of the nitrification inhibitor 2-ethynylpyridine.

In a study on spatial distribution of methane oxidation in an unplanted flooded field, methane-oxidizing activity, analysed in soil samples under laboratory conditions, decreased with increasing depth (25 cm and beyond). In a flooded field planted to rice, rates of methane oxidation followed the order : rhizosphere (collected from roots at 10-20 cm depth) > surface soil at (0-1 cm) > subsurface soil at 10-20 cm depth, diagonally 10-15 cm away from the centre of hill. Application of ammonium sulfate and, to a lesser extent, urea to surface, rhizosphere and subsurface soil samples from flooded field planted to rice effected a distinct inhibition of methane oxidation. Nitrification inhibitors (thiourea, sodium thiosulfate and dicyandiamide) were also effective in inhibiting methane oxidation. Both surface and rhizosphere soil samples harbored higher populations of methane-oxidizing bacteria than the subsurface soil. Inhibition of methane oxidation in surface and rhizosphere soil samples concomitant with the suppression of autotrophic ammonium oxidizers by nitrification inhibitors implicates an active involvement of autotrophic ammonium oxidizers in methane oxidation.

Injection of cattle slurry into a grassland soil decreases NH₃ volatilisation and increases N utilisation by the sward, but may also increase denitrification losses. Denitrification rates were measured using a soil core incubation technique involving acetylene inhibition, following injection of cattle slurry (67 t ha⁻¹) into a grassland soil. The slurry was injected, either with or without a nitrification inhibitor (DCD), on 8 December 1989. Two-weekly measurements were carried out up to 18 weeks after injection. Compared to the control plot, denitrification rates were significantly higher after slurry injection. Addition of DCD to the slurry almost eliminated this effect. Estimated N-losses during 18 weeks after injection were 0.9 (control), 4.1 (+ DCD), and 13.7 (-DCD) kg N ha⁻¹. Denitrification losses were 7% of the injected NH₄-N and decreased to 2% of the injected NH₄-N when DCD was added. Denitrification could account for about 19% of the difference in apparent recovery of N from slurry injected with and without DCD. The results suggested that considerable amounts of $NO_3^ - $ were lost due to leaching.

The effects of select monoterpenes on nitrogen (N) mineralization and nitrification potentials were determined in four separate laboratory bioassays. The effect of increasing monoterpene addition was an initial reduction in NO3--N production (nitrification inhibition), followed by a reduction in the sum of NH4+-N and NO3--N (inhibition of net N mineralization and net immobilization at high monoterpene additions. Monoterpenes could produce this pattern by inhibiting nitrification, reducing net N mineralization, enhancing immobilization of NO3--N relative to NH4+-N, and/or stimulating overall net immobilization of N by carbon-rich material. Initial monoterpene concentrations in the assay soils were about 5% of the added amount and were below detection after incubation in most samples. Potential N mineralization-immobilization, nitrification, and soil monoterpene concentrations were determined by soil horizon for four collections from a ponderosa pine (Pinus ponderosa) stand in New Mexico. Concentrations of monoterpenes declined exponentially with soil depth and varied greatly within a horizon. Monoterpene content of the forest floor was not correlated with forest floor biomass. Net N mineralization was inversely correlated with total monoterpene content of all sampled horizons. Nitrification was greatest in the mineral soil, intermediate in the F-H horizon, and never occurred in the L horizon. Nitrification in the mineral soil was inversely correlated with the amount of monoterpenes in the L horizon that contain terminal unsaturated carbon-carbon bonds r2=0.37, P≤ 0.01). This pattern in the field corresponded to the pattern shown in the laboratory assays with increasing monoterpene additions.

Denitrification rates (d) in a flooded alkaline clay were measured following addition of either to the floodwater, by collecting evolved N2 + N2O in an enclosure in the absence or presence of rice plants. Similar estimates of d were obtained in the treatment when the isotopic composition of the enclosed atmosphere was determined using arc redistribution or direct mass spectrometric analysis. Approximately 90% of the gaseous products of denitrification were physically trapped in the soil five days after addition. Mechanical shaking of the soil-water system was an effective method for releasing entrapped gas. Denitrification showed a marked diurnal variation in both and treatments planted to rice, with higher rates during the day than at night. Measured rates of denitrification were higher in planted than in unplanted pots for both and treatments for normal gas sampling. However, evidence was obtained that this was not a real effect, but was due to release of entrapped gas. Denitrification losses corrected for gas entrapment were estimated at <5% of applied . The 15N mass balance indicated that a much larger amount of applied ammonium (15–25%) was lost by NH3 volatilisation. The rate of denitrification corrected for gas entrapment was similar to the rate of nitrification estimated by inhibition of ammonium oxidation. Although the inhibitors 2-ethynylpyridine and acetylene prevented denitrification by effectively inhibiting nitrification of , the total recovery of 15N in the soil-plant system did not increase. The total recovery of was 7–9% higher in the presence than in the absence of rice.

Three techniques for estimating nitrification rates in flooded soils were evaluated in short-term incubation experiments using three soils. The techniques were based on inhibition of either ammonium or nitrite oxidation and 15N isotope dilution. Of four inhibitors of ammonium oxidation evaluated, one (allylthiourea) was ineffective and two (2-ethynylpyridine or phenyl acetylene dissolved in ethanol) promoted immobilization of ammonium. Emulsified 2-ethynylpyridine and acetylene were equally effective inhibitors of ammonium oxidation and had little or no effect on gross rates of N mineralization and immobilization. Four inhibitors of nitrite oxidation were evaluated, but this approach was compromised by the nonspecificity of three of the compounds--potassium cyanide, 2-ethylamino-4-isopropylamino-6-methylthio s-triazine (ametryne) and 3-(3,4-dichlorophenyl)-1-methylurea (DMU)--and by the partial effectiveness of another (potassium chlorate). Two methods based on isotope dilution gave similar estimates of nitrification rates. These rates were similar to those estimated by inhibition of ammonium oxidation in one soil but were lower in the other two soils. In the latter two soils, nitrification of labeled ammonium derived from dissimilatory nitrate reduction resulted in underestimation of nitrification rates by isotope dilution