Atmospheric heavy metal deposition plumes adjacent to a primary lead-zinc smelter.

A method for the determination of atmospheric heavy metal deposition rates has been developed using 0.5-m2 deposition trays at 0.1 m from the ground. Trays were spaced at 150-m intervals along a 1500-m line 500 m east of a Pb-Zn smelter. Ten sampling events of 1-3-h duration were conducted under westerly wind conditions so as to determine the sources of heavy metals deposited near the smelter. Deposited materials were sampled from the trays using wipes. There was good agreement between deposition trays placed side-by-side and exposed in pairs. Under certain conditions, however, the method is not appropriate owing to the potential for local contamination. Geometric mean deposition rates for Pb, Zn, Fe, Cu, As and Cd averaged over a nominal plume width of 600 m amounted to 18.8, 22.2, 12.2, 0.614, 0.403 and 0.052 mg m-2 day-1, respectively. Gaussian deposition profiles were seen for Pb, Zn, Fe, Cu, As and Cd downwind from the blast furnace, sinter plant, and refinery area. Zinc deposition could also be attributed to a northern Zn production area. This northern site was not generally associated with elevated Pb deposition. On the basis of this work, the deposition of heavy metals in residential areas adjoining the smelter is likely to occur downwind from the smelter site, with deposition rates increasing with wind speed. The strategic measurement of heavy metal dry-deposition rates over short periods of time using large collection surfaces provides source-specific information not obtainable by conventional long-term 'passive' deposition sampling. Lower detection limits than those achieved here are likely to be achieved in non-smelter settings. Previous suggestions implicating a sink of city surface dusts as the probable source of Pb recontamination of residential settings in the absence of ongoing smelter emissions are not supported by this work.     

Atmospheric heavy metal deposition in Finland during 1985-2000 using mosses as bioindicators

Heavy metal deposition and changes in the deposition patterns were investigated on the basis of surveys carried out in 1985, 1990, 1995 and 2000. The concentrations of 10 elements (Cd, Cr, Cu, Fe, Ni, Pb, Zn and V; and As and Hg since 1995) were determined on moss (Hylocomium splendens, Pleurozium schreberi) samples collected from the same permanent sample plots in each survey. The heavy metal concentrations, apart from those in southernmost Finland and close to a number of major emission sources, were relatively low. The mean concentrations of all the heavy metals decreased during the period covered by the surveys. The metals that showed the strongest decrease in concentration since 1985 were Pb (78%), V (70%) and Cd (67%). The concentrations of the other heavy metals decreased by 16-34%. The concentrations of Cr, Cu and Ni were clearly associated with local emission point sources and changes in emission levels. The concentrations of As and Hg, which were measured for the first time during the 1995 survey, decreased on the average by 26% and 10%, respectively.     

Atmospheric metal deposition in a moss data correlation study with mortality and disease in the Netherlands

The present paper addresses the correlations between moss metal concentrations and epidemiological data on health and mortality rates in The Netherlands. Attention was given to both total and fractionated metal concentrations in the moss tissues, the latter by factor-analytical (mathematical) approaches, and to both grouped and specific diseases. Better than 95% probability correlations were found both for total moss elements and mortality due to specific diseases and for fractionated moss elements and mortality rates summed for grouped diseases. Overall, the presented data suggest that correlation studies between biomonitoring data on metal air pollution and (epidemiological) health data may prove valuable in turning attention to specific metal-health issues and in directing further study into possible dose-response mechanisms in air-associated metal epidemiology.     

Atmospheric mercury deposition in Guizhou, China

The atmospheric deposition of mercury including total gas phase mercury (TGM), gas phase divalent mercury (Hg2+), and gas phase monomethyl mercury (MMHg) was investigated. Samples were collected from central cities and nature reserve areas across the province. Techniques and equipment including moss bags, KCl-coated denuder and GARDIS-1A portable mercury vapor analyzer were employed for sample collection and analysis. The reliability of techniques and analytical methods used for the project was evaluated. The deposition of atmospheric mercury was reported in species in this important mercury polluted province for the first time. The spatial and temporal variability of mercury emissions were investigated and reported. Contribution of coal mercury emissions to the atmosphere mercury deposition of the province was also investigated.     

Atmospheric deposition of iron from mining activities in northern Ontario

Samples of Sphagnum moss were collected at varying distances from two iron-mining and processing centres in northern Ontario, Canada--Atikokan and Sudbury--and analyzed for Fe. All samples were collected in ombrotrophic bogs which receive chemical inputs strictly from atmospheric deposition. Mosses from the Atikokan sites exhibited elevated concentrations of Fe up to 7352 mg kg-1 near the local sources, and declined exponentially with distance to lows of 1443 mg kg-1. Atikokan, a mining and ore-processing centre, caused elevated Fe levels up to 50 km distance from the town, while Sudbury exhibited a greater influence due to the tall stack there. At Sudbury, levels ranged from 2478 mg kg-1 near the town down to 382 mg kg-1 in remote sites. Results from these moss analyses were similar to those obtained from precipitation sampling of previous authors.     

Trends in the deposition of sulphate and total solids in London

The earliest measurements of sulphate deposit in London were made in 1870, although they can be used to construct a contour map indicating elongation along the direction of the prevailing wind and rather higher values in the lee of the city they cannot be used to establish a deposition rate. However, an initially fragmentary record for the east part of the city of London begins in the 1880's and a gradual decrease of sulphate deposit is evident for much of the period. The record of the deposit of solid matter begins in 1914 and shows a decline throughout the measurements. The period of decline precedes air pollution control legislation and is attributed to social and geographic changes.     

Atmospheric nitrogen in the Mississippi River Basin--emissions, deposition and transport

Atmospheric deposition of nitrogen has been cited as a major factor in the nitrogen saturation of forests in the north-eastern United States and as a contributor to the eutrophication of coastal waters, including the Gulf of Mexico near the mouth of the Mississippi River. Sources of nitrogen emissions and the resulting spatial patterns of nitrogen deposition within the Mississippi River Basin, however, have not been fully documented. An assessment of atmospheric nitrogen in the Mississippi River Basin was therefore conducted in 1998-1999 to: (1) evaluate the forms in which nitrogen is deposited from the atmosphere; (2) quantify the spatial distribution of atmospheric nitrogen deposition throughout the basin; and (3) relate locations of emission sources to spatial deposition patterns to evaluate atmospheric transport. Deposition data collected through the NADP/NTN (National Atmospheric Deposition Program/National Trends Network) and CASTNet (Clean Air Status and Trends Network) were used for this analysis. NOx Tier 1 emission data by county was obtained for 1992 from the US Environmental Protection Agency (Emissions Trends Viewer CD, 1985-1995, version 1.0, September 1996) and NH3 emissions data was derived from the 1992 Census of Agriculture (US Department of Commerce. Census of Agriculture, US Summary and County Level Data, US Department of Commerce, Bureau of the Census. Geographic Area series, 1995:1b) or the National Agricultural Statistics Service (US Department of Agriculture. National Agricultural Statistics Service Historical Data. Accessed 7/98 at URL, 1998. http://www.usda.gov/nass/pubs/hisdata++ +.htm). The highest rates of wet deposition of NO3- were in the north-eastern part of the basin, downwind of electric utility plants and urban areas, whereas the highest rates of wet deposition of NH4+ were in Iowa, near the center of intensive agricultural activities in the Midwest. The lowest rates of atmospheric nitrogen deposition were on the western (windward) side of the basin, which suggests that most of the nitrogen deposited within the basin is derived from internal sources. Atmospheric transport eastward across the basin boundary is greater for NO3- than NH4+, but a significant amount of NH4+ is likely to be transported out of the basin through the formation of (NH4)2SO4 and NH4NO3 particles--a process that greatly increases the atmospheric residence time of NH4+. This process is also a likely factor in the atmospheric transport of nitrogen from the Midwest to upland forest regions in the North-East, such as the western Adirondack region of New York, where NH4+ constitutes 38% of the total wet deposition of N.     

Atmospheric deposition of nitrogen at five subtropical forested sites in South China

Elevated concentrations of reactive nitrogen (N) in precipitation have been reported for many cities in China. Due to increased use of fossil fuels and expansion in agriculture, further increases in deposition of ammonia (NHx) and reactive N oxides (NOy) are predicted. Increased deposition of reactive N is likely to affect N dynamics and N runoff in forest ecosystems. Yet, in China little work has been done to quantify the levels of atmospheric N deposition in such systems. Here, we assess the deposition of inorganic N (ammonium, NH4+ and nitrate, NO3-) for five subtropical forest ecosystems in remote and urban areas of South China. Annual volume-weighted concentrations in bulk precipitation range from 0.18 to 1.55 mg NH4+ -N L(-1) and from 0.12 to 0.74 mg NO3- -N L(-1). These values are large and several times greater than those reported for remote sites of the world. The fluxes of total inorganic N (TIN) in wet-only deposition range from 0.8 to 2.3 g N m(-2) yr(-1), with NH4+ -N contributing 54% to 77%. Both the tree canopy and the ground vegetation layer are important in determining the net N flux reaching the forest floor, but the net effect varies from site to site. At TieShanPing (TSP), close to Chongqing city, and at CaiJiaTang (CJT), near Shaoshan (Hunan province), the canopy represents a net source of N, probably due to dry deposition. At the other three sites (LiuChongGuan (LCG), LeiGongShan (LGS), both in Guizhou province, and LiuXiHe (LXH) in Guangdong), a net loss of reactive N from precipitation water occurs in the canopy, probably due to uptake processes. The total annual atmospheric TIN load is estimated to range from at least 0.8 g N m(-2) yr(-1) to 4.0 g N m(-2) yr(-1), with a considerable contribution from dry deposition. Concentrations and fluxes of inorganic N in tree canopy throughfall are greater than those in North America. Also the contribution of NH4+ -N to TIN fluxes in throughfall (40% to 70%) is greater than in North America. Our sites have N deposition levels and NH4+ -N contributions similar to those found in Northwest and central Europe. The TIN loads at TSP and CJT far exceed 2.5 g N m(-2) yr(-1), which is the N deposition load above which NO3- leaching is expected in temperate and boreal forests.     

Biomonitoring of metal deposition in northern Spain by moss analysis

The results of the first survey carried out in northern Spain to determine atmospheric deposition of metals by analysis of terrestrial mosses, are described. Samples of different mosses, mainly Hypnum cupressiforme and Scleropodium purum, were collected from 134 sampling sites, between 1995 and 1996. Levels of Al, As, Cr, Cu, Fe, Hg, Ni, Pb and Zn, were determined by flame atomic absorption or atomic fluorescence spectrophotometry. Regression analysis was used to compare the capacity of the selected moss species to accumulate the elements, and intercalibration of accumulation in these species was carried out where necessary. Distribution maps were prepared to allow the zones most affected by metal deposition to be identified and to relate this to known sources of contamination: electricity power stations and other industries (e.g. Hg and Ni), edaphic contamination (e.g. Al and Cr) and road traffic (Pb). Background levels of metals in each species were also determined for the study area.     

Atmospheric deposition of carbon and nutrients across an arid metropolitan area

Urbanization is increasing rapidly in semi-arid environments and is predicted to alter atmospheric deposition of nutrients and pollutants to cities as well as to ecosystems downwind. We examined patterns of wet and coarse dry deposition chemistry over a five-year period at 7 sites across the Central Arizona-Phoenix (CAP) study area, one of two urban sites within the National Science Foundation's Long-Term Ecological Research (LTER) program. Wet and dry deposition of organic carbon (oC) were significantly elevated in the urban core; in contrast, mean annual wet and dry fluxes of nitrogen (N) were low (<6 kg ha(-1) yr(-1)) compared to previous estimates and did not differ significantly among sites. Wet deposition of sulfate (SO(4)2-) was high across CAP (mean 1.39 kg ha(-1) yr(-1) as S) and represented the dominant anion in rainfall. Dry deposition rates did not show strong seasonal trends with the exception of oC, which was 3-fold higher in winter than in summer; ammonium (NH4+) deposition was high but more variable. Dry deposition of NO3- and oC was strongly correlated with particulate base cations and dust-derived soluble reactive phosphorus (SRP), suggesting that urban-derived dust is scrubbing the atmosphere of acidic gases and entrained particles and increasing local deposition. Differences between measured and predicted rates of dry N deposition to the urban core may be explained by incomplete collection of gas phase N on surrogate deposition surfaces in this hot and arid environment. The extent of urban enhancement of cations and oC inputs to desert ecosystems appears to be restricted to the urbanized metropolitan area rather than extending far downwind, although a low number of sites make it difficult to resolve this spatial pattern. Nevertheless, wet and dry inputs may be important for biogeochemical cycles in nutrient and carbon-poor desert ecosystems within and near arid cities.     

Atmospheric deposition of lead in Norway: spatial and temporal variation in isotopic composition

Moss samples collected from 22 sites all over Norway at five different times during 1977-2000 were analysed for stable lead isotope ratios. These data together with total lead concentrations and relevant literature lead isotope data from UK, western/central Europe and eastern Europe/Russia were used to elucidate major source regions for lead deposited in different parts of the country at different times. The southernmost part of the country was most affected from western/central Europe around 1975, but the deposition declined rapidly and UK became a more significant source region in the 1980s. Recently, the influence is mostly from Eastern Europe. In the west, UK was the dominant source region during the whole period. In the middle and northern regions, the deposition was low but also decreasing regularly, and the main source region was probably the North Atlantic. In the far north-east, influence from Russia and eastern Europe was dominant during the whole period.     

Atmospheric deposition of persistent organic pollutants to the East Rongbuk Glacier in the Himalayas

To assess levels and seasonal trends of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in a high-altitude mountain region, a 2.1 m snowpack sample was collected from the East Rongbuk Glacier at 6572 ma.s.l. on Mt. Everest in September 2005. This snowpack covered a full year period from the fall of 2004 to the summer of 2005 and reflected the major meteorology of the monsoon and non-monsoon seasons. The most abundant compounds detected in the snow samples were γ-hexachlorocyclohexane (γ-HCH) and α-HCH with mean concentrations of 123 pg L^− 1 and 92 pg L^− 1, respectively. This is the first detection of these compounds in recent snow samples from the Himalayas. Backward air trajectory analysis indicated that the Himalayas could be influenced by the major HCH source regions in both India and China. Among the seven marker PCB congeners (PCB 28, 52, 101, 118, 138, 153, and 180) quantified, PCB 28 and PCB 52 were the only dominant PCB congeners detected, with mean concentrations of 17 pg L^− 1 and 6 pg L^− 1, respectively. In addition, DDT metabolites, p,p′-DDE and p,p′-DDD were detected in some snow samples and mean concentrations of DDTs were 24 pg L^− 1. Seasonal differences were observed for α- and γ-HCH concentrations increasing from the non-monsoon season to the monsoon season. Meanwhile, PCB 28 and HCB showed uniform variations with peak concentrations resulting from an effective scavenging by snowfalls between the monsoon and non-monsoon interval. Compared to other high mountain areas, the levels of POPs deposited into the East Rongbuk Glacier were relatively low, resulting from the highest altitude and remoteness from source regions.     

Trace metal determination in total atmospheric deposition in rural and urban areas

The wet, dry and total atmospheric depositions of some metals (Al, Cd, Cr, Cu, Fe, Na, Pb and Zn) were sampled at two sites and atmospheric fallout fluxes were determined for these locations. This work, led by two different research groups, allowed to reach two main goals: to define a simple analytical procedure to secure accurate shipboard sampling and analysis of atmospheric deposition, and to assess anthropogenic impacts of heavy metals to the environment. The first step about the validation step showed that the prevalent deposition type was dry deposition which represents 40, 60 and 80% for Cd, Cu and Pb, respectively. This prevalence of dry deposition in total atmospheric fallout supported the necessity of funnel wall rinsing which contains 30, 50 and 40% of collected Cd, Cu and Pb, respectively. Moreover, the reproducibility of atmospheric deposition collection was determined. The second step was performed by comparing two sampling sites. A rural sampling site, situated in Morvan's regional park (250 km south-east of Paris), was chosen for its isolation from any local and regional contamination sources. Fluxes obtained in this area were compared with those obtained at an urban site (Créteil, suburb of Paris) allowing comparison between urban and rural areas and demonstrating the impact of anthropogenic activities on atmospheric deposition of Cr, Cu and Pb.     

Atmospheric particulate mercury concentration and its dry deposition flux in Changchun City, China.

From July 1999 to January 2000, we determined the particulate mercury [Hg(p)] concentration in the atmosphere of five function sites and one contrast site in the city of Changchun, China. During non-heating season, the Hg(p) concentration in air in urban areas ranged from 0.022 to 0.398 ng m(-3) with an average of 0.145 ng m(-3), and at the contrast site with an average of 0.084 ng m(-3). During the heating season, the Hg(p) concentration in urban areas was in the range of 0.148-1.984 ng m(-3) with an average of 0.461 ng m(-3) and with an average of 0.211 ng m(-3) at the contrast site. The Hg(p) concentration during heating season is two times higher than that during non-heating time. Coal burning and wind-blown soil material are the two important sources of Hg(p). Wind-blown soil material contributes 7.9-38.5% to the Hg(p) with an average of 24.1% in urban area. A theoretical model was used to estimate the dry deposition flux, with results of 43.06 microg m(-2) a(-1) in the urban area and 21.28 microg m(-2) a(-1) at the contrast site.     

Atmospheric deposition of polycyclic aromatic hydrocarbons (PAHs) in mosses (Hypnum cupressiforme) in Hungary

The atmospheric deposition of polycyclic aromatic hydrocarbons (PAHs) was investigated in Hungary by analyzing a moss (Hypnum cupressiforme) species as a bioindicator. In the autumn of 1997, samples were collected at 29 sites distributed across Hungary. The concentrations of total PAH at these sites were in the range of 0.1567-10.45 x 10(4) microg kg(-1) with a mean value of 1.87 x 10(4) microg kg(-1). More than 99% of the total PAHs atmospheric deposition were low molecular weight PAHs (up to 3 ring compounds). The total PAH values showed no correlation with metal concentrations. However, most of the sites in this region showed a positive linear relationship between PAHs levels and traffic volume (r2 = 0.83; P < 0.001) while no relationship existed between PAH levels and population (r2 = 0.01; P > 0.1). Atmospheric deposition of PAHs at different regions in Hungary may be due to incomplete combustion of fuel. The total concentrations of PAHs were compared to the PAH levels in vegetation samples collected from different regions around the world. The highest PAHs concentrations accumulated were found in Hypnum cupressiforme than other vegetation species. A greater affinity for PAH compounds by Hypnum cupressiforme than other moss species probably caused larger amounts of accumulation. A relationship between accumulations of PAH compounds in Hypnum cupressiforme and octanol-air partition coefficients was obtained and is briefly discussed.     

Atmospheric deposition of arsenic and selenium across Canada using Sphagnum moss as a biomonitor

A biomonitoring study was made of the atmospheric deposition of arsenic and selenium across northern Canada utilizing Sphagnum fuscum moss. Intensive sampling was carried out adjacent to the smelter at Rouyn-Noranda, Quebec. An average background concentration of arsenic in the moss of 0.66 mg kg-1 was determined, while most selenium concentrations were below the detection limit of 0.2 mg kg-1. Elevated arsenic concentrations were found in the vicinity of the mining and smelting areas of Flin Flon, Manitoba, and Atikokan, Ontario. High concentrations of selenium were detected only near Rouyn-Noranda. Both arsenic and selenium occurred in moss at concentrations lower than found in Canadian soils.     

First national survey of atmospheric heavy metal deposition in Hungary by the analysis of mosses

The atmospheric deposition of Cd, Cr, Cu, Fe, Ni, Pb, V and Zn in Hungary was investigated by using moss species as bioindicators. Our research was part of an international mapping project (Atmospheric Heavy Metal Deposition in Europe) [NORD 21 (1987) 1-44; NORD 9 (1994)] carried out in the most European countries in the 1990s to determine and to compare atmospheric heavy metal background pollution by standardized methods. Sampling was performed at 116 sites distributed over Hungary in the autumn of 1997. Moss species of Hypnum cupressiforme (72.4%) were preferred. But where it could not be collected, other species were taken. Unwashed, dried samples were digested with H(2)O(2)/HNO(3), and the concentrations of heavy metals were determined by ICP-AES. The results reflect local emission points. Background mean levels of Cd, Fe and Ni were mildly elevated in comparison to European means [NORD 9 (1994)]. Probably, that was due not only to pollution, but to the use of Hypnum cupressiforme, which can accumulate higher concentrations of heavy metals compared to other species. The results are presented on colored contour maps obtained with the SURFER program (Golden Software Inc. Co).     

Atmospheric metal and phosphorus concentrations, inputs, and their biogeochemical significances in the Japan/East Sea

Atmospheric metals and phosphorus over the southern Japan/East Sea were investigated in order to evaluate their sources, concentrations and inputs, and to identify their biogeochemical roles in this marginal sea. Aerosols were collected on the east coast of Korea from February 2002 to April 2003 (n = 101) as well as at a remote island (Ulleung) and on a ship from February 2002 to June 2003 (n = 13). The aerosols were analyzed for Al, Co, Cu, Ni, P, Pb and Zn. Simultaneous collections of aerosols at both coast and offshore were performed, and several high dust aerosols (Al > 5 μg m^− 3) were collected at both regions. At the coastal site, both dust mineral and pollutants were transported by westerly winds from the Asian continent, but local emissions were significant (e.g., Cu, Ni, P and Zn) as well during the summer monsoon (May-August). The experimental relationships between the coast and offshore sites were defined. From these relationships, it was possible to obtain the annually averaged atmospheric metal and P concentrations over the southern Japan/East Sea, which has increased by over 2 times for the last decade. Through the estimation of atmospheric metal and phosphorus fluxes and comparisons with inputs from the Tsushima Warm Current, the atmospheric pathway was found to be a significant source for Al, Pb and Zn.     

An extended study of heavy metal deposition in Galicia (NW Spain) based on moss analysis

This paper describes the first attempt to determine the levels of heavy metal contamination in Galicia (NW Spain) by analysis of moss species. Samples of Scleropodium purum and Hypnum cupressiforme were collected from 75 sites, in 1995 and 1997, and analysed by atomic absorption spectrophotometry and atomic fluorescence for Al, As, Co, Cr, Cu, Fe, Hg, Ni, Pb and Zn. Comparisons were made between the two moss species used and, for those elements present at different concentrations in the two species, regression lines were made for interspecies calibration. Distribution maps were drawn up for each of the elements according to their concentration in the moss. In certain areas it was possible to relate deposition to the existence of known sources of contamination. The study demonstrates that the highest levels of elements were found in the most heavily industrialised and populated areas. Concentrations of As, Cu, Hg and Ni, recorded during the 1997 sampling were significantly higher than those found in 1995, possibly due to agricultural and industrial activities.