Identifying the origins of local atmospheric deposition in the steel industry basin of Luxembourg using the chemical and isotopic composition of the lichen Xanthoria parietina

Trace metal atmospheric contamination was assessed in one of the oldest European industrial sites of steel production situated in the southern part of the Grand-Duchy of Luxembourg. Using elemental ratios as well as Pb, Sr, and Nd isotopic compositions as tracers, we found preliminary results concerning the trace metal enrichment and the chemical/isotopic signatures of the most important emission sources using the lichen Xanthoria parietina sampled at 15 sites along a SW-NE transect. The concentrations of these elements decreased with increasing distance from the historical and actual steel-work areas. The combination of the different tracers (major elements, Rare Earth Element ratios, Pb, Sr and Nd isotopes) enabled us to distinguish between three principal sources: the historical steel production (old tailings corresponding to blast-furnace residues), the present steel production (industrial sites with arc electric furnace units) and the regional background (baseline) components. Other anthropogenic sources including a waste incinerator and major roads had only weak impacts on lichen chemistry and isotopic ratios. The correlation between the Sr and Nd isotope ratios indicated that the Sr-Nd isotope systems represented useful tools to trace atmospheric emissions of factories using scrap metal for steel production.     

Investigating the sources of the labile fraction in sediments from silicate-drained rocks using trace elements,and strontium and lead isotopes

Elemental concentrations of the trace elements Rb, Sr, Th, Pb, Zn, Cu, Ni, Cd and Sb, as well as Sr and Pb isotopic compositions, were determined on the labile fraction (called acid-extracted matter AEM, Négrel et al., Chem. Geol. 166 (2000) 271-85) of soil and sediment along two small rivers located in the centre of France, one flowing from basalt, the other one on granite-gneiss. Oxide-mineral form in AEM (i.e. Fe-Mn oxides), acts as the main carrier phase. Analysis of the relationships between the trace elements, and lead and strontium isotopes allows the origin of the elements (i.e. natural and anthropogenic) and their history, both in the sediment and soil from the small watersheds to be assessed. Lead-isotope compositions in AEM display large fluctuation in the two watersheds and show a large scatter between natural input (basalt and granite), atmospheric input from gasoline, and input from past mining activities. On the basaltic watershed, Pb and other trace elements like Sb deriving from past mining waste are mainly related to atmospheric origin, while on the granitic terrain Pb originates from mineralization. The Sr-isotope compositions of AEM, water and residues are similar in the watershed draining basalt. On the watershed draining granite, AEM and streamwater shows 87Sr/86Sr ratios similar in the upstream part of the watershed and a divergence between the two ratios appears in the downstream part of the watershed implying that oxides have precipitated upstream and are not re-equilibrated during their transport downstream.     

Tree rings as Pb pollution archives? A comparison of 206Pb/207Pb isotope ratios in pine and other environmental media

Tree rings, if validated as an environmental archive for pollution, would provide a convenient, geographically widespread archive for studying the temporal and spatial distribution of atmospheric pollutants. We collected tree-ring records from Scots pine (Pinus sylvestris L.), ranging in age from 100 to 300 years and from one spruce (Picea abies), from sites in southern and northern Sweden and analyzed their stable lead isotopic composition (206Pb/207Pb). These results are compared to the Pb isotopic composition in soil profiles from each of the sites and temporal changes in the 206Pb/207Pb ratio in peat and lake sediment deposits in Sweden. The mineral soils at each site are characterized by high 206Pb/207Pb ratios (> 1.35), while the ratios in the mor layer are low (1.14-1.16) and characterized by atmospheric lead pollution. The 206Pb/207Pb ratios of the tree rings, typically approximately 1.18-1.20, indicate a significant (10-30%) contribution of Pb derived from the underlying mineral soil. While peat and lake sediment records show that the 206Pb/207Pb ratio of atmospheric deposition has varied over time, with a pronounced trough between approximately 1930 and 1990, the tree rings show no similar trend. Further comparison of published Pb isotope data from other tree-ring records with time series from peat bogs and herbarium samples also shows poor agreement, and indicates that tree rings always contain a mixture of pollution Pb and Pb from the underlying mineral soil. The majority of Pb in the wood is derived from atmospheric pollution either directly, through aerial interception, or indirectly, through uptake from the large pool of accumulated pollution Pb in the soil. Since the Pb isotope ratios of the wood indicate that some natural Pb is taken up into the tree, then it must also be concluded that some fraction of the pollution Pb in the wood is likewise taken up from the forest soil. Based on the Pb isotope analyses, we can only conclude that dendrochemical records are not useful in temporal studies of metal pollution.     

The isotopic composition of lead in man and the environment in Finland 1966-1987: isotope ratios of lead as indicators of pollutant source.

The isotopic composition of lead was determined in samples collected between 1966 and 1987, mainly from the Helsinki area, in emission sources (gasoline, incinerator and lead smelter emissions, coal), air, in samples representing long-term deposition (lichen, soil, lake sediments), and in human tissue. Isotope ratios were determined by thermal ionization mass spectrometry after chemical separation of lead by anion exchange and cathodic electrodeposition. The origin of lead in man and the environment in the Helsinki area was evaluated by using the differences in the measured isotope ratios as an indicator. The mean of the ratio in gasoline (206Pb/207Pb 1.124 +/- 0.026) and the ratios in other emission sources in Helsinki (1.149-1.226) were significantly different. However, the wide range of isotope ratios in gasoline (1.063-1.173) reduced the accuracy when assessing the contribution of the different sources. Lead in air samples from Helsinki (1.123 +/- 0.013) could be attributed to gasoline, as could lead in soil near a highway (1.136 +/- 0.003). By contrast, isotope ratios measured in lichen (1.148 +/- 0.006) indicated considerable amounts of lead from sources with higher 206Pb abundances, evidently industrial sources. The isotope ratios in human liver, lung, and bone from individuals dying between 1976-79 (206Pb/207Pb ratio 1.142 +/- 0.015, 1.151 +/- 0.011, and 1.156 +/- 0.013, respectively) reflect the large lead emissions from the incinerators and lead smelters in the Helsinki area in the 1960s and 1970s. In lake sediment cores a correlation was found between the isotope ratios, lead concentration, and depth. The nonanthropogenic lead of high isotope ratios from bedrock was the major component at depths dated older than 100 years. At the surface of the sediment atmospheric lead prevailed, with ratios similar to those of gasoline, air samples and lichen. In the post-1900 layers, anthropogenic lead made up about 40-95% of the total sedimentary lead.     

Metal contamination in urban, suburban, and country park soils of Hong Kong: a study based on GIS and multivariate statistics

The urban environment quality is of vital importance as the majority of people now live in cities. Due to the continuous urbanisation and industrialisation in many parts of the world, metals are continuously emitted into the terrestrial environment and pose a great threat on human health. An extensive survey was conducted in the highly urbanised and commercialised Hong Kong Island area (80.3 km2) of Hong Kong using a systematic sampling strategy of five soil samples per km2 in urban areas and two samples per km2 in the suburban and country park sites (0-15 cm). The analytical results indicated that the surface soils in urban and suburban areas are enriched with metals, such as Cu, Pb, and Zn. The Pb concentration in the urban soils was found to exceed the Dutch target value. The statistical analyses using principal component analysis (PCA) and cluster analysis (CA) showed distinctly different associations among trace metals and the major elements (Al, Ca, Fe, Mg, Mn) in the urban, suburban, and country park soils. Soil pollution maps of trace metals (Cd, Co, Cr, Cu, Ni, Pb, and Zn) in the surface soils were produced based on geographical information system (GIS) technology. The hot-spot areas of metal contamination were mainly concentrated in the northern and western parts of Hong Kong Island, and closely related to high traffic conditions. The Pb isotopic composition of the urban, suburban, and country park soils showed that vehicular emissions were the major anthropogenic sources for Pb. The 206Pb/207Pb and 208Pb/207Pb ratios in soils decreased as Pb concentrations increased in a polynomial line (degree=2).     

Pb contamination and isotopic composition of urban soils in Hong Kong

In the urban environment, intense human activities can lead to degradation of environmental quality and have potential long-term effects on human health. In the present study, Pb contamination of urban soil cores in Hong Kong was investigated using a combination of the 'total' concentration, chemical partitioning and isotopic composition of Pb in the soils. The analytical results showed that urban soil cores in close vicinity to high traffic volumes (> 40000 vehicles per day) were usually contaminated with Pb, suggesting atmospheric deposition of Pb as a consequence of vehicular emissions arising from the combustion of leaded gasoline in the past. Increasing Pb concentrations were generally associated with decreasing 206Pb/207Pb ratios of the contaminated soil cores, offering strong evidence of accumulation of Pb derived from anthropogenic sources. In selected contaminated soil cores, the 206Pb/207Pb ratios tended to increase in the order: carbonate < exchangeable < Fe-Mn oxide < organic < residual fractions. The distribution of the 206Pb/207Pb ratios in the five operationally defined chemical fractions showed that the 206Pb/207Pb ratios generally increased with increasing stability, demonstrating preferential association of anthropogenic Pb with the carbonate, exchangeable, Fe-Mn oxide and organic fractions in the soils.     

A chemical and mineralogical reconstruction of Zn-smelter emissions in the Kempen region (Belgium), based on organic pool sediment cores

The atmospheric pollution history of a former Belgian Zn-smelter complex is preserved in organic sediments of a nearby peat bog pool. The stratigraphy of trace metals, Pb-isotope ratios and mineralogy indicate extreme heavy metal pollution in recent sediments. In the pollutant trend, extremes coincide with maxima in 20th century metal production, minima during major war conflicts and the final shutdown of the smelter. Peak pollution concentrations measure up to 4.7 wt.% Zn, 1.1 wt.% Pb and 0.1 wt.% Cd, which correspond to calculated atmospheric deposition rates of 9.0, 1.6 and 0.16 g m(-2) yr(-1), respectively. 206Pb/207Pb isotope ratios show higher values in the polluted interval (1.135-1.162) relative to local geogenic values deeper down-core (1.194-1.215). Within the polluted interval, three significantly different 208Pb/206Pb plateaus are recognized and suggested to indicate changes in the origins of processed ores. Microprobe analyses on sediment thin sections show extensive in situ FeS2 and ZnS precipitation, which suggests that anoxic processes are responsible for the immobilization of the atmospheric metal inputs. The occurrence of oxidized smelter dusts in an independent surface soil sample indicates a rapid diagenetic transformation of metal oxides into sulfides. Morphology and chemical characteristics allow the distinction between smelter related and diagenetic mineral deposits, and give evidence for dust from open-air ore repositories, as well as smelter operation without dust filters.     

A Pb isotope and trace element study of rainwater from the Massif Central (France)

Lead isotope ratios and Zn, Pb, Cu, Cd, Sb and Rb contents were measured in samples of rainwater collected over a period of 15 months from the Massif Central (France). Each sample, collected automatically at monthly intervals, represents a series of rainfall events. Rainwater chemistry was interpreted in terms of the chemical contributions from wet deposition and from different source regions for dust in the centre of France. Trace element concentrations in rainwater samples showed a wide range, particularly for Pb (1.30-465 microg/l), with variations decreasing for Cd (0.07-1.70 microg/l), Zn (1.00-54.00 microg/l), Cu (0.20-25.00 microg/l), Sb (approximately 0-0.33 microg/l) and Ni (approximately 0-15.00 microg/l). Trace element contents do not correlate with rainfall amount and no inter-element correlations are evident in the data. Lead is the most common trace metal found in the rainwater (mean value = 996 microg/m2/y) while Sb is the least common element measured (mean value = 1.12 microg/m2/y). The composition of rainwater collected from the Massif Central shows a range in Pb isotope ratios from 17.935 to 19.22 (206Pb/204Pb), 15.578 to 15.73 (207Pb/204Pb) and 37.559 to 38.606 (208Pb/204Pb). A five-component mixing model involving contributions from the natural background, gasoline inputs from industrial and agricultural activity and a source resulting from mining waste may be used to explain both the Pb isotope signature and the fluctuations in trace metal contents of Massif Central rainwater.     

Comparative study of the temporal evolution of atmospheric lead deposition in Scotland and eastern Canada using blanket peat bogs

The temporal evolution of atmospheric lead deposition and its possible sources were assessed in eastern Canada and in western Scotland, using blanket peat bogs as geochemical archives. Short cores were taken from two remote sites located close to the sea. Significant lead enrichments in the upper layers at both sites reflect the increasing emission of lead into the atmosphere due to anthropogenic activities during the last century. At the Scottish site, a region under aeolian influence from Europe, anthropogenic derived lead could be recognized by the distinctive unradiogenic composition (206Pb/207Pb ratios down to approximately 1.115), being clearly different from the pre-industrial values (206Pb/207Pb approximately 1.166). In contrast, the lead pollution in eastern Canada (influenced by North American sources) is identified by a more radiogenic lead isotope composition (206Pb/207Pb ratios up to approximately 1.199) compared to preindustrial values (206Pb/207Pb approximately 1.161). Emission inventories and isotope characteristics suggest that industrial (coal burning, mining) and traffic (leaded gasoline) outputs are the most likely sources during the first and the second half of the 20th century, respectively, in both, western Scotland and eastern Canada alike. The Scottish record is in line with previous studies of past atmospheric lead deposition. However, the Canadian deposit suggests that the wind derived, pre-industrial lead, is less radiogenic as previously implied using sediment archives. These results are thus the first to report pre-industrial lead isotope ratios and concentrations of atmospheric derived aerosols in North America.     

Seltenerdelement-, Yttrium-Gehalte und Bleiisotope in Thermal- und Mineralwässern des Schwarzwaldes

In the Black Forest, mineral waters from five wells in crystalline basement (granite and gneisses), their probable source rocks and the experimental leachates were evaluated for rare earth elements (REE), yttrium contents, and lead isotope ratios. The distribution of REE and Y, and the Pb-isotope ratios are powerful tools to identify the most likely type of rock that controls cation contents of the mineral water. Granites and gneisses lead to REE patterns with varying negative europium anomalies in waters; i. e., gneisses have a tendency for positive or only slightly negative europium anomalies in fluids, whereas granites exhibit negative anomalies. The comparison of REE and Y in the leachates and waters shows that these elements are characteristically redistributed during water-rock inter-action between rock-forming and accessory minerals, surface layers and adsorption films. REE and Y are leachable in the aquifer rocks, in which light REE are partially impoverished. REE and Y in samples from surface outcrops show enhanced leachable fractions. In alterated rocks, large fractions of ²⁰⁶ Pb are definitely leached from other solid phases than ²⁰⁷ Pb and ²⁰⁸ Pb.     

Assessment of pollution aerosols sources above the Straits of Dover using lead isotope geochemistry.

We assess the capability of lead isotopes to study the transport of pollution aerosols above the Straits of Dover by collecting atmospheric aerosols above the Eastern Channel and the Southern Bight of the North Sea. During the same period, we characterized the lead isotopic signature of the main industrial sources on the French coast near the Straits of Dover. Urban and automobile-derived aerosols were also collected. Due to the phasing out of lead in gasoline, the urban isotopic composition (206Pb/207Pb = 1.158 +/- 0.003) has become more radiogenic, although it is highly variable. On a regional scale, major industrial emissions have a well-defined isotopic composition (1.13 < 206Pb/207Pb < 1.22), more radiogenic than the petrol-lead signature (1.06 < 206Pb/207Pb < 1.12). These results together with those measured near the main coastal highway show that the automobile source has become a minor component of particulate lead in air. On a local scale, Dunkerque, the most urbanized and industrialized area along the Straits of Dover, may transiently control elevated lead concentrations. Except for the occurrence of local and regional range transport episodes, lead concentrations in the Straits of Dover can be related to remote or semi-remote pollution source emissions. Combining air mass retrospective trajectories and related lead abundances and isotopic compositions, it can be shown that lead aerosols originating from eastern Europe have an isotopic signature (1.145 < 206Pb/207Pb < 1.169) different from the isotopic composition of west-European lead aerosols (1.111 < 206Pb/207Pb < 1.142). The influence of remote North American sources is suggested, with caution, due to uncertainties in meteorological calculations.     

Sources and characteristics of lead pollution in the urban environment of Guangzhou

Guangzhou, the capital of the southeastern province of Guangdong, is one of the largest and most rapidly developing industrial cities in China. In recent years its rapid economic development has brought great prosperity to the Pearl River Delta (PRD) region, but has also given rise to a wide variety of environmental problems. The current level of lead (Pb) contamination (75-926 mg/kg) in the surface environment of Guangzhou remains a major concern, even though the use of leaded petrol in the city was banned in 1997. The Pb isotope ratios (206Pb/207Pb(min-max) : 1.1612-1.1961 and 208Pb/207Pb(min-max) : 2.4495-2.4838) of the urban dusts from unconfined (road dusts and gully sediments) and relatively confined (vehicular tunnel) settings in Guangzhou remains in a relatively narrow range, comparable with those of the regional natural and anthropogenic sources. This study highlights the inherent shortcomings of the Pb isotope fingerprinting technique for provenancing Pb sources, as both the target media (urban dusts) and potential sources have similar and highly radiogenic Pb isotope values. This could not only lead to an overestimation of the effectiveness of phasing-out of leaded petrol, but also an underestimation of the ever-increasing relative contributions from other potential sources of pollution, including coal combustion, industrial emissions of local Pb-ores and non-additive Pb contents of crude oils. Re-suspended Pb-bearing particulates deposited from early vehicular exhaust emission of leaded petrol with distinctly low Pb isotope compositions are still an important source of Pb pollution in the region.     

Lead isotopes and lead shot ingestion in the globally threatened marbled teal (Marmaronetta angustirostris) and white-headed duck (Oxyura leucocephala)

Lead isotope ratios ((206)Pb/(207)Pb and (208)Pb/(207)Pb) and concentrations in the livers and bones of marbled teal and white-headed duck found dead or moribund were determined in order to establish the main lead source in these waterfowl species. Lead concentrations in bone (dry weight) and liver (wet weight) were found to be very high in many of the white-headed ducks (bone: geometric mean=88.9 ppm, maximum=419 ppm; liver: geometric mean=16.8 ppm, maximum=57.0 ppm). Some of the marbled teal had high lead levels in the bones but liver lead levels were all low (bone: geometric mean=6.13 ppm, maximum=112 ppm; liver: geometric mean=0.581 ppm, maximum=4.77 ppm). Ingested lead shot were found in 71% of the white-headed duck and 20% of the marbled teal. The (206)Pb/(207)Pb ratio in livers and bones of white-headed ducks and marbled teals showed no significant differences compared to the ratios obtained from lead shot. The (206)Pb/(207)Pb ratio in bones of marbled teal ducklings with the highest lead concentrations tended to resemble the ratios of lead shot, which supports our hypothesis that the lead was derived from the hens. We also found that the lead ratios of lead shot and lead ratios described for soils in the area overlapped, but also that the isotopic ratio (206)Pb/(207)Pb in lead shot used in Spain has a narrow range compared with those used in North America. The principal source of lead in many of these birds was, however, most likely lead shot, as supported by the similar isotopic ratios, high lead concentrations in tissues and evidence of ingested shot.     

Influence of bacteria on lanthanide and actinide transfer from specific soil components (humus, soil minerals and vitrified municipal solid waste incinerator bottom ash) to corn plants: Sr-Nd isotope evidence

Experiments have been performed to test the stability of vitrified municipal solid waste (MSW) incinerator bottom ash under the presence of bacteria (Pseudomonas aeruginosa) and plants (corn). The substratum used for the plant growth was a humus-rich soil mixed with vitrified waste. For the first time, information on the stability of waste glasses in the presence of bacteria and plants is given. Results show that inoculated plant samples contained always about two times higher lanthanide and actinide element concentrations. Bacteria support the element transfer since plants growing in inoculated environment developed a smaller root system but have higher trace element concentrations. Compared with the substratum, plants are light rare earth element (LREE) enriched. The vitrified bottom ash has to some extent been corroded by bacteria and plant activities as indicated by the presence of Nd (REE) and Sr from the vitrified waste in the plants. (87)Sr/(86)Sr and (143)Nd/(144)Nd isotope ratios of plants and soil components allow the identification of the corroded soil components and confirm that bacteria accelerate the assimilation of elements from the vitrified bottom ash. These findings are of importance for landfill disposal scenarios, and similar experiments should be performed in order to better constrain the processes of microbially mediated alteration of the MSW glasses in the biosphere.     

European isotopic signatures for lead in atmospheric aerosols: a source apportionment based upon 206Pb/207Pb ratios

To investigate the capability of the lead isotope signature technique to support a source apportionment study at a Continental scale, atmospheric particulate matter was collected at Cap Gris-Nez (Eastern Channel, northern France), over one year (1995-1996). Four days retrospective trajectories of air masses were available during each sampling experiment. Twenty-eight samples, for which the origin of aerosols was unambiguously determined, were selected for isotopic measurements. Considering the Enrichment Factors, EF(Crust) of lead and its size distribution, we show that lead is mostly from anthropogenic origin and mainly associated with [0.4 < diameter < 0.9 microm] particles. The extent to which various Continental sources influence the lead abundance in aerosols is exhibited by considering both the lead concentration and the origin of air masses. Lead concentration is higher by a factor of approximately seven, when air masses are derived from Continental Europe, by comparison with marine air masses. Taking into account these concentrations and the vertical movements of air masses, we compare the different isotopic compositions using a statistical non-parametric test (Kolmogorov-Smirnov). We produce evidence that, for most of the cases, air masses originating from Continental Europe exhibit a more radiogenic composition (1.134 < 206Pb/207Pb < 1.172) than air masses coming from the United Kingdom (1.106 < 206Pb/207Pb < 1.124). Generally, lead isotopic compositions in aerosols are clearly distinct from the gasoline signatures in European countries, strongly suggesting that automotive lead is no longer the major component of this metal in the air. Gasoline and industrial isotopic signatures could explain the origin of lead in our aerosol samples. A source apportionment based upon 206Pb/207Pb ratios, suggests that the difference between British (206Pb/207Pb = 1.122 +/- 0.038) and Continental (206Pb/207Pb = 1.155 +/- 0.022) signatures may be largely explained by differences in the petrol lead content of aerosols (23-62% in Great Britain vs. 10-36% in Continental Europe).     

Temporal trends of pollution Pb and other metals in east-central Baffin Island inferred from lake sediment geochemistry

Concentrations and stable isotope ratios of lead (Pb) from lake sediments were used to quantify temporal patterns of anthropogenic Pb pollution in the Clyde River region of Baffin Island, Arctic Canada. Surface sediments from eight lakes on eastern Baffin Island and one from northern-most Greenland, spanning a gradient of 20° latitude, showed great variability with respect to Pb concentration and stable isotopic Pb ratios, with little apparent latitudinal trend. To constrain the temporal evolution of regional Pb pollution, a well-dated core from one of the sites, Lake CF8 on east-central Baffin Island, was analyzed geochemically at high stratigraphic resolution. A pronounced decrease in the ²⁰⁶Pb/²⁰⁷Pb ratio occurs in sediments deposited between 1923 and the mid-1970s, likely reflecting alkyl-Pb additives derived from the combustion of fossil fuels at a global scale. A two-component mixing model indicates that 17-26% of the Pb in the labile fraction of sediments deposited in Lake CF8 between 2001 and 2005 is from anthropogenic input. A Pb-Pb co-isotopic plot (²⁰⁶Pb/²⁰⁷Pb vs.²⁰⁸Pb/²⁰⁶Pb ratios) of the Lake CF8 time series data indicates multiple possible sources of industrial Pb pollution. Despite widespread reductions in industrial Pb emissions since the 1970s, there is no evidence for attendant reductions of pollution Pb at Lake CF8. Enhanced scavenging from increased primary production as well as changing precipitation rates as climate warms may represent important factors that modulate Pb deposition to Lake CF8, and Arctic lakes elsewhere.     

The origin of lead in the organic horizon of tundra soils: atmospheric deposition, plant translocation from the mineral soil or soil mineral mixing?

Knowledge of the anthropogenic contribution to lead (Pb) concentrations in surface soils in high latitude ecosystems is central to our understanding of the extent of atmospheric Pb contamination. In this study, we reconstructed fallout of Pb at a remote sub-arctic region by using two ombrotrophic peat cores and assessed the extent to which this airborne Pb is able to explain the isotopic composition (²⁰⁶Pb/²⁰⁷Pb ratio) in the O-horizon of tundra soils. In the peat cores, long-range atmospheric fallout appeared to be the main source of Pb as indicated by temporal trends that followed the known European pollution history, i.e. accelerated fallout at the onset of industrialization and peak fallout around the 1960s-70s. The Pb isotopic composition of the O-horizon of podzolic tundra soil (²⁰⁶Pb/²⁰⁷Pb = 1.170 ± 0.002; mean ± SD) overlapped with that of the peat (²⁰⁶Pb/²⁰⁷Pb = 1.16 ± 0.01) representing a proxy for atmospheric aerosols, but was clearly different from that of the parent soil material (²⁰⁶Pb/²⁰⁷Pb = 1.22-1.30). This finding indicated that long-range fallout of atmospheric Pb is the main driver of Pb accumulation in podzolic tundra soil. In O-horizons of tundra soil weakly affected by cryoturbation (cryosols) however, the input of Pb from the underlying mineral soil increased as indicated by ²⁰⁶Pb/²⁰⁷Pb ratios of up to 1.20, a value closer to that of local soil minerals. Nevertheless, atmospheric Pb appeared to be the dominant source in this soil compartment. We conclude that Pb concentrations in the O-horizon of studied tundra soils - despite being much lower than in boreal soils and representative for one of the least exposed sites to atmospheric Pb contaminants in Europe - are mainly controlled by atmospheric inputs from distant anthropogenic sources.     

Lead fluxes, isotopic and concentration profiles in a peat deposit near a lead smelter (Príbram, Czech Republic)

The content and the isotopic composition of lead (Pb) were studied in a peat deposit on the ridge of the Brdy Hills, in the vicinity of the Príbram metallurgical works, in the Czech Republic. Quadrupole ICP MS was employed to determine the elemental composition and (206)Pb/(207)Pb and (208)Pb/(206)Pb isotope ratios. The individual layers were dated using alpha spectrometric measurement of the (210)Pb activity. The historical time period covered by the studied cores reached back to the 18th century. The Pb concentration in the studied profiles varied from 10 to 550 mg kg(-1). The (206)Pb/(207)Pb ratio varied in the range from 1.154 to 1.194 in the individual parts of the profile. The metallurgy of the Pb ores ((206)Pb/(207)Pb approximately 1.16), lithogenic Pb ((206)Pb/(207)Pb approximately 1.2), metallurgical processing of automobile batteries ((206)Pb/(207)Pb approximately 1.17) and the combustion of coal ((206)Pb/(207)Pb approximately 1.17-1.19) yield isotopic signatures that determine the isotope compositions of the individual profiles. Deposition rates between 15 mg m(-2) year(-1) at the beginning of the 19th century and 320 mg m(-2) year(-1) in the 1980s were determined in the dated profiles. The increased deposition rates determined on the dated profiles correspond to the increasing production of Pb ores in the Príbram mining area at the turn of the 19th and 20th centuries. The maximum for metallurgical production corresponds to the highest deposition rates recorded in 1960s and 1970s. The current deposition rate of 5-89 mg m(-2) year(-1) Pb is related to erosion of contaminated soils and waste dumps.     

Effectiveness of leaded petrol phase-out in Tianjin, China based on the aerosol lead concentration and isotope abundance ratio

The phase-out of leaded petrol has been a measure widely used to reduce atmospheric lead pollution. Since the 1980s, China began to promote unleaded petrol. In order to assess the effectiveness of the measure an isotope fingerprint technique was applied for aerosol samples in the city of Tianjin. After dilute acid leaching, the lead concentration and isotope abundance ratios were determined for 123 samples collected in Tianjin during eight years (1994-2001). The 206Pb/207Pb ratio was lower in summer, when coal combustion emission was low and vehicle exhaust became more important, indicating that the 206Pb/207Pb ratio of leaded petrol in Tianjin is lower than that of aerosol samples. The 206Pb/207Pb ratio gradually increased from 1994 to 2001, a trend that suggests that the contribution from vehicle exhaust was diminishing. Overall, the measurements matched well with national statistical data of leaded and unleaded petrol production. After the nationwide switch to unleaded gasoline, comprehensive control measures are urgently needed to reduce air lead pollution in China, as aerosol lead reduced slightly but remains at a relatively high level.     

Historical changes in lead concentrations in tree-rings of sycamore,oak and Scots pine in north-west England

Lead concentrations in tree rings of sycamore (Acer pseudoplatanus L.), oak (Quercus robur L.) and Scots pine (Pinus sylvestris L.) sampled at a parkland in north-west England were measured in wood formed since the mid-1800s. Concentrations of Pb in Scots pine and oak peaked in wood formed between 1900 and 1940, most likely because of Pb accumulation in heartwood, indicating that oak and Scots pine are unsuitable for monitoring temporal changes in Pb deposition at the study site. In contrast, Pb concentrations in sycamore, a species that has similar heartwood and sapwood chemistry, were relatively constant in wood formed between the mid-1800s and 1950. Lead concentrations decreased steadily in sycamore tree rings formed after the 1950s, and decreased more abruptly in wood formed after 1985. This sharp decrease in wood Pb cannot be due to decreases in soil Pb concentration. Stable Pb isotope analysis was used to further investigate Pb patterns in sycamore wood. Excess 206Pb/207Pb ratios in tree-rings of sycamore were relatively constant, approximately 1.17, in wood formed prior to the 1930s, but decreased steadily thereafter reaching a minimum value of approximately 1.16 in wood formed between 1975 and 1985 after which time 206Pb/207Pb ratios increased. This pattern is consistent with changes in Pb isotope ratios measured in peat, sediment and aerosol samples in the UK. However, the magnitude of the decrease in 206Pb/207Pb (largely due to gasoline Pb) is considerably lower than in other studies and our estimates indicate that less than 20% of the total Pb in sycamore wood measured since the mid-1800s is derived from gasoline emissions. A more likely explanation for the pattern of Pb observed in sycamore tree rings is that soil Pb accumulates within rings of the diffuse porous wood over a number of years. Such uptake patterns would result in lower Pb concentrations in the outer (more recently formed) tree rings, which coincide with recent reductions in Pb deposition in the UK. Overall, this study indicates that tree ring chemistry is unsuitable for monitoring historical changes in Pb deposition at the study site.