Nitric oxide and nitrous oxide emission from Hungarian forest soils; linked with atmospheric N-deposition

Studies of forest nitrogen (N) budgets generally measure inputs from the atmosphere in wet and dry deposition and outputs via hydrologic export. Although denitrification has been shown to be important in many wetland ecosystems, emission of N oxides from forest soils is an important, and often overlooked, component of an ecosystem N budget. During 1 year (2002–03), emissions of nitric oxide (NO) and nitrous oxide (N₂O) were measured from Sessile oak and Norway spruce forest soils in northeast Hungary. Accumulation in small static chambers followed by gas chromatography-mass spectrometry detection was used for the estimation of N₂O emission flux. Because there are rapid chemical reactions of NO and ozone, small dynamic chambers were used for in situ NO flux measurements. Average soil emissions of NO were 1.2 and 2.1 μg N m⁻² h⁻¹, and for N₂O were 15 and 20 μg N m⁻² h⁻¹, for spruce and oak soils, respectively. Due to the relatively high soil water content, and low C/N ratio in soil, denitrification processes dominate, resulting in an order of magnitude greater N₂O emission rate compared to NO. The previously determined N balance between the atmosphere and the forest ecosystem was re-calculated using these soil emission figures. The total (dry+wet) atmospheric N-deposition to the soil was 1.42 and 1.59 g N m⁻² yr⁻¹ for spruce and oak, respectively, while the soil emissions are 0.14 and 0.20 g N m⁻² yr⁻¹. Thus, about 10–13% of N compounds deposited to the soil, mostly as and , were transformed in the soil and emitted back to the atmosphere, mostly as greenhouse gas (N₂O).     

The contribution of dry deposited ammonia and sulphur dioxide to the composition of precipitation from continuously open gauges

A series of experiments using bulk precipitation collectors of the type used in the UK precipitation chemistry network measured the amounts of NH₄⁺, SO₄²⁻ and other ions that could be washed from funnels (diameter 15 cm) exposed to a wide range of NH₃ and SO₂ concentrations over periods from hours to days. In dry conditions, the average deposition flux of NH₃ was between 50 and 120 nmol NH₄⁺ funnel⁻¹ d⁻¹ (0.1–0.3 kg N ha⁻¹ yr⁻¹), and was independent of the concentration of NH₃. Dry deposition of NH₃ to wet funnels at small NH₃ concentrations was almost 5 times that to dry funnels under the same conditions (average 240 nmol funnel⁻¹ d⁻¹; 0.7 kg ha⁻¹ yr⁻¹), and increased with increasing NH₃ concentrations. The amount of NH₄⁺ ions remaining on the funnel surface was inversely proportional to the vapour pressure deficit during the experiment. This result was interpreted as a dependence on the duration of surface wetness, with greater deposition of NH₄⁺ when evaporation rates of surface water were small.The amount of SO₂ deposited on funnel surfaces was closely related to the amount of NH₃ deposited, in both wet and dry conditions, but was not strongly correlated with the SO₂ concentration. At low NH₃ and SO₂ concentrations the average deposition to dry funnels was 70 nmol SO₄²⁻ funnel⁻¹ d⁻¹ (0.5 kg ha⁻¹ yr⁻¹), and to wet funnels was approximately 2.5 times larger. The results are interpreted in terms of the balance between the rate of evaporation of surface water, and the rate of oxidation of SO₂, which leads to the ‘fixing’ of NH₄⁺ ions on the surface as involatile salts.It is predicted that dry deposition of NH₃ to funnel surfaces across the UK Secondary Network could account for as much as one-half of the measured bulk wet deposition at sites where wet deposition of NH₄–N is small. The amount of dry deposition depends on how long and how often funnel surfaces are wetted by rain or dew, and on the air concentrations of NH₃. These predictions are based on funnels being wetted only once per day. More frequent wetting would increase the contribution from dry deposition, and the consequent overestimate of wet deposition of NH₄–N across the UK by using data obtained from bulk collectors. To some extent this overestimate may be offset by microbial degradation and loss of NH₄–N in weekly bulk precipitation samples during collection and storage.     

Atmospheric deposition and canopy exchange processes in alpine forest ecosystems (northern Italy)

Throughfall and bulk precipitation chemistry were studied for five years (June 1994–May 1999) at two high elevation forest sites (Val Gerola and Val Masino) which were known to differ in terms of tree health, as assessed by live crown condition. The ion concentration of bulk precipitation samples did not differ significantly between sites, except for Mg²⁺, while the throughfall concentrations differed in the measured values of H⁺, N-NO₃⁻, Cl⁻, Na⁺, K⁺, DOC and weak organic acids. The results of the application of the canopy exchange model indicated a higher contribution from the dry deposition of N-NO₃⁻, N-NH₄⁺ and H⁺ at Val Gerola, where the damage symptoms were more evident. In addition, the canopy leaching of Ca²⁺, K⁺ and weak organic acids were 47%, 21% and 27% higher at Val Gerola than at Val Masino. Annual SO₄²⁻ deposition fluxes (21.3 kg ha⁻¹ yr⁻¹ at Val Masino and 23.6 kg ha⁻¹ yr⁻¹ at Val Gerola) were similar to those reported for moderately polluted European and U.S. sites. Annual N loads were 13.6 and 13.1 kg ha⁻¹ yr⁻¹ in the bulk input, and 15.0 and 18.0 kg ha⁻¹ yr⁻¹ in throughfall inputs, at Val Masino and Val Gerola, respectively. The contribution of the organic fraction to the total N atmospheric deposition load is significant, constituting 17% of the bulk flux and 40% of the throughfall flux. Measured nitrogen loads exceed the critical nutrient loads by several kg N ha⁻¹ at both stations. In particular the nitrogen throughfall load at Val Gerola was about 3 times higher than the critical values.     

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.     

Mercury deposition/accumulation rates in the vicinity of a lead smelter as recorded by a peat deposit

Mercury (Hg) concentration profiles and historical accumulation rates were determined in three ²¹⁰Pb-dated cores from a peat deposit in the vicinity of a lead (Pb) smelter at Příbram, Czech Republic. The Hg concentrations in peat samples ranged from 66 to 701 μg kg⁻¹. Cumulative Hg inventories from each core (for the past 150 yr) varied by a factor of 1.4 (13.6–18.5 mg Hg m⁻²), indicating variations of net Hg accumulation rate within the peat deposit. Historical changes in vegetation cover (leading to variable interception by trees) are probably responsible for this variation in space and time. The uncorrected Hg accumulation rates peaked between the 1960s and 1980s (up to 226 μg m⁻² yr⁻¹). Recent findings show that Hg records from peat tend to overestimate historical levels of Hg deposition. Therefore we used the mass loss compensation factor (MLCF) to normalize Hg accumulation rates. These corrected Hg accumulation rates were significantly lower (maximum 129 μg m⁻² yr⁻¹) and better corresponded to changes in historical smelter emissions, which were highest in the 1960s. The agreement between the corrected Hg accumulation rates in the uppermost peat sections (2–38 μg m⁻² yr⁻¹) and biomonitoring of atmospheric deposition by mosses in several recent years (4.7–34.4 μg m⁻² yr⁻¹) shows the usefulness of MLCF application on Hg accumulation in peat archives. However, the MLCF correction was unsuitable for Pb. The recent Pb deposition rates obtained by an independent biomonitoring study using mosses (0.5–127 mg m⁻² yr⁻¹) were better correlated with net Pb accumulation rates recorded in peat (7–145 mg m⁻² yr⁻¹) than with corrected rates obtained by the MLCF approach (1–28 mg m⁻² yr⁻¹).     

Net ecosystem CO2 exchange over a larch forest in Hokkaido, Japan

Larch forests are distributed extensively in the east Eurasian continent and are expected to play a significant role in the terrestrial ecosystem carbon cycling process. In view of the fact that studies on carbon exchange for this important biome have been very limited, we have initiated a long-term flux observation in a larch forest ecosystem in Hokkaido in northern Japan since 2000. The net ecosystem CO₂ exchange (NEE) showed large seasonal and diurnal variation. Generally, the larch forest ecosystem released CO₂ in nighttime and assimilated CO₂ in daytime during the growing season from May to October. The ecosystem started to become a net carbon sink in May, reaching a maximum carbon uptake as high as 186 g C m⁻² month⁻¹ in June. With the yellowing, senescing and leaf fall, the ecosystem turned into a carbon source in November. During the non-growing season, the larch forest ecosystem became a net source of CO₂, releasing an average of 16.7 g C m⁻² month⁻¹. Overall, the ecosystem sequestered 141–240 g C m⁻² yr⁻¹ in 2001. The NEE was significantly influenced by environmental factors. Respiration of the ecosystem, for example, was exponentially dependent on air temperature, while photosynthesis was related to the incident PAR in a manner consistent with the Michaelis–Menten model. Although the vapor pressure deficit (VPD) was scarcely higher than 15 hPa, the CO₂ uptake rate was also depressed when VPD surpassed 10 hPa.     

Nitric oxide emission from a typical vegetable field in the Pearl River Delta, China

Croplands contribute to atmospheric nitric oxide (NO), but very limited data are available about NO fluxes from intensively managed croplands in China. In this study, NO fluxes were measured in a typical vegetable field planted with flowering Chinese cabbage (Brassica campestris L. ssp. Chinensis var. utilis Tsen et Lee), which is the most widely cultivated vegetable in Guangdong province, south China. NO emission drastically increased after nitrogen fertilizer application, and other practices involving loosening the soil also enhanced NO emission. Mean NO emission flux was 47.5 ng N m⁻² s^–1 over a complete growth cycle. Annual NO emission from the vegetable field was about 10.1 kg N ha⁻¹ yr⁻¹. Fertilizer-induced NO emission factor was estimated to be 2.4%. Total NO emission from vegetable fields in Guangdong province was roughly estimated to be 11.7 Gg N yr⁻¹ based on the vegetable field area and annual NO emission rate, and to be 13.3 Gg N yr⁻¹ based on fertilizer-induced NO emission factor and background NO emission. This means that NO emission from vegetable fields was approximately 6% of NO_x from commercial energy consumption in Guangdong province.     

Measurement and modeling of urban atmospheric PCB concentrations on a small (8 km) spatial scale

Atmospheric transport and deposition of polychlorinated biphenyls (PCBs) is an important problem for ecosystems around the world. Data from several monitoring networks demonstrate that atmospheric PCB concentrations are dramatically elevated in urban areas compared to rural or background regions, such that these urban emissions of PCBs support the regional and global transport and deposition of PCBs to more remote areas. Identifying and controlling the sources of urban atmospheric PCBs is thus essential in minimizing the regional and global transport and deposition of these compounds. From December 1999 to November 2000, gas-phase PCB concentrations were measured at two monitoring locations, 8 km apart, within the New York City metropolitan area, at Jersey City and Bayonne, NJ. Concentrations, congener patterns, and temporal patterns of PCBs differ dramatically at the two sites, suggesting that a significant source of atmospheric PCBs exists within 8 km of the Bayonne site, resulting in spikes in gas-phase PCB concentration at Bayonne that are not observed at Jersey City. The Regional Atmospheric Model System (RAMS) coupled with the Hybrid Particle and Concentration Transport model (HYPACT) was used to estimate that the PCB source near Bayonne emits a flux of ΣPCBs on the order of 100 g d⁻¹. Extrapolation of this source magnitude to the area of New York City suggests that this urban area emits at least 300 kg yr⁻¹ ΣPCBs to the regional atmosphere, similar in magnitude to the flow of ΣPCB out of the Upper Hudson River into the New York/New Jersey Harbor.     

Levels and congener profiles of PCDD/Fs, PCBs and PBDEs in seafood from China

A nationwide investigation into polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in market seafood was conducted for the first time in this study. Total PCDD/F concentrations in fatty fish ranged from 0.13 to 8.64 pg g⁻¹ wet weight (mean 2.05 pg g⁻¹ wet weight), total PCB concentrations ranged from 38.9 to 3514 pg g⁻¹ wet weight (mean 1133 pg g⁻¹ wet weight), and total PBDE concentrations ranged from 42.8 to 913 pg g⁻¹ wet weight (mean 322 pg g⁻¹ wet weight). Corresponding mean toxicity equivalent (TEQ) values for total PCDD/F and dioxin-like PCB were 0.25 pg g⁻¹ wet weight (WHO 98-TEQ) and 0.32 pg g⁻¹ wet weight (WHO 98-TEQ), respectively. OCDD, PCB-138 and PBDE-47 were the dominant compounds according to their respective congeners. WHO 98-TEQ _{PCDD/PCDF/PCB} for fatty fish and shell fish were 0.60 and 0.070 pg g⁻¹ wet weight, respectively, lower than the standard set by the European Commission. The contamination levels and profiles were compared with those documented in previous publications.     

Description and evaluation of a model of deposition velocities for routine estimates of dry deposition over North America. Part II: review of past measurements and model results

Numerical sensitivity tests and four months of complete model runs have been conducted for the Routine Deposition Model (RDM). The influence of individual model inputs on dry deposition velocity as a function of land-use category (LUC) and pollutant (SO₂, O₃, SO²⁻₄ and HNO₃) were examined over a realistic range of values for solar radiation, stability and wind speed. Spatial and temporal variations in RDM deposition velocity (V_d) during June – September 1996 time period generated using meteorological input from a mesoscale model run at 35 km resolution over north-eastern North America were also examined. Comparison of RDM V_d values to a variety of measurements of dry deposition velocities of SO₂, O₃, SO²⁻₄ and NHO₃ that have been reported in the literature demonstrated that RDM produces realistic results. Over northeastern NA RDM monthly averaged dry deposition velocities for SO₂ vary from 0.2 to 3.0 cm s⁻¹ with the highest deposition velocities over water surfaces. For O₃, the monthly averaged dry deposition velocities are from 0.05 to 1.0 cm s⁻¹ with the lowest values over water surfaces and the highest over forested areas. For HNO₃, the monthly averaged dry deposition velocities have the range of 0.5 to 6 cm s⁻¹, with the highest values for forested areas. For SO²⁻₄, they range from 0.05–1.5 cm s⁻¹, with the lowest values over water and the highest over forest. The monthly averaged dry deposition velocities for SO₂ and O₃ are higher in the growing season compared to the fall, but this behaviour is not apparent for HNO₃ and sulphate. In the daytime, the hourly averaged dry deposition velocities for SO₂, O₃, SO²⁻₄ and HNO₃ are higher than that in the nighttime over most of the vegetated area. The diurnal variation is most evident for surfaces with large values for leaf area index (LAI), such as forests. Based on the results presented in this paper, it is concluded that RDM V_d values can be combined with measured air concentrations over hourly, daily or weekly periods to determine dry deposition amounts and with wet deposition measurements to provide seasonal estimates of total deposition and estimates of the relative importance of dry deposition.     

Study on dissolved organic carbon in precipitation in Northern China

Dissolved organic carbon (DOC) was measured in 483 precipitation samples collected at 10 sites in Northern China from December 2007 to November 2008. The annual volume-weighted mean (VWM) concentrations and wet deposition fluxes of DOC for 10 sites ranged from 2.4 to 3.9 mg C/L and 1.4 to 2.7 g C m^?2 yr^?1, respectively. The proportion of DOC to total organic carbon (TOC) was 79% on average, suggesting that a significant fraction of TOC was present as insoluble particulate organic carbon. Due to intensive domestic coal use for house heating and smaller dilution of scavenged organic carbon, higher VWM concentrations of DOC were observed during winter and spring than during summer and autumn. When precipitation events were classified via air mass back-trajectories, the mixed trajectories from SE and NW always corresponded to significantly higher DOC than those from SE or NW alone, coinciding with the centre of a low pressure system moved eastward and the wind direction changed from southeast to northwest. The results also showed that each site had a similar seasonal variation for DOC wet deposition flux. The largest flux occurred during the rainy season, and the lowest flux appeared during winter months. The product of the TC/DOC ratio and the DOC flux yielded an average TC wet deposition flux of 3.2 g C m^?2 yr^?1 in Northern China, accounting for 8.6% and 22% of the carbon sink magnitude (37 g C m^?2 yr^?1) in terrestrial ecosystems and anthropogenic carbon emissions (14 g C m^?2 yr^?1), respectively. This indicates that atmospheric wet deposition of TC is a significant carbon flux that cannot be neglected in regional models of the carbon cycle, and should be considered along with dry deposition in the removal mechanism for carbon from regional atmosphere.     

Trans-boundary air pollution over remote islands in Japan: observed data and estimates from a numerical model

Observations of air pollutants were conducted in remote Japanese islands (Oki Island and Okinawa Island) in early spring to clarify the extent of trans-boundary air pollution from the Asian continent. A three-dimensional Eulerian model calculation, which included parameters on emission, transport and transformation of sulfur oxides, nitrogen oxides and ammonia, was performed to compile sulfate isosurface concentrations over the observational sites. Concentrations of non-sea-salt sulfate (nss-SO₄²⁻) of greater than 10 μg m⁻³ were observed at Oki after the northeastward passage of low-pressure systems in the Sea of Japan. At these times, the weather showed a typical winter pattern and air pollutants over China were transported southeastward to Japan with the northwesterly wind. The model calculation reproduced the observed variations of nss-SO₄²⁻ concentration well, except for one case in which the model calculation could not reproduce the extremely low nss-SO₄²⁻ concentration observed on 8 March. In Hedo (Okinawa Island), we observed long-lasting (3 days) medium concentrations of nss-SO₄²⁻ (approximately 5 μg m⁻³). Although the model reproduced these observed medium concentrations well, in general the observed results were reproduced better for Oki than for Hedo. Under the synoptic weather conditions of early spring, high concentrations of nss-sulfate were sometimes transported to these remote Japanese islands from areas of continental Asia with a strong outflow of air pollutants.     

Concentrations of carbon monoxide and methane at two heights above a grass field and their deposition onto the field

To investigate whether wind is a significant driving force in the diffusion of CO and CH₄ from the atmosphere into soil, we measured the concentrations of these two gases at two heights above a temperate grass field in Japan and estimated their deposition velocities using micrometeorological techniques. The concentrations were inversely correlated with wind speed, indicating that the local concentrations were influenced by ground sources. The CO and CH₄ concentrations at 0.33 m were usually lower than those at 1.3 m. Although nocturnal data are suspected to be non-stationary, by selecting several periods when the changes of the concentrations were small but larger than analytical precision, we obtained a CO velocity of 2.9 and 3.9×10⁻² cms⁻¹, agreeing with a CO deposition velocity, 3.4×10⁻² cms⁻¹, obtained by applying a method using CO₂ as a tracer. The CH₄ influx obtained by the method using CO₂ as a tracer was 13 ngm⁻² s⁻¹. The ranges of the CO deposition velocity and CH₄ influx were similar to those obtained in previous studies in grassfields and in a nearby arable field using a closed-chamber technique. This shows that light winds do not greatly accelerate CO and CH₄ uptake by soil.     

Spatial character of polychlorinated biphenyls from soil and respirable particulate matter in Taiyuan, China

As one of China’s great metropolises, Taiyuan is affected by heavy chemical industry and manufacture of chemical products, and faces pollution from polychlorinated biphenyls (PCBs). Therefore, this study was conducted to determine the PCB concentrations in various environmental media in Taiyuan. We collected 15 soil samples, 34 respirable particulate matter (PM) samples (17 of PM_2.5 and 17 of PM₁₀) from urban areas of Taiyuan, and measured a total of 144 PCB congeners (including some coeluting PCB congeners). The total PCB concentrations were 51–4.7 × 10³ pg g⁻¹ in soil, 27–1.4 × 10² pg m⁻³ in PM_2.5 and 16–1.9 × 10² pg m⁻³ in PM₁₀. Of the PCB homologues, the dominant PCBs detected in the various media were all tri-CBs. Soil was relatively the most polluted media. Furthermore, principal-component analysis revealed that the major PCB source in Taiyuan may be associated with the main commercial PCB through long-range transmission. Toxic equivalency (TEQ) concentrations (based on ten dioxin-like PCBs) ranged from N.D. to 5.9 × 10⁻³ pg-WHO TEQ g⁻¹ in soil, 2.0 × 10⁻⁴–3.4 × 10⁻³ pg-WHO TEQ m⁻³ and 1.0 × 10⁻⁴–1.2 × 10⁻³ pg-WHO TEQ m⁻³ in PM_2.5 and PM₁₀, respectively. In previous studies, PCBs were not a severe component of contaminant in Taiyuan; however, this study suggested there is a potential threat of human exposure to PCBs for residents of Taiyuan.     

Description and evaluation of a model of deposition velocities for routine estimates of air pollutant dry deposition over North America.: Part I: model development

This paper describes the development of a detailed dry deposition model for routine computation of dry deposition velocities of SO₂, O₃, HNO₃ and fine particle SO₄²⁻ across much of North America. Four different dry deposition/surface exchange sub-models have been combined with the current Canadian weather forecast model (Global Environmental Multiscale model) with a 3 h time resolution and a horizontal spatial resolution of 35 km. The present model uses the US Geological Survey North American Land Cover Characteristics data to obtain fourteen different land use and five seasonal categories. The four sub-models used are a multi-layer model for gaseous species over taller canopy land-use types, a big-leaf model for gaseous species over lower canopies (including bare soil and water) and for HNO₃ under all surface types and, two different models for SO₄²⁻, one for tall canopies and the other for short canopies. All necessary parameters for each sub-model, chemical species, land-use and seasonal categories have been selected from available data libraries or from the values reported in the literature. The purpose for developing this model (referred to as the Routine Deposition Model (RDM)), when coupled with air concentration data, is to provide estimates of seasonal dry deposition, which can be combined with wet deposition to produce total deposition estimates. Model theory is discussed in this paper and model sensitivity tests and results will be presented in a companion paper.     

Historical deposition of mercury and selected trace elements to high-elevation National Parks in the Western U.S. inferred from lake-sediment cores

Atmospheric deposition of Hg and selected trace elements was reconstructed over the past 150 years using sediment cores collected from nine remote, high-elevation lakes in Rocky Mountain National Park in Colorado and Glacier National Park in Montana. Cores were age dated by ²¹⁰Pb, and sedimentation rates were determined using the constant rate of supply model. Hg concentrations in most of the cores began to increase around 1900, reaching a peak sometime after 1980. Other trace elements, particularly Pb and Cd, showed similar post-industrial increases in lake sediments, confirming that anthropogenic contaminants are reaching remote areas of the Rocky Mountains via atmospheric transport and deposition. Preindustrial (pre-1875) Hg fluxes in the sediment ranged from 5.7 to 42 μg m^?2 yr^?1 and modern (post-1985) fluxes ranged from 17.7 to 141 μg m^?2 yr^?1. The average ratio of modern to preindustrial fluxes was 3.2, which is similar to remote lakes elsewhere in North America. Estimates of net atmospheric deposition based on the cores were 3.1 μg m^?2 yr^?1 for preindustrial and 11.7 μg m^?2 yr^?1 for modern times. Current-day measurements of wet deposition range from 5.0 to 8.6 μg m^?2 yr^?1, which are lower than the modern sediment-based estimate of 11.7 μg m^?2 yr^?1, perhaps owing to inputs of dry-deposited Hg to the lakes.     

The use of clays to sequestrate organic pollutants. Leaching experiments

Leaching experiments are performed from clay-pollutant systems in order to evaluate the capability of clays to sequestrate organic pollutants from wastewaters. Reference kaolinite KGa-1b, montmorrillonite SWy-2 and reference soil BCR^®-700 are the sorbent materials. 2,4,6-trichloroaniline (2,4,6-TCA) and 4-chlorophenol (4-CP) are the typical pollutants, sorbed at amounts of 10.0 mg g⁻¹ and 5.8 mg g⁻¹ on SWy-2 and 7.3 mg g⁻¹ and 2.2 mg g⁻¹ on KGa-1b, respectively.The leaching agents are ultrapure water and model solutions of acid rain and surface waters that simulate meteoric leaching. 1.0 mM HNO₃, 1.0 mM H₂SO₄ solutions and a methanol/water 50/50 (v/v) mixture simulate leaching agents of industrial source.The results are compared and the preferential capability of the clays to sequestrate the more lipophilic 2,4,6-TCA is evidenced.The bond interactions are discussed and explained through preferential adsorption reactions. For montmorrillonite also a simultaneous intercalation in the phyllosilicate interlayer is proposed.     

Depleted N carryover, leaching and uptake for three years of irrigated corn

Deep percolation of nitrate can contribute to the deterioration of groundwater resources. Leaching of nitrate is a complex process affected by fertilizer and irrigation practices, efficiency of N use by the crop, and how the soil's water holding capacity and water transmission properties are affected by soil texture. Depleted (¹⁵NH₄)₂SO₄ fertilizer at N rates of 0, 125, 250 and 375 kg ha⁻¹ was applied annually for 3 years to continuous corn grown within three different water regimes. This time period and the labeled N permitted an evaluation of N use efficiency by the crop and NO₃ leaching and carryover on a Weld silty clay loam, a fine-textured soil, typical of the “hardland” soils of the semi-arid Great Plains. Three water regimes, W₁ ( 1.5 ET), W₂ ( ET) and W₃ ( 0.8 ET), were used. Beneath each plot within each water regime, Duke-Haise vacuum trough extractors were installed under undisturbed soil profiles at 1.22-m depth to measure weekly percolate and the NO₃ concentration in the percolate. The corn was harvested in the fall in the dent stage to measure the total above-ground biomass N uptake. Soil profiles (1.8 m) were sampled annually in the fall after crop harvest to determine NO₃---N in the soil or carryover.Great variability was encountered in measuring the amount of extractor water and its NO₃ content under each water regime, which made estimates of N03 leaching losses unreliable. Also, the variability demonstrates formidable problems in quantifying percolation losses with vacuum trough extractors under undisturbed fine-textured soil profiles. With the highest N rate of 376 kg ha⁻¹ yr⁻¹ and within the water regime W₁, where leaching was expected to be greatest, only 1% of the cumulative labeled N applied was found in extractor waters and most movement of the labeled N into extractors occurred the third year. The 125-kg-ha⁻¹ yr⁻¹ fertilizer N rate significantly increased the crop yield over the unfertilized plots without increasing residual NO₃---N accumulation; whereas fertilizer N rates of > 125 kg ha⁻¹ yr⁻¹ did not appreciably increase plant yields over the 125-kg-ha⁻¹-N rate, but did appreciably increase residual NO₃.     

Transport and transformation of sulfur compounds over East Asia during the TRACE-P and ACE-Asia campaigns

On the basis of the recently estimated emission inventory for East Asia with a resolution of 1×1°, the transport and chemical transformation of sulfur compounds over East Asia during the period of 22 February through 4 May 2001 was investigated by using the Models-3 Community Multi-scale Air Quality (CMAQ) modeling system with meteorological fields calculated by the regional atmospheric modeling system (RAMS). For evaluating the model performance simulated concentrations of sulfur dioxide (SO₂) and aerosol sulfate (SO₄²⁻) were compared with the observations on the ground level at four remote sites in Japan and on board aircraft and vessel during the transport and chemical evolution over the Pacific and Asian Pacific regional aerosol characterization experiment field campaigns, and it was found that the model reproduces many of the important features in the observations, including horizontal and vertical gradients. The SO₂ and SO₄²⁻ concentrations show pronounced variations in time and space, with SO₂ and SO₄²⁻ behaving differently due to the interplay of chemical conversion, removal and transport processes. Analysis of model results shows that emission was the dominant term in regulating the SO₂ spatial distribution, while conversion of SO₂ to SO₄²⁻ in the gas phase and the aqueous phase and wet removal were the primary factors that controlled SO₄²⁻ amounts. The gas phase and the aqueous phase have the same importance in oxidizing SO₂, and about 42% sulfur compounds (25% in SO₂) emitted in the model domain was transported out, while about 57% (35% by wet removal processes) was deposited in the domain during the study period.     

Bottom-up uncertainty estimates of global ammonia emissions from global agricultural production systems

Here we present an uncertainty analysis of NH₃ emissions from agricultural production systems based on a global NH₃ emission inventory with a 5×5 min resolution. Of all results the mean is given with a range (10% and 90% percentile). The uncertainty range for the global NH₃ emission from agricultural systems is 27–38 (with a mean of 32) Tg NH₃-N yr⁻¹, N fertilizer use contributing 10–12 (11) Tg yr⁻¹ and livestock production 16–27 (21) Tg yr⁻¹. Most of the emissions from livestock production come from animal houses and storage systems (31–55%); smaller contributions come from the spreading of animal manure (23–38%) and grazing animals (17–37%). This uncertainty analysis allows for identifying and improving those input parameters with a major influence on the results. The most important determinants of the uncertainty related to the global agricultural NH₃ emission comprise four parameters (N excretion rates, NH₃ emission rates for manure in animal houses and storage, the fraction of the time that ruminants graze and the fraction of non-agricultural use of manure) specific to mixed and landless systems, and total animal stocks. Nitrogen excretion rates and NH₃ emission rates from animal houses and storage systems are shown consistently to be the most important parameters in most parts of the world. Input parameters for pastoral systems are less relevant. However, there are clear differences between world regions and individual countries, reflecting the differences in livestock production systems.