Application of the nested grid STEM to an early summer acid rain in South Korea

The nested grid Sulfur Transport Eulerian Model (STEM) was developed and used to simulate the acid rain in Korea that occurred on 10 June 1996. The present nested grid system consists of three-grid systems. The coarsest grid system includes China, Korean Peninsula and Japan with the horizontal grid size of 80 km and the finest grid system includes only Korea with the horizontal grid size of 8.9 km. The calculated gas-phase SO₂ and O₃ concentrations agree relatively well with the field measurements. In addition, the model successfully reproduces the measured sulfate and nitrate concentrations in the rain water and futhermore identified the high concentration regions of liquid-phase sulfate and nitrate. In the present simulation conditions, most of the gas-phase of SO₂ and HNO₃ were washed out. A close relationship between wet deposition fluxes and precipitation rates were found for sulfate and nitrate. Finally, the model results also showed that a fine grid size is required to accurately calculate gas-phase concentrations as well as acid deposition fluxes.     

Modelling the behaviour of PAHs during atmospheric transport from the UK to the Arctic

Persistent organic pollutants (POPs) such as PAHs are subject to long-range atmospheric transport, which can result in the contamination of remote areas such as the Arctic. A simple model was developed to describe the removal processes of four PAHs; fluorene (FLU), phenanthrene (PHEN), fluoranthene (FLA) and benzo[a]pyrene (B[a]P) transported over a 5 day period from a source area over the UK to the Russian Arctic. The purpose of this model was to study processes affecting the PAHs within the atmosphere, rather than their interaction with the earth's surface. The components to the model included gas/particle partitioning, reaction with OH radicals and dry and wet deposition (both rain and snow). Atmospheric/meteorological parameters for the geographical region of interest were generated from three-dimensional atmospheric models. Air concentrations were prescribed in the source area with no additional PAH inputs along the transect, both winter and summer scenarios were modelled. Reaction with OH was a major removal mechanism for gas-phase FLU, PHEN and FLA, most notably in the temperate atmosphere. Wet deposition in the form of snow accounted for the majority of PAH loss in the winter, although the gas and particle scavenging ratios used in this model ranged over several orders of magnitude. Using a 5 day transport scenario in a `1-hop’ event, the model predicted that a primary emission of FLA and B[a]P to the atmosphere of the southern UK, would not reach the Russian Arctic at a distance of ∼3500 km, assuming a constant windspeed of 10 m s⁻¹. However, both FLU and PHEN with calculated half-lives of >60 h during the winter could be transported to this area under this scenario.     

Platinum-group elements (Rh,Pt, Pd) and Au distribution in snow samples from the Kola Peninsula,NW Russia

In April 1996 snowpack samples were collected from the surroundings of the ore roasting and dressing plant at Zapoljarnij and the nickel smelters at Nikel and Monchegorsk, Kola Peninsula, NW Russia. In the laboratory, filter residues of snowpack samples (fraction>0.45 μm) from 15 localities (close to the nickel processing centres) were chemically for precious metals (Rh, Pt, Pd, Au) and Te by graphite furnace atomic absorption spectrometry (GFAAS) analysis, and for Cu and Ni by ICP-MS. Values up to 2770 ng/l Pd, 650 ng/l Pt and 186 ng/l Au were found in the filter residues. Additionally, platinum-group elements (PGE) and Au contents in ore samples from Noril’sk¹, as well as in technogenic products (“Cu–Ni-feinstein” and copper concentrate) processed at the Monchegorsk smelter complex, were analysed using flameless atomic absorption spectroscopy (FAAS) for comparison with results obtained from snow. Rh, Pt, Pd and Au distribution data show the presence of two ore components (Noril’sk and Pechenga). Concentrations of these metals decrease with distance from the industrial sources and with the prevailing wind direction (generally north–south). Microscopic investigations and electron microprobe analysis of polished sections of snow filter residues (>0.45 μm) also reveal differences between particles from the two sources.     

Importance of wet precipitation as a removal and transport process for atmospheric water soluble carbonyls

Carbonyl compounds exist in the atmosphere as either gases or aerosols. Some of them are water soluble and known as oxidation products of biogenic and/or anthropogenic hydrocarbons. Five carbonyl compounds, glyoxal (GO), 4-oxopentanal (4-OPA), glycolaldehyde (GA), hydroxyacetone (HA) and methylglyoxal (MG) have been identified in a temporal series of 12 rain samples. The concentrations of the compounds in the samples were high at the beginning of the rain event and decreased with time to relatively low and fairly constant levels, indicating that the compounds were washed out from the atmosphere at the start of the rain event. Possibly, these compounds also existed in the cloud condensation nuclei (CCN). Wet deposition rates of the carbonyl compounds were calculated for nine samples collected during a 20 h period. The deposition rates ranged from 0 (4-OPA) to 1.2×10⁻¹ mg C m⁻² h⁻¹ (MG) with the average of 2.9×10⁻² mg C m⁻² h⁻¹. Production rates of isoprene oxidation products (GA, HA and MG) in the area surrounding the sampling site were estimated with a chemical box model. The deposition rates exceeded the production rates in most samples. This indicates that the rainfall causes a large net flux of the water soluble compounds from the atmosphere to the ground. Insoluble carbonyl compounds such as n-nonanal and n-decanal were expected to be present in the atmosphere, but were not detected in the rain during the sampling period, suggesting that an aerosol containing these insoluble compounds does not effectively act as a CCN.     

The record of anthropogenic pollution in snow and ice in Svalbard,Norway

From the examination of the spatial distribution of pollutants and of the record from ice cores, it is demonstrated that Svalbard is strongly affected by anthropogenic pollution. This pollution has caused an increase of approximately 90% in the acidity of the snow deposited in the Archipelago since the beginning of the Industrial Revolution. High concentrations of H⁺, frequently greater than 10 μeq l⁻¹ (i.e. with pHs lower than 5.0), associated with high concentrations of sulphates, indicate that Svalbard is experiencing the phenomenon of acid deposition. The first part of this work reviews the existing knowledge of atmospheric, snow, and ice pollution in Svalbard. This is followed by an examination of the acidity time series, supported by excess-sulphate measurements, performed on an ice core from central-eastern Spitsbergen that provide a historical record of acid deposition over a 54 year period. An ice core recovered from Austfonna, Nordaustlandet provided baseline values and also a record of acidity in precipitation before and during the entire industrial period, thereby allowing the evolution of acid deposition in the Archipelago to be traced. The records of these two Svalbard cores also reflect the overall regional trends.     

Snow-to-air exchanges of mercury in an Arctic seasonal snow pack in Ny-Ålesund,Svalbard

The study of mercury (Hg) cycle in Arctic regions is a major subject of concern due to the dramatic increases of Hg concentrations in ecosystem in the last few decades. The causes of such increases are still in debate, and an important way to improve our knowledge on the subject is to study the exchanges of Hg between atmosphere and snow during springtime. We organized an international study from 10 April to 10 May 2003 in Ny-Ålesund, Svalbard, in order to assess these fluxes through measurements and derived calculations.Snow-to-air emission fluxes of Hg were measured using the flux chamber technique between ∼0 and 50 ng m⁻² h⁻¹. A peak in Gaseous Elemental Mercury (GEM) emission flux from the snow to the atmosphere has been measured just few hours after an Atmospheric Mercury Depletion Event (AMDE) recorded on 22 April 2004. Surprisingly, this peak in GEM emitted after this AMDE did not correspond to any increase in Hg concentration in snow surface. A peak in GEM flux after an AMDE was observed only for this single event but not for the four other AMDEs recorded during this spring period.In the snow pack which is seasonal and about 40 cm depth above permafrost, Hg is involved in both production and incorporation processes. The incorporation was evaluated to ∼5–40 pg m² h. Outside of AMDE periods, Hg flux from the snow surface to the atmosphere was the consequence of GEM production in the air of snow and was about ∼15–50 ng m⁻² h⁻¹, with a contribution of deeper snow layers evaluated to ∼0.3–6.5 ng m⁻² h⁻¹. The major part of GEM production is then mainly a surface phenomenon. The internal production of GEM was largely increasing when snow temperatures were close to melting, indicating a chemical process occurring in the quasi-liquid layer at the surface of snow grains.     

Modelling atmospheric bulk deposition of Pb,Zn and Cd near a former Pb–Zn mine in West Greenland using transplanted Flavocetraria nivalis lichens

Atmospheric deposition of lead (Pb), zinc (Zn) and cadmium (Cd) was investigated near the former Black Angel Pb–Zn mine in Maarmorilik, West Greenland during 2010–2011. Thalli of the lichen Flavocetraria nivalis were transplanted from an uncontaminated site into sites near the mine and collected the following year. At 20 of the total 21 sites, concentrations of Pb, Zn and Cd were significantly elevated in lichens after 1 year of transplantation compared to initial concentrations. Elevated concentrations were observed within a distance of approx. 20 km from the mining area. Concentrations decreased with increasing distance from the mine and the relation was well described using a power function with a negative exponent (r² = 0.90; 0.83 and 0.83 for Pb; Zn and Cd). To examine the relation between metal concentrations/uptake in lichen transplants and atmospheric bulk deposition, 10 Bergerhoff dust samplers were placed near lichen transplants and samplers and lichens were collected after a 7-weeks exposure period. A significant linear correlation was observed between metal concentrations in lichen transplants and atmospheric bulk metal deposition (r² = 0.94; 0.88 and 0.89 for Pb; Zn and Cd). Combining the results and including an area distribution within a defined metal deposition area, the “annual” deposition of Pb, Zn and Cd as dust was estimated during the 2010–2011 snow-free period (～5 months). The results reveal that 20 years after mine closure, 770 kg Pb, 3700 kg Zn and 24 kg Cd were still being deposited as dust per year (snow-free period only) within a distance of 20 km from the mine.     

Atmospheric distribution of polycyclic aromatic hydrocarbons and deposition to Galveston Bay,Texas, USA

Estimates of the atmospheric deposition to Galveston Bay of polycyclic aromatic hydrocarbons (PAHs) are made using precipitation and meteorological data that were collected continuously from 2 February 1995 to 6 August 1996 at Seabrook, TX, USA. Particulate and vapor phase PAHs in ambient air and particulate and dissolved phases in rain samples were collected and analyzed. More than 95% of atmospheric PAHs were in the vapor phase and about 73% of PAHs in the rain were in the dissolved phase. Phenanthrene and napthalene were the dominant compounds in air vapor and rain dissolved phases, respectively, while 5 and 6 ring PAH were predominant in the particulate phase of both air and rain samples. Total PAH concentrations ranged from 4 to 161 ng m⁻³ in air samples and from 50 to 312 ng l⁻¹ in rain samples. Temporal variability in total PAH air concentrations were observed, with lower concentrations in the spring and fall (4–34 ng m ⁻³) compared to the summer and winter (37–161 ng m⁻³). PAHs in the air near Galveston Bay are derived from both combustion and petroleum vaporization. Gas exchange from the atmosphere to the surface water is estimated to be the major deposition process for PAHs (1211 μg m^{− 2} yr^{− 1}), relative to wet deposition (130 μg m⁻² yr^{− 1}) and dry deposition (99 μg m⁻² yr^{− 1}). Annual deposition of PAHs directly to Galveston Bay from the atmosphere is estimated as 2  t yr⁻¹.     

Modelling base cations in Europe—sources,transport and deposition of calcium

The deposition of the base cations calcium, magnesium and potassium from the atmosphere needs to be quantified in the calculation of the total deposited acidity in the critical loads approach. Of these base cations, calcium has been found to be the most important in terms of mass deposited. However, the sources of calcium to the atmosphere are not well understood. Recently, the first spatially disaggregated inventory of industrial calcium emissions for Europe was presented by Lee and Pacyna (1998) who estimated a total European emission of 0.7–0.8 Mt yr^-1. However, it is thought that wind blown dust from soils contributes a substantial fraction to the deposition of calcium. In this work, the source strength of calcium from arid regions within the EMEP modelling domain was estimated using the global mineral dust emission data base of Tegen and Fung (1994) and an estimation of the calcium content of soils. This results in a “natural” calcium emission of 6 Mt yr^-1. A long-range transport model, TRACK, was used to calculate the wet and dry deposition of calcium arising from these industrial and natural sources to the UK which resulted in a total deposition of 29–30 kt yr^-1. Of this annual deposition, 0.6–0.7 kt arises from cement manufacturing, 0.02–0.03 kt from iron and steel manufacturing, 0.8–0.83 kt from a large point source power generation, and 28 kt from power generation from a small boiler plant. The natural emissions of calcium from arid regions result in a deposition of calcium to the UK of 0.5 kt yr^-1. The measured wet deposition of calcium to the UK is 89 kt yr^-1 and the estimated dry deposition 14 kt yr^-1. The short-fall in the modelled deposition of calcium is thus of the order of 70 kt yr^-1, which is suggested to arise from wind-blown dust from agricultural land in the UK and mainland Europe. The estimated emissions, and thus modelled deposition are rather uncertain, such that estimating deposition of calcium attributable to agricultural soil emissions by differencing has a large uncertainty. However, this is the first such study of its kind for Europe and represents a first step towards understanding the sources of calcium and their contribution to mitigating deposited acidity from acidifying pollutants such as sulphur dioxide, nitrogen oxides and ammonia.     

Modeling of mercury emission,transport and deposition in North America

Most studies on the atmospheric behaviour of mercury in North America have excluded a detailed treatment of natural mercury emissions. The objective of this work is to report a detailed simulation of the atmospheric mercury in a domain that covers a significant part of North America and includes not only anthropogenic mercury emissions but also those from natural sources including vegetation, soil and water.The simulations were done using a natural mercury emission model coupled with the US EPA's SMOKE/CMAQ modelling system. The domain contained 132×90 grid cells at a resolution of 36 km, covering the continental United States, and major parts of Canada and Mexico. The simulation was carried out for 2002, using boundary conditions from a global mercury model. Estimated total natural mercury emission in the domain was 230 tonnes (1 tonne=1000 kg) and the ratio of natural to anthropogenic emissions varied from 0.7 in January to 3.2 in July. Average total gaseous mercury (TGM) concentration ranged between 1 and 4 ng m⁻³. Good agreement was found between the modelled results and measurements at three Ontario sites for ambient mercury concentrations, and at 72 mercury deposition network sites in the domain for wet deposition. The correlation coefficient between the simulated and the measured values of the daily average TGM at three monitoring sites varied between 0.48 and 0.64. When natural emissions were omitted, the correlation coefficients dropped to between 0.15 and 0.40. About 335 tonnes of mercury were deposited in the domain during the simulation period but overall, it acted as a net source of mercury and contributed about 21 tonnes to the global pool. The net deposition of mercury to the Great Lakes was estimated to be about 2.4 tonnes. The estimated deposition values were similar to those reported by other researchers.     

Assessment of metal concentrations in atmospheric particles from Burnaby Lake,British Columbia,Canada

Trace metals were assessed in atmospheric particulates at Burnaby Lake, in the greater Vancouver area of British Columbia to assess concentrations, particle size distributions and deposition rates to an urban watershed. Week-long samples were collected over a period of 18 weeks in 1995 using a 13 stage low pressure impactor (LPI). Samples were analysed using inductively coupled plasma atomic emission spectroscopy (ICP). Aluminum, boron, calcium, iron, magnesium, manganese, sodium and strontium had a similar time series pattern and particle size distribution. For these metals, maximum concentrations occurred during weeks of low precipitation and exhibited a large peak in mid June. Their particle size distribution was mostly dominated by a large peak between 1.7–18.4 μm with a secondary peak at <0.08 μm. Metal concentrations were generally one to three orders of magnitude higher than those measured in a rural location 100 km away from Burnaby Lake but similar to those measured in urban Taipei, Taiwan. Concentrations of the highly toxic metals, arsenic, cadmium and lead were within current air quality guidelines, however boron exceeded the Ontario Ministry of Environment ambient air quality standard in two of the 16 samples. Deposition velocities ranged between 0.22 and 13 cm s⁻¹ with the largest values corresponding to the coarse particle mode. Mean deposition rates ranged between 4.0 μg m⁻² d⁻¹ and 650 mg m⁻² d⁻¹. Depending on the metal, yearly loadings to the watershed ranged from 90 kg to several thousand tonnes. Calcium, aluminum, boron and magnesium had the highest metal loadings to the watershed. Manganese also had relatively high loadings, a reflection of the high traffic density in the area. The relatively high metal deposition rates indicate that metal contribution from atmospheric sources may represent a significant portion of the total metal load to the Burnaby Lake watershed.     

The soil–air exchange characteristics of total gaseous mercury from a large-scale municipal landfill area

The cycle of mercury (Hg) from a gigantic landfill area (area ∼2.72 km²) was investigated by conducting micrometeorological measurements of its exchange rates across soil–air boundary during the spring season of 2000. Based on this field campaign, we attempted to provide various insights into the Hg exchange processes, especially with respect to the decoupling of the mixed signatures of complex source processes. According to our analysis, the cycle of Hg in the study site appeared to be affected significantly by the vent processes; excessive amount of Hg was expected to be released via ventpipes penetrating up to 60 m depths of the deep landfilled waste layer. The influence of these vent source processes was reflected very sensitively by the windrose pattern. The data collected during the non-easterly winds were representing the typical pattern for a strong source area in which upward emission is predominant in both strength and frequency. On the other hand, the data collected from the easterly winds were characterized by excessive deposition of Hg which we suspect is due mostly to the nearest vent located easterly from our measurement spot. The unique characteristics of each data group, divided by windrose pattern, were consistent from apparent difference in: (1) the absolute magnitude of gradient/flux data sets, (2) frequency of exchange for each of two vertical directions, and (3) E/D (emission/deposition) ratios for most relevant parameters. The analysis of the short-term variability of exchange patterns over a 24-h scale, also exhibited that the patterns for two different conditions were quite contrasting as a function of time. The magnitude of bidirectional fluxes in the present study is significantly high with values of 254±224 (N=71 emissions out of 79 fluxes quantified during non-easterly winds) and −1164±1276 ng m⁻² h⁻¹ (N=14 depositions out of 16 fluxes during easterly winds), respectively. If the computed emission rate is extrapolated, we estimate that annual emission of Hg from the study area can amount to approximately 6 kg which is comparable with the estimates for other areas around the globe under strong Hg-pollution.     

Seasonal patterns of heavy metal deposition to the snow on Lambert Glacier basin,East Antarctica

Al, V, Mn, Fe, Cu, As, Cd, Ba, Pb, Bi and U were determined in a continuous series of 46 snow samples from a 2.3-m snow pit, covering the time period from austral spring 1998 to summer 2002, at a site on the east side of the Lambert Glacier basin in East Antarctica. Concentrations are very low for all metals and differ by orders of magnitude from one metal to another, with the mean concentrations ranging from 0.028 pg g⁻¹ for Bi to 165 pg g⁻¹ for Al. It is estimated that anthropogenic contributions are dominant for Cu, Pb and probably As, in the snow in our study area while the natural contributions from rock and soil dust, sea-salt spray and volcanic emissions account for most of the measured concentrations of the other metals. Our snow profiles show pronounced seasonal variations for Mn, As, Ba, Pb and Bi throughout the year, but a very different situation is observed between different metals. These observations suggest that heavy metals determined in our samples are controlled by different transport and deposition mechanisms related to physical and chemical alterations in the properties and sources of aerosol.     

Receptor modeling of source apportionment of Hong Kong aerosols and the implication of urban and regional contribution

Understanding the spatial–temporal variations of source apportionment of PM_2.5 is critical to the effective control of particulate pollution. In this study, two one-year studies of PM_2.5 composition were conducted at three contrasting sites in Hong Kong from November 2000 to October 2001, and from November 2004 to October 2005, respectively. A receptor model, principal component analysis (PCA) with absolute principal component scores (APCS) technique, was applied to the PM_2.5 data for the identification and quantification of pollution sources at the rural, urban and roadside sites. The receptor modeling results identified that the major sources of PM_2.5 in Hong Kong were vehicular emissions/road erosion, secondary sulfate, residual oil combustion, soil suspension and sea salt regardless of sampling sites and sampling periods. The secondary sulfate aerosols made the most significant contribution to the PM_2.5 composition at the rural (HT) (44 ± 3%, mean ± 1σ standard error) and urban (TW) (28 ± 2%) sites, followed by vehicular emission (20 ± 3% for HT and 23 ± 4% for TW) and residual oil combustion (17 ± 2% for HT and 19 ± 1% for TW). However, at the roadside site (MK), vehicular emissions especially diesel vehicle emissions were the major source of PM_2.5 composition (33 ± 1% for diesel vehicle plus 18 ± 2% for other vehicles), followed by secondary sulfate aerosols (24 ± 1%). We found that the contribution of residual oil combustion at both urban and rural sites was much higher than that at the roadside site (2 ± 0.4%), perhaps due to the marine vessel activities of the container terminal near the urban site and close distance of pathway for the marine vessels to the rural site. The large contribution of secondary sulfate aerosols at all the three sites reflected the wide influence of regional pollution. With regard to the temporal trend, the contributions of vehicular emission and secondary sulfate to PM_2.5 showed higher autumn and winter values and lower summer levels at all the sites, particularly for the background site, suggesting that the seasonal variation of source apportionment in Hong Kong was mainly affected by the synoptic meteorological conditions and the long-range transport. Analysis of annual patterns indicated that the contribution of vehicular emission at the roadside was significantly reduced from 2000/01 to 2004/05 (p < 0.05, two-tail), especially the diesel vehicular emission (p < 0.001, two-tail). This is likely attributed to the implementation of the vehicular emission control programs with the tightening of diesel fuel contents and vehicular emission standards over these years by the Hong Kong government. In contrast, the contribution of secondary sulfate was remarkably increased from 2001 to 2005 (p < 0.001, two-tail), indicating a significant growth in regional sulfate pollution over the years.     

Bioconcentration of metals in the moss Scleropodium purum in the area surrounding a power plant. A geotopographical predictive model for mercury

Samples of the moss Scleropodium purum collected in 1995 and 1997 were used to biomonitor the deposition of metals in the area surrounding a thermal power plant. Significantly higher levels of Cu (p<0.05), Fe (p<0.01), As and Hg (p<0.001) were found in the 1997 samples than in the 1995 samples, due to changes in atmospheric conditions. The influence on bioconcentration of the orientation of the sampling sites relative to the source of emission was studied. It was found that the increase recorded in 1997 generally occurred in the sampling sites in the south east of the study area. Analysis of the effect of distance from the source of emission revealed that the increase in metal levels in 1997 took place close to the power station (10–30 km). Finally, multiple regression analysis was used to construct a model that related different topographical variables to the concentrations of Hg in moss. The model, constructed using the data collected in both sampling periods, included the orientation of the sampling sites relative to the source of emission as well as the height of sampling sites in 1995 and the distance from the emission point in 1997. The model allowed us to determine the extent of the area affected by deposition and to establish the magnitude of deposition.     

Black carbon concentrations in precipitation and near surface air in and near Halifax,Nova Scotia

Black carbon (soot) concentrations have been measured in rain water, snow samples and near surface air at several locations in Nova Scotia, Canada. The average black carbon concentration in near surface air in summer was found to be 0.54 μg m^-3 compared to 1.74 μg m^-3 in the winter season. These values are comparable to black carbon concentrations found in other mid-size urban areas. The black carbon concentration in rain water and snow samples varied between an undetectable amount to about 20 μg kg^-1 of rain (or melt) water. The relatively low concentrations of black carbon in precipitation are attributed to extratropical cyclones that often develop off-shore to the east and south of Nova Scotia in relatively clean conditions of the marine boundary layer.     

Influence of air mass trajectories on the chemical composition of precipitation in India

Chemical composition of precipitation was measured with wet-only samplers at a rural site at Bhubaneswar in eastern India during 1997–1998. All rain events were compared with trajectories and precipitation fields from the ECMWF. The pH and ionic concentrations were found to vary systematically with the origin of air and the amount of rainfall along the trajectory. A seasonal cycle for pH was found with a monthly median pH below 5.0 during October–December. The highest monthly median concentration of Ca²⁺ was found in May with 20 μmol l⁻¹ and for SO₄²⁻ in January with 52 μmol l⁻¹. Samples with trajectories within 400 km from Bhubaneswar during the last 5 days were found to have a median pH slightly below 5.0 as an average. These samples also had the highest concentration for all measured ions, indicating large pollution sources within the region. Samples with continental origin showed a decrease of ∼70% in concentration if there had been rain during >50% of the last 5 days compared to rain during <50% of the last 5 days. High concentrations of Na⁺ and Cl⁻ were also found in continental samples. Resuspension of previously deposited sea salt is believed to be the reason. The data were compared with data from three other sites in western India and higher concentrations of almost all ions (NH₄⁺ being the exception) compared to Bhubaneswar were found at the west coast in monsoon samples.     

Sphagnum mosses as archives of recent and past atmospheric lead deposition in Switzerland

Sphagnum mosses received from a herbarium and collected recently from a peat bog surface, were used to assess the isotopic character of past and recent atmospheric Pb deposition in Switzerland and to constrain possible Pb sources. Lead removed from the moss surface was isotopically similar to that measured in the corresponding solid plant, suggesting that neither preservative actions for the herbarium samples nor dust had affected the isotopic composition of the samples. The addition of HCl to aqueous extracts to remove surface particles from the plants released more Pb compared to H₂O alone. The changes in isotope ratios between Sphagnum collected during the past c. 130 yr were significantly greater than the small fluctuations between and among species collected at any one time. Three isotope ratio plots and emission inventories indicated that the most likely source of atmospheric Pb was coal-burning at the turn of the century, fly ash from waste incineration until approximately 1950, and gasoline combustion after that. The pollution record derived from the Sphagnum plants is in good agreement with other archives from Switzerland (peat, sediment, ice) and with other herbarium records in Europe.     

Intra- and inter-annual variability of VOC emissions from natural and semi-natural vegetation in Europe and neighbouring countries

Biogenic VOC emission estimates from the earth's surface are crucial input parameters in air quality models. Knowledge accumulated in the last years about BVOC source distributions and chemical compound species emission profiles in Europe as well as the demand of air quality modellers for a finer resolution in space and time of BVOC estimates have led to the set-up of new emission modelling systems. An updated fast BVOC emission modelling platform explicitly considering the seasonality of emission potentials and leaf temperature gradients in forest canopies by the semi-empirical emission module (seBVOC) will be proposed and used for estimating hourly values of chemical compound-specific emissions in Europe (33–68° north; 10° west to 40° east) in the years 1997, 2000, 2001, and 2003. Spatial resolution will be 10 km by 10 km. The database used contains latest land and forest distributions, updated foliar biomass densities, leaf area indices (LAI), and plant as well as chemical compound-specific emission potentials, if available. Meteorological input parameters for the respective years will be generated using the non-hydrostatic meteorological model MM5. Highest BVOC emissions occur in daytime hours around noon from the end of May to mid-August in the Mediterranean area and from the mid of June to the end of July in the boreal forests. Comparison of 3 BVOC model approaches will reveal that for July 2003, the European isoprene and monoterpene totals range from 1124 Gg to 1446 Gg and from 338 Gg to 1112 Gg, respectively. Small-scale deviations may be as high as ±0.6 Mg km^?2 for July 2003, reflecting the current uncertainty range for BVOC estimates. Key sources of errors in inventories are still insufficiently detailed land use data for some areas and lacking chemically speciated plant-specific emission potentials in particular in boreal, south-eastern, and northern African landscapes. The hourly emissions of isoprene, speciated terpenes, and oxyVOC have been made available by the NatAir database.     

Modelling atmospheric mercury transport and deposition across Europe and the UK

There are inadequate measurements of surface ambient concentrations of mercury species and their deposition rates for the UK deposition budget to be characterized. In order to estimate the overall mercury flux budget for the UK, a simple long-term 1D Lagrangian trajectory model was constructed that treats emissions (1998), atmospheric transformation and deposition across Europe. The model was used to simulate surface concentrations of mercury and deposition across Europe at a resolution of 50 km×50 km and across the UK at 20 km×20 km. The model appeared to perform adequately when compared with the few available measurements, reproducing mean concentrations of elemental gaseous mercury at particular locations and the magnitude of regional gradients. The model showed that 68% of the UK's mercury emissions are exported and 32% deposited within the UK. Of deposition to the UK, 25% originates from the Northern Hemisphere/global background, 41% from UK sources and 33% from other European countries. The total mercury deposition to the UK is in good agreement with other modelling, 9.9 tonne yr⁻¹ cf. 9.0 tonne yr⁻¹, for 1998. However, the attribution differs greatly from the results of other coarser-scale modelling, which allocates 55% of the deposition to the UK from UK sources, 4% from other European countries and 60% from the global background atmosphere. The model was found to be sensitive to the speciation of emissions and the dry deposition velocity of elemental gaseous mercury. The uncertainties and deficiencies are discussed in terms of model parameterization and input data, and measurement data with which models can be validated. There is an urgent requirement for measurements of removal terms, concentrations, and deposition with which models can be parameterized and validated.