Dry deposition of ammonia,nitric acid,ammonium, and nitrate to alpine tundra at Niwot Ridge,Colorado

Micrometeorological measurements and ambient air samples, analyzed for concentrations of NH₃, HNO₃, NH₄⁺, and NO₃⁻, were collected at an alpine tundra site on Niwot Ridge, Colorado. The measured concentrations were extremely low and ranged between 5 and 70 ng N m⁻³. Dry deposition fluxes of these atmospheric species were calculated using the micrometeorological gradient method. The calculated mean flux for NH₃ indicates a net deposition to the surface and indicates that NH₃ contributed significantly to the total N deposition to the tundra during the August–September measurement period. Our pre-measurement estimate of the compensation point for NH₃ in air above the tundra was 100–200 ng N m⁻³; thus, a net emission of NH₃ was expected given the low ambient concentrations of NH₃ observed. Based on our results, however, the NH₃ compensation point at this alpine tundra site appears to have been at or below about 20 ng N m⁻³. Large deposition velocities (>2 cm s⁻¹) were determined for nitrate and ammonium and may result from reactions with surface-derived aerosols.     

Concentration-dependent NH3 deposition processes for mixed moorland semi-natural vegetation

Dry deposition modelling typically assumes that canopy resistance (R_c) is independent of ammonia (NH₃) concentration. An innovative flux chamber system was used to provide accurate continuous measurements of NH₃ deposition to a moorland composed of a mixture of Calluna vulgaris (L.) Hull, Eriophorum vaginatum L. and Sphagnum spp. Ammonia was applied at a wide range of concentrations (1–100 μg m⁻³). The physical and environmental properties and the testing of the chamber are described, as well as results for the moorland vegetation using the ‘canopy resistance’ and ‘canopy compensation point’ interpretations of the data.Results for moorland plant species demonstrate that NH₃ concentration directly affects the rate of NH₃ deposition to the vegetation canopy, with R_c and cuticular resistance (R_w) increasing with increasing NH₃ concentrations. Differences in R_c were found between night and day: during the night R_c increases from 17 s m⁻¹ at 10 μg m⁻³ to 95 s m⁻¹ at 80 μg m⁻³, whereas during the day R_c increases from 17 s m⁻¹ at 10 μg m⁻³ to 48 s m⁻¹ at 80 μg m⁻³. The lower resistance during the day is caused by the stomata being open and available as a deposition route to the plant. R_w increased with increasing NH₃ concentrations and was not significantly different between day and night (at 80 μg m⁻³ NH₃ day R_w=88 s m⁻¹ and night R_w=95 s m⁻¹). The results demonstrate that assessments using fixed R_c will over-estimate NH₃ deposition at high concentrations (over ∼15 μg m⁻³).     

Ammonia fluxes and derived canopy compensation points over non-fertilized agricultural grassland in The Netherlands using the new gradient ammonia—high accuracy—monitor (GRAHAM)

During a measurement period from June till November 2004, ammonia fluxes above non-fertilized managed grassland in The Netherlands were measured with a Gradient Ammonia—High Accuracy—Monitor (GRAHAM). Compared with earlier ammonia measurement systems, the GRAHAM has higher accuracy and a quality control system.Flux measurements are presented for two different periods, i.e. a warm, dry summer period (from 18 July till 15 August) and a wet, cool autumn period (23 September till 23 October). From these measurements canopy compensation points were derived. The canopy compensation point is defined as the effective surface concentration of ammonia. In the summer period (negative) deposition fluxes are observed in the evening, night and early morning due to leaf surface wetness, while in the afternoon emission fluxes are observed due to high canopy compensation points. The mean NH₃-flux in this period was 4 ng m⁻² s⁻¹, which corresponds to a net emission of 0.10 kg N ha⁻¹ over the 28 day sampling period. The NH₃-flux in the autumn period mainly shows (negative) deposition fluxes due to small canopy compensation points caused by low temperatures and a generally wet surface. The mean NH₃-flux in this period is −24 ng m⁻² s⁻¹, which corresponds to a net deposition of 0.65 kg N ha⁻¹ over the 31 day sampling period.Frequency distributions of the NH₃-concentration and flux show that despite higher average ambient NH₃-concentrations (13.3 μg m⁻³ in the summer period vs. 6.4 μg m⁻³ in the autumn period) there are more emission events in the summer period than in the autumn period (about 50% of the time in summer vs. 20% in autumn). This is caused by the high canopy compensation points in summer due to high temperatures and a dry surface. In autumn, deposition dominates due to a generally wet surface that induces low canopy compensation points.For our non-fertilized agricultural grassland site, the derived canopy compensation points (at temperatures between 7 and 29 °C) varied from 0.5 to 29.7 μg m⁻³ and were on an average 7.0 μg m⁻³, which is quite high for non-fertilized conditions and probably caused by high nitrogen inputs in the past or high dry deposition amounts from local sources. The average value for the ratio between NH₄⁺ and H⁺ concentration in the canopy, Γ_c, that was derived from our data was 2200.     

Atmospheric concentrations of ammonia and ammonium at an agricultural site in the southeast United States

In this study, we present ∼1 yr (October 1998–September 1999) of 12-hour mean ammonia (NH₃), ammonium (NH₄⁺), hydrochloric acid (HCl), chloride (Cl⁻), nitrate (NO₃⁻), nitric acid (HNO₃), nitrous acid (HONO), sulfate (SO₄²⁻), and sulfur dioxide (SO₂) concentrations measured at an agricultural site in North Carolina's Coastal Plain region. Mean gas concentrations were 0.46, 1.21, 0.54, 5.55, and 4.15 μg m⁻³ for HCl, HNO₃, HONO, NH₃, and SO₂, respectively. Mean aerosol concentrations were 1.44, 1.23, 0.08, and 3.37 μg m⁻³ for NH₄⁺, NO₃⁻, Cl⁻, and SO₄²⁻, respectively. Ammonia, NH₄⁺, HNO₃, and SO₄²⁻ exhibit higher concentrations during the summer, while higher SO₂ concentrations occur during winter. A meteorology-based multivariate regression model using temperature, wind speed, and wind direction explains 76% of the variation in 12-hour mean NH₃ concentrations (n=601). Ammonia concentration increases exponentially with temperature, which explains the majority of variation (54%) in 12-hour mean NH₃ concentrations. Dependence of NH₃ concentration on wind direction suggests a local source influence. Ammonia accounts for >70% of NH_x (NH_x=NH₃+NH₄⁺) during all seasons. Ammonium nitrate and sulfate aerosol formation does not appear to be NH₃ limited. Sulfate is primarily associated ammonium sulfate, rather than bisulfate, except during the winter when the ratio of NO₃⁻–NH₄⁺ is ∼0.66. The annual average NO₃⁻–NH₄⁺ ratio is ∼0.25.     

Gaseous emissions from outdoor concrete yards used by livestock

Measurements of ammonia (NH₃), nitrous oxide (N₂O) and methane (CH₄) were made from 11 outdoor concrete yards used by livestock. Measurements of NH₃ emission were made using the equilibrium concentration technique while closed chambers were used to measure N₂O and CH₄ emissions. Outdoor yards used by livestock proved to be an important source of NH₃ emission. Greatest emission rates were measured from dairy cow feeding yards, with a mean of 690 mg NH₃-N m⁻² h⁻¹. Smaller emission rates were measured from sheep handling areas, dairy cow collecting yards, beef feeding yards and a pig loading area, with respective mean emission rates of 440, 280, 220 and 140 mg NH₃-N m⁻² h⁻¹. Emission rates of N₂O and CH₄ were much smaller and for CH₄, in particular, emission rates were influenced greatly by the presence or absence of dung on the measurement area.     

Concentration-dependent NH3 deposition processes for moorland plant species with and without stomata

Currently, in operational modelling of NH₃ deposition a fixed value of canopy resistance (R_c) is generally applied, irrespective of the plant species and NH₃ concentration. This study determined the effect of NH₃ concentration on deposition processes to individual moorland species. An innovative flux chamber system was used to provide accurate continuous measurements of NH₃ deposition to Deschampsia cespitosa (L.) Beauv., Calluna vulgaris (L.) Hull, Eriophorum vaginatum L., Cladonia spp., Sphagnum spp., and Pleurozium schreberi (Brid.) Mitt. Measurements were conducted across a wide range of NH₃ concentrations (1–140 μg m⁻³).NH₃ concentration directly affects the deposition processes to the vegetation canopy, with R_c, and cuticular resistance (R_w) increasing with increasing NH₃ concentration, for all the species and vegetation communities tested. For example, the R_c for C. vulgaris increased from 14 s m⁻¹ at 2 μg m⁻³ to 112 s m⁻¹ at 80 μg m⁻³. Diurnal variations in NH₃ uptake were observed for higher plants, due to stomatal uptake; however, no diurnal variations were shown for non-stomatal plants. R_c for C. vulgaris at 80 μg m⁻³ was 66 and 112 s m⁻¹ during day and night, respectively. Differences were found in NH₃ deposition between plant species and vegetation communities: Sphagnum had the lowest R_c (3 s m⁻¹ at 2 μg m⁻³ to 23 at 80 μg m⁻³), and D. cespitosa had the highest nighttime value (18 s m⁻¹ at 2 μg m⁻³ to 197 s m⁻¹ at 80 μg m⁻³).     

Measurement and analysis of atmospheric ammonia emissions from anaerobic lagoons

Ammonia-nitrogen flux (NH₃-N=(14/17)NH₃) was determined from six anaerobic swine waste storage and treatment lagoons (primary, secondary, and tertiary) using the dynamic chamber system. Measurements occurred during the fall of 1998 through the early spring of 1999, and each lagoon was examined for approximately one week. Analysis of flux variation was made with respect to lagoon surface water temperature (∼15 cm below the surface), lagoon water pH, total aqueous phase NH_x(=NH₃+NH₄⁺) concentration, and total Kjeldahl nitrogen (TKN). Average lagoon temperatures (across all six lagoons) ranged from approximately 10.3 to 23.3^°C. The pH ranged in value from 6.8 to 8.1. Aqueous NH_x concentration ranged from 37 to 909 mg N l⁻¹, and TKN varied from 87 to 950 mg N l⁻¹. Fluxes were the largest at the primary lagoon in Kenansville, NC (March 1999) with an average value of 120.3 μg N m⁻² min⁻¹, and smallest at the tertiary lagoon in Rocky Mount, NC (November 1998) at 40.7 μg N m⁻² min⁻¹. Emission rates were found to be correlated with both surface lagoon water temperature and aqueous NH_x concentration. The NH₃-N flux may be modeled as ln(NH₃-N flux)=1.0788+0.0406T_L+0.0015([NH_x]) (R²=0.74), where NH₃-N flux is the ammonia flux from the lagoon surface in μg N m⁻² min⁻¹, T_L is the lagoon surface water temperature in ^°C, and [NH_x] is the total ammonia-nitrogen concentration in mg N l⁻¹.     

Direct emission factor for N2O from rice–winter wheat rotation systems in southeast China

A field experiment was conducted in a rice–winter wheat rotation agroecosystem to quantify the direct emission of N₂O for synthetic N fertilizer and crop residue application in the 2002–2003 annual cycle. There was an increase in N₂O emission accompanying synthetic N fertilizer application. Fertilizer-induced emission factor for N₂O (FIE) averaged 1.08% for the rice season, 1.49% for the winter wheat season and 1.26% for the whole annual rotation cycle. The annual background emission of N₂O totaled 4.81 kg N₂O–N ha⁻¹, consisting of 1.24 kg N₂O–N ha⁻¹ for rice, 3.11 kg N₂O–N ha⁻¹ for wheat seasons. When crop residue and synthetic N fertilizer were both applied in the fields, crop residue-induced emission factor for N₂O (RIE) was estimated as well. When crop residue was retained at the rate of 2.25 and 4.50 t ha⁻¹ for each season, the RIE averaged 0.64% and 0.27% for the whole annual rotation cycle, respectively. Based on available multi-year data of N₂O emissions over the whole rice–wheat rotation cycle at 3 sites in southeast China, the FIE averaged 1.02% for the rice season, 1.65% for the wheat season. On the whole annual cycle, the FIE for N₂O ranged from 1.05% to 1.45%, with an average of 1.25%. Annual background emission of N₂O averaged 4.25 kg ha⁻¹, ranging from 3.62 to 4.87 kg ha⁻¹. It is estimated that annual N₂O emission in paddy rice-based agroecosystem amounts to 169 Gg N₂O–N in China, accounting for 26–60% of the reported estimates of total emission from croplands in China.     

Ammonia concentrations and fluxes over a forest in the midwestern USA

We present measurements of ammonia (NH₃) over a deciduous forest in southern Indiana collected during four field campaigns; two in the spring during the transition to leaf-out and two during the winter. Above canopy NH₃ concentrations measured continuously using two Wet Effluent Diffusion Denuders indicate mean concentrations of 0.6–1.2 μg m⁻³ during the spring and 0.3 μg m⁻³ during the winter. Measurements suggest that on average the forest act as a sink of NH₃, with a representative daily deposition flux of 1.8 mg-NH₃ m⁻² during the spring. However, on some days during the spring inverted concentration gradients of NH₃ were observed resulting in an apparent upward flux of nearly 0.2 mg-NH₃ m⁻² h⁻¹. Analyses suggest that this apparent emission flux may be due to canopy emission but evaporation of ammonium nitrate particles may also be partly responsible for the observed inverted concentration gradients.     

Nitrous oxide emissions from mineral and organic soils of a Norway spruce stand in South–West Germany

Due to the high temporal and spatial variability of N₂O fluxes, estimates of N₂O emission from temperate forest ecosystems are still highly uncertain, particularly at larger scales. Although highest N₂O emissions with up to 7.0 kg N ha⁻¹ yr⁻¹ were mainly reported for soils affected by stagnant water, most of the reported gas flux measurements were performed at forest sites with well-aerated soils yielding mostly to low mean annual emission rates less than 1.0 kg N ha⁻¹ yr⁻¹. This study compares N₂O fluxes from upland (Cambisols) and temporally water-logged (Gleysols, Histosols) soils of the Central Black Forest (South-West Germany) over a period of 2 yr. Mean annual N₂O fluxes from investigated soils ranged between 0.2 and 3.9 kg N ha⁻¹ yr⁻¹. The fluxes showed a large variability between the different soil types. Emissions could be clearly ranked in the following order: Cambisols (0.26–0.75 kg N ha⁻¹ yr⁻¹)<Gleysols (1.37–2.68 kg N ha⁻¹ yr⁻¹)<Histosol (3.66–3.95 kg N ha⁻¹ yr⁻¹). Although the Cambisols cover two-thirds of the investigated area, only about half of the overall N₂O is emitted from this soil type. Therefore, regional or national N₂O fluxes from temperate forest soils are underestimated if soils characterised by intermediate aeration conditions are disregarded.     

Size-resolved sulfate and ammonium measurements in marine boundary layer over the North and South Pacific

Marine background levels of non-sea-salt- (nss-) SO₄²⁻ (5.0–9.7 neq m⁻³), NH₄⁺ (2.1–4.4 neq m⁻³) and elemental carbon (EC) (40–80 ngC m⁻³) in aerosol samples were measured over the equatorial and South Pacific during a cruise by the R/V Hakuho-maru from November 2001 to March 2002. High concentrations of nss-SO₄²⁻ (47–94 neq m⁻³), NH₄⁺ (35–94 neq m⁻³) and EC (130–460 ngC m⁻³) were found in the western North Pacific near the coast of the Asian continent under the influence of the Asian winter monsoon. Particle size distributions of ionic components showed that the equivalent concentrations of nss-SO₄²⁻ were balanced with those of NH₄⁺ in the size range of 0.06<D<0.22 μm, whereas the concentration ratios of NH₄⁺ to nss-SO₄²⁻ in the size range of D>0.22 μm were decreased with increase in particle size. We estimated the source contributions of those aerosol components in the marine background air over the equatorial and South Pacific. Biomass burning accounted for the large fraction (80–98% in weight) of EC and the minor fraction (2–4% in weight) of nss-SO₄²⁻. Marine biogenic source accounted for several tens percents of NH₄⁺ and nss-SO₄²⁻. In the accumulation mode, 70% of particle number existed in the size range of 0.1<D<0.2 μm. In the size rage of 0.06<D<0.22 μm, the dominant aerosol component of (NH₄)₂SO₄ would be mainly derived from the marine biogenic sources.     

Nitric oxide emissions from soils amended with municipal waste biosolids

Land spreading nitrogen-rich municipal waste biosolids (NO₃⁻-N<256 mg N kg⁻¹ dry weight, NH₃-N∼23,080 mg N kg⁻¹ dry weight, Total Kjeldahl N∼41,700 mg N kg⁻¹ dry weight) to human food and non-food chain land is a practice followed throughout the US. This practice may lead to the recovery and utilization of the nitrogen by vegetation, but it may also lead to emissions of biogenic nitric oxide (NO), which may enhance ozone pollution in the lower levels of the troposphere. Recent global estimates of biogenic NO emissions from soils are cited in the literature, which are based on field measurements of NO emissions from various agricultural and non-agricultural fields. However, biogenic emissions of NO from soils amended with biosolids are lacking. Utilizing a state-of-the-art mobile laboratory and a dynamic flow-through chamber system, in-situ concentrations of nitric oxide (NO) were measured during the spring/summer of 1999 and winter/spring of 2000 from an agricultural soil which is routinely amended with municipal waste biosolids. The average NO flux for the late spring/summer time period (10 June 1999–5 August 1999) was 69.4±34.9 ng N m⁻² s⁻¹. Biosolids were applied during September 1999 and the field site was sampled again during winter/spring 2000 (28 February 2000–9 March 2000), during which the average flux was 3.6±1.7 ng N m⁻² s⁻¹. The same field site was sampled again in late spring (2–9 June 2000) and the average flux was 64.8±41.0 ng N m⁻² s⁻¹. An observationally based model, developed as part of this study, found that summer accounted for 60% of the yearly emission while fall, winter and spring accounted for 20%, 4% and 16% respectively. Field experiments were conducted which indicated that the application of biosolids increases the emissions of NO and that techniques to estimate biogenic NO emissions would, on a yearly average, underestimate the NO flux from this field by a factor of 26. Soil temperature and % water filled pore space (%WFPS) were observed to be significant variables for predicting NO emissions, however %WFPS was found to be most significant during high soil temperature conditions. In the range of pH values found at this site (5.8±0.3), pH was not observed to be a significant parameter in predicting NO emissions.     

Spatial distribution of wet deposition of nitrogen in South Korea

A method is developed to estimate wet deposition of nitrogen in a 11×14 km (0.125°Lon.×0.125°Lat.) grid scale using the precipitation chemistry monitored data at 10 sites scattered over South Korea supplemented by the routinely available precipitation rate data at 65 sites and the estimated emissions of NO₂ and NH₃ at each precipitation monitoring site. This approach takes into account the contributions of local NO₂ and NH₃ emissions and precipitation rates on wet deposition of nitrogen. Wet deposition of nitrogen estimated by optimum regression equations for NO₃⁻ and NH₄⁺ derived from annual total monitored wet deposition and that of emissions of NO₂ and NH₃ is incorporated to normalize wet deposition of nitrogen at each precipitation rate class, which is divided into 6 classes. The optimum regression equations for the estimation of wet deposition of nitrogen at precipitation monitoring sites are developed using the normalized wet deposition of nitrogen and the precipitation rate at 10 precipitation chemistry monitoring sites. The estimated average annual total wet depositions of NO₃⁻ and NH₄⁺ are found to be 260 and 500 eq ha⁻¹ yr⁻¹ with the maximum values of 400 and 930 eq ha⁻¹ yr⁻¹, respectively. The annual mean total wet deposition of nitrogen is found to be about 760 eq ha⁻¹ yr⁻¹, of which more than 65% is contributed by wet deposition of ammonium while, the emission of NH₃ is about half of that of NO₂, suggesting the importance of NH₃ emission for wet deposition of nitrogen in South Korea.     

PM2.5–10, PM2.5 and associated water-soluble inorganic species at a coastal urban site in the metropolitan region of Rio de Janeiro

The concentrations of PM_2.5−10, PM_2.5 and associated water-soluble inorganic species (WSIS) were determined in a coastal site of the metropolitan region of Rio de Janeiro, Southeastern Brazil, from October 1998 to September 1999 (n=50). Samples were dissolved in water and analyzed for major inorganic ions. The mean (± standard deviation; median) concentrations of PM_2.5−10 and PM_2.5 were, respectively, 26 (± 16; 21) μg m⁻³ and 17 (± 13; 14) μg m⁻³. Their mean concentrations were 1.7–1.8 times higher in dry season (May–October) than in rainy season (November–April). The WSIS comprised, respectively, 34% and 28% of the PM_2.5−10 and PM_2.5 masses. Chloride, Na⁺ and Mg²⁺ were the predominant ions in PM_2.5−10, indicating a significant influence of sea-salt aerosols. In PM_2.5, SO₄²⁻ (∼97% nss-SO₄²⁻) and NH₄⁺ were the most abundant ions and their equivalent concentration ratio (SO₄²⁻/NH₄⁺ ∼1.0) suggests that they were present as (NH₄)₂SO₄ particles. The mean concentration of (NH₄)₂SO₄ was 3.4 μg m⁻³. The mean equivalent PM_2.5 NO₃⁻ concentration was eight times smaller than those of SO₄²⁻ and NH₄⁺. The PM_2.5 NO₃⁻ concentration in dry season was three times higher than in rainy season, probably due to reaction of NaCl (sea salt) with HNO₃ as a result of higher levels of NO_y during the dry season and/or reduced volatilization of NH₄NO₃ due to lower wintertime temperature. Chloride depletion was observed in both size ranges, although more pronouncely in PM_2.5.     

Historical changes in atmospheric nitrogen deposition to Cape Cod,Massachusetts, USA

We reconstructed the historical trends in atmospheric deposition of nitrogen to Cape Cod, Massachusetts, from 1910 to 1995 by compiling data from literature sources, and adjusting the data for geographical and methodological differences. The reconstructed data suggest that NO₃-N wet deposition to this region increased from a low of 0.9 kg N ha⁻¹ yr⁻¹ in 1925 to a high of approximately 4 kg N ha⁻¹ yr⁻¹ around 1980. The trend in NO₃-N deposition has remained since the early 1980s at around 3.6 kg N ha⁻¹ yr⁻¹. In contrast, NH₄-N wet deposition decreased from more than 4 kg N ha⁻¹ yr⁻¹ in the mid 1920s to about 1.5 kg N ha⁻¹ yr⁻¹ from the late-1940s until today. Emissions of NO_x-N in the Cape Cod airshed increased at a rate of 2.1 kg N ha⁻¹ per decade since 1910, a rate that is an order of magnitude higher than NO₃-N deposition. Estimates of NH₃ emissions to the northeast United States and Canada have decreased slightly throughout the century, but the decrease in reconstructed N-NH₄⁺ deposition rates does not parallel emissions estimates. The trend in reconstructed total nitrogen deposition suggests an overall increase through the century at a rate of 0.26 kg N ha⁻¹ per decade. This overall increase in deposition may expose coastal forests to rates of nitrogen addition that, if exceeded, could induce nitrogen saturation and increase nitrogen loads to adjoining estuaries.     

Sulfuric odorous compounds emitted from pig-feeding operations

The objective of the study was to quantify the concentration and emission levels of sulfuric odorous compounds emitted from pig-feeding operations. Five types of pig-housing rooms were studied: gestation, farrowing, nursery, growing and fattening rooms. The concentration range of sulfuric odorous compounds in these pig-housing rooms were 30–200 ppb for hydrogen sulfide (H₂S), 2.5–20 ppb for methyl mercaptan (CH₃SH), 1.5–12 ppb for dimethyl sulfide (DMS; CH₃SCH₃) and 0.5–7 ppb for dimethyl disulfide (DMDS; CH₃S₂CH₃), respectively. The emission rates of H₂S, CH₃SH, DMS and DMDS were estimated by multiplying the average concentration (mg m⁻³) measured near the air outlet by the mean ventilation rate (m³ h⁻¹) and expressed either per area (mg m⁻² h⁻¹) or animal unit (AU; liveweight of the pig, 500 kg) (mg pig⁻¹ h⁻¹). As a result, the emission rates of H₂S, CH₃SH, DMS and DMDS in the pig-housing rooms were 14–64, 0.8–7.3, 0.4–3.4 and 0.2–1.9 mg m⁻² h⁻¹, respectively, based on pig's activity space and 310–723, 18–80, 9–39 and 5–22 mg AU⁻¹ h⁻¹, respectively, based on pig's liveweight, which indicates that their emission rates were similar, whether based upon the pig's activity space or liveweight. In conclusion, the concentrations and emission rates of H₂S were highest in the fattening room followed by the growing, nursery, farrowing and gestation rooms whereas those of CH₃SH, DMS and DMDS concentrations were largest in the growing room followed by the nursery, gestation and farrowing rooms.     

Validation of DNDC for 22 long-term N2O field emission measurements

Twenty-two long-term measurements of direct N₂O emissions from soils in an intensive agricultural area were used for the validation of the process-based DNDC model (version 8.3P). Model simulations were evaluated for temporal patterns of N₂O, NH₄⁺, NO₃⁻ and water-filled pore space (WFPS) and total N₂O emissions. Several soil and crop input parameter adjustments to the model were evaluated but only the recalculation of the WFPS at wilting point and at field capacity, using pedotransfer functions, resulted in a clear improvement of the simulated variables (WFPS in all cases, N₂O in some cases). Therefore, only this adjustment was made to DNDC 8.3P. This change, however, resulted for some cases (both cropland and grassland) in retardation of nitrate leaching and to a lesser extent of NH₄⁺ to the deeper soil layers. The goodness of fit of the simulated temporal pattern of N₂O varied considerably between sites. The total simulated N₂O emissions from cropland showed a good agreement with the measurements, although there was a systematic overestimation of 7.4 kg N₂O-N ha⁻¹. Grassland soils, in contrast, gave a low agreement between total simulated and measured N₂O losses. On the basis of all measured data a regional emission factor of 3.16 with a 95% confidence interval of −0.89 to 7.21 could be calculated. DNDC simulations resulted in an emission factor of 6.49 with a 95% confidence interval of 4.04–8.93. The overall outcome of the N₂O emission measurements and DNDC simulations were compared with several empirical regression models, which may be applicable for a temperate climate system. All of the tested regression models showed reliable results up to a N₂O emission of 10 kg N₂O-N ha⁻¹. Higher emissions, however, were systematically underestimated. Though DNDC both under- and overestimated specific sites, the general agreement, over the whole range between measurements and simulations of total N₂O losses (simulations=0.82×meas.+6.2), was better than for the different regression models.     

Measurements of atmospheric nitrous acid and nitric acid

A highly sensitive technique for the measurement of atmospheric HONO and HNO₃ is reported. The technique is based on aqueous scrubbing using two coil samplers, followed by conversion of HNO₃ to nitrite, derivatization of nitrite to a highly light-absorbing azo dye with sulfanilamide (SA) and N-(1-naphthyl) ethylenediamine (NED), and high performance liquid chromatography (HPLC) analysis. HNO₃ concentration was obtained by the difference of the two channels. Two scrubbing solutions were used for sampling the two species: a 1-mM phosphate buffer solution (pH 7) for the measurement of HONO and a 180 mM NH₄Cl/NH₃ buffer solution (pH 8.5) for the measurement of HONO+HNO₃. The scrubbing solution flow rate was 0.24 ml min⁻¹ and the gas sampling flow rate was 2 l min⁻¹. HNO₃ in the NH₄Cl/NH₃ buffer solution was quantitatively reduced to nitrite along an on-line 0.8-cm Cd reductor column. Nitrite in both channels was derivatized with 2 mM SA and 0.2 mM NED in 25 mM HCl. Quantitative derivatization was achieved within 5 min at 55°C. The azo dye derivative was then separated from the SA/NED reagent by reversed-phase HPLC and detected with a UV-vis detector at 540 nm. With an on-line SEP-PAK C-18 cartridge for the reagent purification, the method detection limit is estimated to be better than 1 pptv for HONO and about 20 pptv for HNO₃. The sample integration time was about 2 min and the sampling frequency is every 10 min. Data collected in downtown Albany and Whiteface Mountain, NY, are shown as examples of applications of this technique in both urban and remote clean environments.     

Deposition and adsorption of the air pollutant HNO3 vapor to soil surfaces

Deposition of nitric acid (HNO₃) vapor to soils has been evaluated in three experimental settings: (1) continuously stirred tank reactors with the pollutant added to clean air, (2) open-top chambers at high ambient levels of pollution with and without filtration reducing particulate nitrate levels, (3) two field sites with high or low pollution loads in the coastal sage plant community of southern California. The results from experiment (1) indicated that the amount of extractable NO₃⁻ from isolated sand, silt and clay fractions increased with atmospheric concentration and duration of exposure. After 32 days, the highest absorption of HNO₃ was determined for clay, followed by silt and sand. While the sand and silt fractions showed a tendency to saturate, the clay samples did not after 32 days of exposure under highly polluted conditions. Absorption of HNO₃ occurred mainly in the top 1 mm layer of the soil samples and the presence of water increased HNO₃ absorption by about 2-fold. Experiment (2) indicated that the presence of coarse particulate NO₃⁻ could effectively block absorption sites of soils for HNO₃ vapor. Experiment (3) showed that soil samples collected from open sites had about 2.5 more extractable NO₃⁻ as compared to samples collected from beneath shrub canopies. The difference in NO₃⁻ occurred only in the upper 1–2 cm as no significant differences in NO₃⁻ concentrations were found in the 2–5 cm soil layers. Extractable NO₃⁻ from surface soils collected from a low-pollution site ranged between 1 and 8 μg NO₃–N g⁻¹, compared to a maximum of 42 μg NO₃–N g⁻¹ for soils collected from a highly polluted site. Highly significant relationship between HNO₃ vapor doses and its accumulation in the upper layers of soils indicates that carefully prepared soil samples (especially clay fraction) may be useful as passive samplers for evaluation of ambient concentrations of HNO₃ vapor.     

NOX fluxes from three kinds of agricultural lands in the Yangtze Delta,China

Static chamber method was adopted to measure the surface exchanges of NO and NO₂ between three kinds of agricultural lands and the atmosphere during spring–summer period in the Yangtze Delta, China. The average NO fluxes were 20.9, 27.4 and 21.4 ng N m⁻² s⁻¹, respectively, for cabbage (CA, cultivation of celery occurred along with cabbage), potato (PO) and soybean (SY) fields. The average NO₂ fluxes were −1.12, 0.93 and −0.68 ng N m⁻² s⁻¹, respectively, for the cabbage, potato and soybean fields. Apparently, negative linear correlation was found between the NO₂ fluxes from the CK plot (tilled conventionally but did not cultivate any seeds) and its ambient concentrations, and the compensation point was calculated to be 0.92 ppbv. The total NO emission from the vegetable lands and SY land in this region during spring–summer period was roughly estimated to be 15.9 Gg N, which accounted for about 11.2% of the estimated value of total NO emissions in the July of 1999 from Chinese agricultural fields.