Measurements of ammonia concentrations,fluxes and dry deposition velocities to a spruce forest 1991–1995

The dry deposition velocities and fluxes of ammonia have been estimated from measurements of the vertical gradient of ammonia and micrometeorology above a spruce forest in western Jutland, Denmark. Measurements have been made in seven periods, each lasting about one week and covering all seasons and different meteorological situations. Different deposition characteristics were observed, depending on the ammonia concentration and the relative humidity. At conditions with westerly winds, the wind brings air masses from the North Sea with low concentration levels of ammonia to the site, while at conditions with easterly winds, the air have passed central Jutland with large emission areas. Some of the relatively low deposition velocities or emissions were observed during conditions with low ammonia concentration and westerly winds. These observations might relate to a compensation point of the forest, i.e. an ammonia concentration below which the trees and/or the surface emit ammonia due to an equilibrium with the ammonia inside the needles or on the surface. Emission of ammonia was also observed at relatively high ammonia concentration levels (above 2 μg NH₃–N m^-3), mainly during one measuring period characterized by easterly winds with dry conditions and high ammonia concentrations, and the emissions might relate to evaporation from ammonia saturated surfaces or emission from mineralization in the forest soil. In general, relatively high net deposition velocities were observed during conditions with relative humidity above 80% or at ammonia concentrations moderate higher than a given (temperature dependent) compensation point. During stable conditions some observations revealed that the gradient above the canopy not necessarily represents the exchange with the canopy.     

Mass budgets and contribution of individual sources and sinks to the abundance of gamma-HCH, alpha-HCH and PCB 153 in the North Sea

Mass budgets of hexachlorocyclohexanes (alpha-HCH and gamma-HCH) and a polychlorinated biphenyl (PCB 153) for 1995--2001 were calculated based on model simulations and observations for the North Sea as a whole and the German Bight, a coastal shallow subregion. For the North Sea the air-sea fluxes of the three pollutants were net depositional and dominated by local sources (gamma-HCH and PCB 153) or atmospheric deposition (alpha-HCH). The air-sea fluxes were net volatilizational in the German Bight. Unlike HCH, PCB 153 does not show a downward trend in the North Sea marine environment during the study period. Due to its physicochemical properties it is expected to readily enter the food chains. Model results suggest that during studied period, the North Sea was a sink for PCB 153 and a source of HCHs for the outer world.     

Atmospheric concentrations and air-sea exchanges of nonylphenol, tertiary octylphenol and nonylphenol monoethoxylate in the North Sea

Concentrations of nonylphenol isomers (NP), tertiary octylphenol (t-OP) and nonylphenol monoethoxylate isomers (NP1EO) have been simultaneously determined in the sea water and atmosphere of the North Sea. A decreasing concentration profile appeared following the distance increasing from the coast to the central part of the North Sea. Air-sea exchanges of t-OP and NP were estimated using the two-film resistance model based upon relative air-water concentrations and experimentally derived Henry's law constant. The average of air-sea exchange fluxes was -12+/-6 ng m(-2)day(-1) for t-OP and -39+/-19 ng m(-2)day(-1) for NP, which indicates a net deposition is occurring. These results suggest that the air-sea vapour exchange is an important process that intervenes in the mass balance of alkylphenols in the North Sea.     

Atmospheric pathways of chlorinated pesticides and natural bromoanisoles in the northern Baltic Sea and its catchment

Long-range atmospheric transport is a major pathway for delivering persistent organic pollutants to the oceans. Atmospheric deposition and volatilization of chlorinated pesticides and algae-produced bromoanisoles (BAs) were estimated for Bothnian Bay, northern Baltic Sea, based on air and water concentrations measured in 2011–2012. Pesticide fluxes were estimated using monthly air and water temperatures and assuming 4 months ice cover when no exchange occurs. Fluxes were predicted to increase by about 50 % under a 2069–2099 prediction scenario of higher temperatures and no ice. Total atmospheric loadings to Bothnian Bay and its catchment were derived from air–sea gas exchange and “bulk” (precipitation + dry particle) deposition, resulting in net gains of 53 and 46 kg year^?1 for endosulfans and hexachlorocyclohexanes, respectively, and net loss of 10 kg year^?1 for chlordanes. Volatilization of BAs releases bromine to the atmosphere and may limit their residence time in Bothnian Bay. This initial study provides baseline information for future investigations of climate change on biogeochemical cycles in the northern Baltic Sea and its catchment.     

Estimation of nitrogen balance between the atmosphere and Lake Balaton and a semi natural grassland in Hungary

The paper summarises the results to determine the fluxes of different N-compounds within the atmosphere and an aquatic and a terrestrial ecosystems, in Hungary. In the exchange processes of N-compounds between atmosphere and various ecosystems the deposition dominates. The net deposition fluxes are -730, -1270 and -1530 mg Nm(-2)yr(-1) for water, grassland, and forest ecosystems, respectively. For water, the main source of nitrogen compounds is the wet deposition. Ammonia gas is close to the equilibrium between the water and the air. For grassland the dry flux of nitric acid and ammonia is also an important term beside the wet deposition. Dry deposition to terrestrial ecosystems is roughly two times higher than wet deposition. A total of 8-10% of the nitrates and NH(x) deposited to terrestrial ecosystems are re-emitted into the air in the form of nitrous oxide (N2O) greenhouse gas.     

Seasonal dependence of the chiral composition of alpha-HCH in coastal deposition at the North Sea

The environmental pollutant alpha-HCH was analysed in seawater, air and bulk deposition samples from the North Sea. Enantioselective analyses of the sample extracts gave evidence of the change of the direction of net air-water gas transfer of the contaminant in dependence on the season. Due to warmer water surface temperatures during late summer to early autumn the equilibrium of alpha-HCH between air and water is dominated rather by volatilisation than deposition. The volatilisation of non-racemic alpha-HCH, as known to occur from seawater, changes the enantiomeric ratio in air, which is reflected in the observed ratio in rain that passes the air column.     

Application of micrometeorological approaches to measure methane exchange in a dry paddy field in the western coast of Korea

The exchange processes of CH₄ were investigated in a paddy field in the Hari area of Kang Hwa Island over an 8 day period in late April 2002. The quantification of CH₄ fluxes was made under dry field condition of early spring by concurrently measuring its concentrations (at the two heights of 1 and 5 m) and the relevant micrometeorological parameters. To help elucidate the factors determining the mobilization characteristics of CH₄, the results of our measurement data were examined using a number of approaches. The results of the trajectory analysis indicated that its concentration changed very sensitively with the influence of different source types, as seen from the air mass movement patterns. The concentrations and fluxes of methane, when examined over this short-term scale, showed moderately strong patterns across 24 h period in which higher values tend to occur during morning or evening. The overall results of our field measurements suggest that CH₄ exchange processes in the paddy area proceeded in a fairly complicated manner. The study area behaved as a net source of CH₄ to the atmosphere with a net daily emission rate of 3.6 mg m⁻² despite the fact that downward deposition was observed more frequently than upward emission.     

Organophosphorus flame retardants and plasticizers in the atmosphere of the North Sea

Air samples collected in the German part of the North Sea from March to July 2010 were investigated for organophosphorus compounds (OPs) being applied as flame retardants and plasticizers. The ∑₈OPs concentration ranged from 110 to 1400 pg m⁻³ while tris(2-chloroisopropyl) phosphate (TCPP) dominated all samples with individual concentrations up to 1200 pg m⁻³. The highest concentrations were observed in continental air masses showing the high influence of industrialized regions including production sites on atmospheric emissions and concentrations. The occurrence of OPs even in oceanic/Arctic air masses shows that OPs can undergo long-range atmospheric transport. Dry particle-bound deposition fluxes from 9 to 240 ng m⁻² d⁻¹ for ∑₈OPs were estimated leading to a minimum annual flux of 710 ± 580 kg y⁻¹ OPs into the German North Sea. This study presents the first occurrence of OPs in the marine atmosphere together with important information on their long-range transport potential.     

Error estimations of dry deposition velocities of air pollutants using bulk sea surface temperature under common assumptions

It is well known that skin sea surface temperature (SSST) is different from bulk sea surface temperature (BSST) by a few tenths of a degree Celsius. However, the extent of the error associated with dry deposition (or uptake) estimation by using BSST is not well known. This study tries to conduct such an evaluation using the on-board observation data over the South China Sea in the summers of 2004 and 2006. It was found that when a warm layer occurred, the deposition velocities using BSST were underestimated within the range of 0.8–4.3%, and the absorbed sea surface heat flux was overestimated by 21 W m^?2. In contrast, under cool skin only conditions, the deposition velocities using BSST were overestimated within the range of 0.5–2.0%, varying with pollutants and the absorbed sea surface heat flux was underestimated also by 21 W m^?2. Scale analysis shows that for a slightly soluble gas (e.g., NO₂, NO and CO), the error in the solubility estimation using BSST is the major source of the error in dry deposition estimation. For a highly soluble gas (e.g., SO₂), the error in the estimation of turbulent heat fluxes and, consequently, aerodynamic resistance and gas-phase film resistance using BSST is the major source of the total error. In contrast, for a medium soluble gas (e.g., O₃ and CO₂) both the errors from the estimations of the solubility and aerodynamic resistance are important. In addition, deposition estimations using various assumptions are discussed. The largest uncertainty is from the parameterizations for chemical enhancement factors. Other important areas of uncertainty include: (1) various parameterizations for gas-transfer velocity; (2) neutral-atmosphere assumption; (3) using BSST as SST, and (4) constant pH value assumption.     

Deposition of atmospheric ammonia to moorlands

Micrometeorological methods were applied to measure fluxes of atmospheric ammonia (NH3) to moorlands. Measurements were made in a wide variety of surface conditions and included both Calluna vulgaris (L.) Hull and Eriophorum vaginatum L. dominated sites. NH3 was found to deposit rapidly to all the sites investigated, providing large deposition velocities (Vd, typically 10-40 mm s(-1)) and usually minimal surface resistances (rc). A small number of measurements were made in frozen conditions and suggest a possible exception to this pattern with mean rc of 50-200 s m(-1). The effect of vegetation drying was also investigated and a possible increase in rc observed, though this was small (< 10 s m(-1)). The results are interpreted in terms of the processes controlling exchange; it is shown that NH3 deposition is predominantly to the leaf surfaces and that the net NH3 compensation point approaches zero. Annual estimates show that dry deposition of NH3 is a major source of atmospheric nitrogen to moorland ecosystems. For two typical UK sites subject to background air concentrations, NH3 dry deposition is of similar magnitude to equivalent NH4+ inputs in wet deposition. In the vicinity of emission sources, NH3 dry deposition is expected to dominate inputs of atmospheric nitrogen.     

The air-water exchange of polychlorinated biphenyls and polybrominated diphenyl ethers at an urban lake, a receipt water body for the effluent from a municipal sewage treatment plant

The effluents and sludge from municipal sewage treatment plants (MSTPs) are considered as potential sources of many contaminants to the ambient environments. In the present work, the air-water exchange of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) was studied using passive air samplers at an urban lake, which receives the effluents from a MSTP in Beijing, China. The concentrations of PCBs and PBDEs in atmosphere were in the range 15.5-108 ng sample⁻¹ and 2.37-27.8 ng sample⁻¹, respectively, during the sampling period (August, 2007-July, 2008). The predominant PCBs and PBDEs were lowly halogenated congeners. The calculation for the exchange fluxes of PCBs and PBDEs using fugacity model showed that, the net exchange fluxes in different seasons were closely related to the halogen number of different congeners. Except for CBs-28 and 52, the net exchange fluxes was mainly directed from air to water for most of predominant congeners, which implied that the lower chlorinated CBs were dominated by volatilization process rather than the dry/wet depositions and diffusion between air-water interface, additionally, for heavy congeners, the dry/wet deposition process was an important source of PCBs and PBDEs in this lake.     

MEAD: an interdisciplinary study of the marine effects of atmospheric deposition in the Kattegat

This paper summarises the results of the EU funded MEAD project, an interdisciplinary study of the effects of atmospheric nitrogen deposition on the Kattegat Sea between Denmark and Sweden. The study considers emissions of reactive nitrogen gases, their transport, transformations, deposition and effects on algal growth together with management options to reduce these effects. We conclude that atmospheric deposition is an important source of fixed nitrogen to the region particularly in summer, when nitrogen is the limiting nutrient for phytoplankton growth, and contributes to the overall eutrophication pressures in this region. However, we also conclude that it is unlikely that atmospheric deposition can, on its own, induce algal blooms in this region. A reduction of atmospheric nitrogen loads to this region will require strategies to reduce emissions of ammonia from local agriculture and Europe wide reductions in nitrous oxide emissions.     

Methanesulphonic acid (MSA) stratigraphy from a Talos Dome ice core as a tool in depicting sea ice changes and southern atmospheric circulation over the previous 140 years

Firn core methanesulphonic acid (MSA) stratigraphy from Talos Dome (East Antarctica) was compared with anomalies of the satellite-measured sea ice extent (1973–1995) in the Ross Sea and Wilkes Land oceanic sector. In spite of the sparseness of sea ice data, the MSA maxima fit with many positive sea ice anomalies in the Ross Sea. This evidence suggests that marine biogenic activity enhanced by large sea ice cover is an important, but not exclusive, factor in controlling MSA concentration in snow precipitation at Talos Dome. Other than source intensity, differences in regional atmospheric transport mechanisms affect the arrival of MSA-rich aerosol at Talos Dome. To clarify the role of transport processes in bringing biogenic aerosol to Talos Dome, a spectral analysis was applied to the MSA, SOI (South Oscillation Index), and SAM (Southern Annular Mode) record. Synchronicity or phase shift between the chemical signature and atmospheric circulation modes were tested. The variations in the MSA profile have a periodicity of 6.9, 4.9, 3.5, and 2.9 years. The 6.9 and 2.9 year periodicities show a strong positive correlation and are synchronous with corresponding SOI periodicity. This variability could be related to an increase in MSA source intensity (by dimethylsulphide from phytoplanktonic activity) linked to the sea ice extent in the Ross Sea area, but also to an increased strength in transport processes. Both of these factors are correlated with La Niña events (SOI positive values). Furthermore, SAM positive values are related to an increased sea ice extent in the Ross Sea sector and show two main periodicities 3.3 and 3.8 years. These periodicities determine the MSA variability at 3.5 years. However, the effect of intensification of the polar vortex and the consequent reduction in transport process intensity, which reduce the delivery of air masses enriched in MSA from oceanic areas to Talos Dome, make the effect of the SAM on the MSA concentration at Talos Dome less active than the SOI. In this way, snow deposition at the Talos Dome records larger MSA concentration by the combined effects of increased source emissions and more efficient transport processes. The MSA record from Talos Dome can therefore be considered a reliable proxy of sea ice extent when the effect of changes in transport processes in this region of Antarctica is considered. Over the previous 140 years, these conditions occur with a periodicity of 6.9 years.     

The influence of aerosol dynamics on indoor exposure to airborne DEHP

A mass-balance model was extended to investigate the influence of aerosol particles on the accumulation of indoor airborne DEHP, which allows the consideration of a variable particle concentration. The calculated gas-phase di-2-ethylhexyl phthalate (DEHP) concentration is consistent with those measured within residences in both the United States and Europe. Model predictions suggest that there are differences of more than 10% of particle-phase DEHP concentrations between the variable-particle-concentration case and the constant one for over half (578 days) within the calculation time of 1000 days. Airborne DEHP consists primarily of a particle phase. The exposure data indicate that the influence of particle dynamics remains significant throughout the calculation period, and the size fraction of 0–0.5 μm contributes the most, at 39.1%, to the total exposure to particle-phase DEHP as a result of a strong “source” effect which brings particles into the indoor air and a weak “sink” effect which removes particles from the indoor air. The sensitivity analysis indicates that deposition exhibits the most apparent influence, and particle emission from cooking is a significant factor, as cooking is the main source of particles in the size fraction of 0–0.5 μm. The sensitivity analysis also shows that particle penetration has a less obvious influence on the exposure to airborne DEHP because air exchange rate caused penetration introduces and removes particles simultaneously, thus having a limited influence on the airborne DEHP; while resuspension exhibits the weakest influence because it contributes little to the small particles which are the main component of aerosol particles indoors. Strategies for enhancing deposition and reducing particle emissions from cooking and penetration may be helpful to reduce residents’ exposure to airborne SVOCs.     

Challenges in quantifying biosphere-atmosphere exchange of nitrogen species

Recent research in nitrogen exchange with the atmosphere has separated research communities according to N form. The integrated perspective needed to quantify the net effect of N on greenhouse-gas balance is being addressed by the NitroEurope Integrated Project (NEU). Recent advances have depended on improved methodologies, while ongoing challenges include gas-aerosol interactions, organic nitrogen and N(2) fluxes. The NEU strategy applies a 3-tier Flux Network together with a Manipulation Network of global-change experiments, linked by common protocols to facilitate model application. Substantial progress has been made in modelling N fluxes, especially for N(2)O, NO and bi-directional NH(3) exchange. Landscape analysis represents an emerging challenge to address the spatial interactions between farms, fields, ecosystems, catchments and air dispersion/deposition. European up-scaling of N fluxes is highly uncertain and a key priority is for better data on agricultural practices. Finally, attention is needed to develop N flux verification procedures to assess compliance with international protocols.     

Development and application of a regional-scale atmospheric mercury model based on WRF/Chem: a Mediterranean area investigation

The emission, transport, deposition and eventual fate of mercury (Hg) in the Mediterranean area has been studied using a modified version of the Weather Research and Forecasting model coupled with Chemistry (WRF/Chem). This model version has been developed specifically with the aim to simulate the atmospheric processes determining atmospheric Hg emissions, concentrations and deposition online at high spatial resolution. For this purpose, the gas phase chemistry of Hg and a parametrised representation of atmospheric Hg aqueous chemistry have been added to the regional acid deposition model version 2 chemical mechanism in WRF/Chem. Anthropogenic mercury emissions from the Arctic Monitoring and Assessment Programme included in the emissions preprocessor, mercury evasion from the sea surface and Hg released from biomass burning have also been included. Dry and wet deposition processes for Hg have been implemented. The model has been tested for the whole of 2009 using measurements of total gaseous mercury from the European Monitoring and Evaluation Programme monitoring network. Speciated measurement data of atmospheric elemental Hg, gaseous oxidised Hg and Hg associated with particulate matter, from a Mediterranean oceanographic campaign (June 2009), has permitted the model’s ability to simulate the atmospheric redox chemistry of Hg to be assessed. The model results highlight the importance of both the boundary conditions employed and the accuracy of the mercury speciation in the emission database. The model has permitted the reevaluation of the deposition to, and the emission from, the Mediterranean Sea. In light of the well-known high concentrations of methylmercury in a number of Mediterranean fish species, this information is important in establishing the mass balance of Hg for the Mediterranean Sea. The model results support the idea that the Mediterranean Sea is a net source of Hg to the atmosphere and suggest that the net flux is ≈30 Mg year^?1 of elemental Hg.     

Dry and wet deposition of water-insoluble dust and water-soluble chemical species during spring 2007 in Tsukuba,Japan

Dry and wet depositions were sampled daily in Tsukuba, Japan, in spring 2007. Temporal variations in the dry and wet deposition fluxes of dust and water-soluble chemical species were controlled largely by air mass origin, the water vapor mixing ratio, and Asian dust events. The contribution of local sources to dry deposition of dust was large when the wind speed was high. Dry deposition fluxes of water-soluble chemical species were larger in humid air masses than in dry air masses. Wet deposition fluxes of dust and water-soluble chemical species indicated that air masses that passed over dust source regions and industrial regions became mixed with the maritime air masses over the coastal site of the Asian continent and western part of the Japanese islands. The total deposition of dust was 4220 mg m^?2 month^?1, and that of water-soluble chemical species ranged from 10 to 636 mg m^?2 month^?1. Wet deposition fluxes of the total deposition flux of dust accounted for 72% and those of water-soluble chemical species was for 72–96%. In particular, the largest wet deposition occurred during a single Asian dust event on 3 April. This event accounted for 23% (950 mg m^?2 month^?1) of the monthly dust deposition flux and for 2–28% (0.43–51 mg m^?2 month^?1) of the monthly deposition flux of water-soluble chemical species. This result implies that the wet deposition flux associated with even one sporadic Asian dust event can have extensive impacts on both terrestrial and oceanic ecosystems in East Asia.     

A modeling assessment of association between East Asian summer monsoon and fate/outflow of α-HCH in Northeast Asia

Using a dynamic numerical atmospheric transport model for organochlorine pesticides (OCPs), the relationship between the East Asian summer monsoon and the fate of α-hexachlorocyclohexane (α-HCH), a banned OCP, in the atmosphere over Northeast Asia was investigated and assessed. The modeled temporal and spatial patterns and variability of α-HCH air concentrations during the summer months of 2005 revealed a strong link between this chemical in the atmosphere over Northeast Asia and the East Asian summer monsoon. At lower atmospheric levels, easterly and southeasterly winds blowing from relatively cold ocean surface convey α-HCH air concentration from southeast China to northeast China. A monsoon front extending from southeast China to Japan, characterized by a strong wind convergence, carried the air concentration to a high elevation of the atmosphere where it was delivered by southerly monsoon flow to northern China and North Pacific Ocean. This summer monsoon associated northward atmospheric transport caused a reversal of the soil/air exchange from outgassing to net deposition during spring–summer period. The modeled wet deposition fluxes of α-HCH agreed well with the changes in the typical summer monsoon rain bands, designated as Meiyu in China, Changma in Korea, and Baiu in Japan. The major wet deposition flux paralleled with the monsoon front as well as the monsoon rain bands. The temporal change in the fluxes exhibits abrupt northward advances, which is associated with a stepwise northward and northeastward advance of the East Asian summer monsoon. The modeled α-HCH outflow in the atmosphere from China occurs mostly in the summer months and through northeast China, featured strongly by the evolution of the summer month. This study suggests that the East Asian summer monsoon provides a major atmospheric pathway and summer outflows to α-HCH over East Asia.     

Integrated analysis of the effects of agricultural management on nitrogen fluxes at landscape scale

The integrated modelling system INITIATOR was applied to a landscape in the northern part of the Netherlands to assess current nitrogen fluxes to air and water and the impact of various agricultural measures on these fluxes, using spatially explicit input data on animal numbers, land use, agricultural management, meteorology and soil. Average model results on NH₃ deposition and N concentrations in surface water appear to be comparable to observations, but the deviation can be large at local scale, despite the use of high resolution data. Evaluated measures include: air scrubbers reducing NH₃ emissions from poultry and pig housing systems, low protein feeding, reduced fertilizer amounts and low-emission stables for cattle. Low protein feeding and restrictive fertilizer application had the largest effect on both N inputs and N losses, resulting in N deposition reductions on Natura 2000 sites of 10% and 12%, respectively.     

Factors contributing to seasonal variations in wet deposition fluxes of trace elements at sites along Japan Sea coast

In this study, we measured the wet deposition fluxes of ten trace elements (As, Cd, Cr, Cu, Mn, Ni, Pb, Sb, V and Zn) from December 2002 to March 2006 at three sites along the Japan Sea coast, which have been strongly affected by the long-range transport of air pollutants from the Asian continent. Also, factors, contributing to their seasonal variations were investigated. At the northern and central sites, the monthly wet deposition fluxes of all or most trace elements greatly increased during the cold season (typically, November–April), along with their monthly average (volume-weighted) concentrations in the precipitation. The cold/warm season ratios for the average concentrations of trace elements in precipitation were within the range of 2.7–5.1 at the northern site and 1.8–5.9 at the central site, which were similar to the average scavenging ratios (= concentration in precipitation/concentration in air) at each site. However, there were small differences (0.47–1.2 at the northern site and 0.73–1.7 at the central site) in the ratios of average concentrations in air between the two seasons. These suggest that the increase in the wet deposition fluxes of trace elements during the cold season is due to increases in their scavenging ratios. On the other hand, the result for the southern site was different from those at the other sites. The number of days when the daily maximum wind speed exceeded 10 m s^?1 at the meteorological observatories near the study sites increased markedly during the cold season at the northern and central sites, showing that strong winds usually blow during the cold season at those sites, but not at the southern site. Higher wind speed transports larger amounts of constituents into the cloud system, which can result in their increased concentrations in precipitation. Thus, high scavenging ratios of trace elements during the cold season may be caused by the increase in their amounts of discharge into the cloud system owing to high wind speed, suggesting that wind speed is an important factor in the seasonal variations in the wet deposition fluxes.