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.     

Multiple Pb sources in marine sediments near the Australian Antarctic Station, Casey

An extensive Pb isotope ratio survey of approximately 100 marine sediment samples from near Casey Station, East Antarctica has been undertaken. Sediment surface grabs and cores were collected over nine years between 1997-2006 and, following HF total digestion, were analysed by magnetic sector ICP-MS. Fifty-two reference samples ([Pb] range 5-26 mg kg(-1)) from 6 non-impacted locations displayed a broad range of Pb isotope ratios representative of the natural background geology of the region ((208)Pb/(204)Pb ratios of 37.5-40; (206)Pb/(204)Pb ratios of 17-19). Potentially impacted sediments from Brown Bay (n=27, [Pb] range 18-215 mg kg(-1)), adjacent to the current and former Australian Stations at Casey (and the associated Thala Valley tip site) showed contamination by Pb characteristic of Broken Hill and Mt Isa Australian deposits ((208)Pb/(204)Pb and (206)Pb/(204)Pb values of 35.5-36 and 16.0-16.1, respectively). The nearby abandoned Wilkes Station was previously manned by both US (1957-59) and Australian (1959-69) expeditioners. Adjacent marine sediment samples (n=24, [Pb] range 13-40 mg kg(-1)) displayed Pb isotopic signatures suggesting anthropogenic input from multiple sources. On a three-isotope diagram Wilkes sediments were found to display Pb ratios lying intermediate between Missouri (US), Broken Hill/Mt Isa (Australia)/Idaho (US), and natural geogenic Pb end members. Discarded Pb batteries, paint samples and fuel spills were all considered in this work as possible point sources of Pb contamination to the local environment. Batteries are thought to be the dominant source.     

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.     

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.     

Lead isotope ratios in tree bark pockets: an indicator of past air pollution in the Czech Republic

Tree bark pockets were collected at four sites in the Czech Republic with differing levels of lead (Pb) pollution. The samples, spanning 1923-2005, were separated from beech (Fagus sylvatica) and spruce (Picea abies). Elevated Pb content (0.1-42.4 microg g(-1)) reflected air pollution in the city of Prague. The lowest Pb content (0.3-2.6 microg g(-1)) was found at the Kosetice EMEP "background pollution" site. Changes in (206)Pb/(207)Pb and (208)Pb/(206)Pb isotope ratios were in agreement with operation times of the Czech main anthropogenic Pb sources. Shortly after the Second World War, the (206)Pb/(207)Pb isotope ratio in bark pockets decreased from 1.17 to 1.14 and the (208)Pb/(206)Pb isotope ratio increased from 2.12 to 2.16. Two dominant emission sources responsible for these changes, lignite and leaded petrol combustion, contributed to the shifts in Pb isotope ratios. Low-radiogenic petrol Pb ((206)Pb/(207)Pb of 1.11) lead to lower (206)Pb/(207)Pb in bark pockets over time. High-radiogenic lignite-derived Pb ((206)Pb/(207)Pb of 1.18 to 1.19) was detected in areas affected by coal combustion rather than by traffic.     

Regional lead isotope study of a polluted river catchment: River Wear, Northern England, UK

High precision, lead isotope analyses of archived stream sediments from the River Wear catchment, northeast England (1986-88), provide evidence for three main sources of anthropogenic lead pollution; lead mining, industrial lead emissions and leaded petrol. In the upper catchment, pollution is totally controlled and dominated by large lead discharges from historic mining centres in the North Pennine Orefield (²⁰⁸Pb/²⁰⁶Pb, ²⁰⁷Pb/²⁰⁶Pb ratios range from 2.0744-2.0954 and 0.8413-0.8554 respectively). In the lower catchment, co-extensive with the Durham Coalfield and areas of high population density, pollution levels are lower and regionally more uniform. Isotope ratios are systematically higher than in the upper catchment (²⁰⁸Pb/²⁰⁶Pb, ²⁰⁷Pb/²⁰⁶Pb ratios range from 2.0856-2.1397 and 0.8554-0.8896 respectively) and far exceed values determined for the geogenic regional background. Here, the pollution is characterised by the atmospheric deposition of industrial lead and petrol lead. Lead derived from the combustion of coal, although present, is masked by the other two sources. Recent sediments from the main channel of the River Wear are isotopically indistinguishable from older, low order stream sediments of the North Pennine Orefield, indicating that contamination of the river by lead mining waste (up to several 1000 mg/kg Pb at some locations) continues to pose an environmental problem; a pattern that can be traced all the way to the tidal reach. Using within-catchment isotope variation and sediment lead concentrations, estimates can be made of the discharges from discrete mines or groups of mines to the overall level of lead pollution in the River Wear. As well as providing information pertinent to source apportionment and on-going catchment remediation measures, the database is a valuable resource for epidemiologists concerned with the health risks posed by environmental lead.     

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.     

Multitracer study of anthropogenic contamination records in the Camargue, Southern France

Contaminants are supplied to the coastal zone by the atmosphere, rivers and point sources like wastewaters or industrial area. Wetlands retain many of these contaminants and can be used to reconstruct sources and magnitudes of contaminant inputs. Radionuclides ((137)Cs, (210)Pb, (239)Pu and (240)Pu) and stable lead isotope ((206)Pb, (207)Pb) profiles were investigated in two cores collected in wetlands of the Rh?ne River delta, south of France (Camargue), to estimate the recent sediment accumulation rates and reconstruct the deposition of pollutants during the last century. One site was affected by storm or flood deposition from the Rh?ne river and showed the influence of Marcoule reprocessing plant releases on the plutonium isotopic ratios. The other site appears suitable for the reconstruction, even if mixing is evidenced at the surface by the radionuclides profiles. Plutonium isotopic ratios are characteristic of global fallout and the (210)Pb inventory of 4240 Bq m(-2) is approximately 30% higher than atmospheric deposit estimation. The pollutant lead inventory is 139 microg cm(-2), slightly higher than previous estimation from direct fallout. This difference can be partly due to an over-collection at this site (due to canopy cover) but also to variations with time in the deposition.     

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 effect of exposure to employees from mining and milling operations in a uranium mine on lead isotopes--a pilot study

Potential exposure during mining and milling of uranium ore has resulted in the industry being highly regulated. Exposure can arise from inhalation of the daughter product radioactive gas radon (222Rn), inhalation of radioactive dust particles from mining and milling, direct irradiation from outside the body, and ingestion of radionuclides (e.g. uranium or radium) in food or water. Making use of the highly unusual lead isotopic signature for uranium ores (high 206Pb/204Pb from the high uranium content, low 208Pb/204Pb from the low Th/U ratio), we undertook a pilot study of nine male mine employees and three controls from the Ranger uranium mine in the Northern Territory Australia to determine if it was feasible to use lead isotopes in blood to identify exposure to uranium-derived materials. The lead isotopic data for the mine employees and controls plot in two distinct fields which are consistent with predicted isotopic patterns. Assuming retention of 10% of the ingested lead, then the increases seen in 206Pb represent intakes of between 0.9 and 15 mg, integrated over the years of exposure. The small amount of lead does not affect blood lead concentrations, but appears to be sufficient to be detectable with sensitive isotopic methods. Further studies, including those on urine, should be undertaken to confirm the veracity of the lead isotope method in monitoring exposure of uranium industry employees.     

A comparison of lead isotope ratios in the bark pockets and annual rings of two beech trees collected in Derbyshire and South Yorkshire, UK

ICP-MS analysis of the bark pockets and annual rings of two beech (Fagus sylvatica L.) trees collected from Longshaw, Derbyshire and Swinton, South Yorkshire in the UK recorded differences in the (206)Pb/(207)Pb isotope ratio. In the Longshaw sample, the (206)Pb/(207)Pb isotope ratio of the bark pockets ( approximately 1914-1998, 78-260 microg g(-1) Pb) declined from approximately 1.16 to 1.12, whilst the annual rings (1899-1998, 0.2-2.5 microg g(-1) Pb) had a (206)Pb/(207)Pb ratio of approximately 1.18. In the Swinton sample, the bark pockets (approximately 1919-1998, 7-78 microg g(-1) Pb) declined from 1.15 to 1.11 and the annual rings (1899-1998, 0.2-0.5 microg g(-1) Pb) from 1.18 to 1.15. The data implied that the bark pockets accumulated lead directly from the atmosphere through wet and dry deposition, whilst the annual rings accumulated lead from the soil via the roots. The bark pockets recorded a relative decline in the accumulation of lead from indigenous sources, such as lead smelting and coal combustion (1.17-1.19), and increase in imported sources such as the smelting of Australian ores (1.04) and leaded petrol usage (1.06-1.09). In contrast, the annual rings at Longshaw recorded ratios typical of indigenous lead, whilst the annual rings in Swinton recorded a relatively small decrease in (206)Pb/(207)Pb reflecting leaded petrol usage. The decline in (206)Pb/(207)Pb of the bark pockets was consistent with the historical decline in (206)Pb/(207)Pb of atmospheric lead recorded in peat, lake sediments and archival herbage at other UK locations.     

A lead isotopic assessment of tree bark as a biomonitor of contemporary atmospheric lead

The outermost bark layer of trees, predominantly Scots pine (Pinus sylvestris), was sampled at 82 non-urban locations from six arbitrarily designated areas (Northwest, Northeast, Central Highlands, Central and East, Central and Southwest, Southeast), throughout Scotland during 2002-2003 and analysed for lead concentration and stable lead isotopes by flame atomic absorption spectrometry (AAS) and inductively coupled plasma-mass spectrometry (ICP-MS), respectively. The mean lead concentration and mean (206)Pb/(207)Pb ratio (+/-1 standard deviation, SD) for bark samples from the areas were as follows: Northwest (8.0 mg kg(-1), 1.121+/-0.014, n=17), Northeast (8.9 mg kg(-1), 1.117+/-0.012, n=12), Central Highlands (11.3 mg kg(-1), 1.130+/-0.010, n=11), Central and East (35.3 mg kg(-1), 1.120+/-0.007, n=10), Central and Southwest (20.6 mg kg(-1), 1.125+/-0.018, n=22) and Southeast (34.4 mg kg(-1), 1.120+/-0.005, n=10), with an overall mean lead concentration of 18.5 mg kg(-1) (range 0.6-146 mg kg(-1), median 8.4 mg kg(-1)) and an overall mean (206)Pb/(207)Pb ratio of 1.122+/-0.014 (range 1.089-1.168, median 1.122). The overall mean (206)Pb/(207)Pb ratio for bark was therefore significantly lower (p<0.01, t test) than the mean atmospheric (206)Pb/(207)Pb ratio of 1.154+/-0.006 (range 1.144-1.167, n=50) and 1.154+/-0.010 (range 1.134-1.171, n=26) as determined in rainwater collected routinely at Glensaugh, Central Highlands, during 2002 and 2003, respectively. The bark (206)Pb/(207)Pb values, 90% of which lay between 1.10 and 1.14, were more akin to those recorded for the atmosphere (via rainwater, atmospheric particulates, moss, etc.) at various locations throughout Scotland during the 1990s, a decade over which the use of leaded petrol (mean (206)Pb/(207)Pb ratio=1.076+/-0.011) declined markedly before its complete withdrawal in 2000. This strongly suggests that the lead content and isotopic composition of tree bark from Scots pine, which reputedly sheds its outer layers every couple of years or so, reflect exposure to atmospherically deposited lead (in the atmosphere or soil) over a much longer time period than just the previous 2-3 years of exposure to contemporary atmospheric lead. The possible influence of soil lead upon tree bark through external attachment was not observed in a comparative sub-set study of 27 paired bark (mean (206)Pb/(207)Pb ratio=1.122+/-0.016) and surface (0-2 cm) soil (mean (206)Pb/(207)Pb ratio=1.145+/-0.022) samples, in only six cases (i.e. 22%) of which did the corresponding (206)Pb/(207)Pb ratios agree within +/-2 SD. Likewise, bark (206)Pb/(207)Pb values exhibited no discernible trend with distance from the nearest road, with similar average values for 0-20 m (1.123+/-0.015, n=34) and 20-700 m (1.122+/-0.012, n=48), although the corresponding mean (and median) lead concentration of 23.5 (10) mg kg(-1) vs. 14.9 (7.5) mg kg(-1) was slightly higher for the former. The influence of airborne dusts from waste deposits related to former mining/smelting of Wanlockhead/Leadhills lead ores ((206)Pb/(207)Pb=1.170+/-0.003) could be seen, however, in the sycamore bark lead concentrations of up to 3050 mg kg(-1) and (206)Pb/(207)Pb ratios (1.168-1.171) observed at a distance of 0.5 km away.     

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).     

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.     

Lead contamination and associated disease in captive and reintroduced red kites Milvus milvus in England

Since 1989, a red kite Milvus milvus reintroduction programme has been underway in the United Kingdom, with 4-6 week old nestlings brought into captivity and held for 6-8 weeks before reintroduction. As scavengers, red kites may consume unretrieved game, and ingest shot or lead (Pb) fragments in their prey's flesh. We evaluated exposure to Pb in captive and wild red kites by taking blood samples from 125 captive young red kites prior to release, through analysing 264 pellets (regurgitated by wild birds) collected from under a roost site, and analysing Pb concentrations in livers and/or bones of 87 red kites found dead between 1995 and 2003. Lead isotope analyses of livers were also conducted in an effort to identify Pb exposure routes. Forty-six (36.8%) kites sampled prior to release had elevated blood Pb concentrations (201-3340 microg l(-1)). The source of this Pb was probably small fragments of lead ammunition in the carcasses of birds or mammals either fed to the nestlings by their parents or, more likely, subsequently whilst in captivity. Once released, kites were also exposed to lead shot in their food, and a minimum of 1.5-2.3% of regurgitated pellets contained Pb gunshot. Seven of 44 red kites found dead or that were captured sick and died within a few days had elevated (>6 mg kg(-1) dry weight [d.w.]) liver Pb concentrations, and six of these (14%) had concentrations of >15 mg kg(-1) d.w., compatible with fatal Pb poisoning. Post-mortem analyses indicated that two of these birds had died of other causes (poisoning by rodenticide and a banned agricultural pesticide); the remaining four (9%) probably died of Pb poisoning. Bone samples from 86 red kites showed a skewed distribution of Pb concentration, and 18 samples (21%) had Pb concentrations >20 mg kg(-1) d.w., indicating elevated exposure to Pb at some stage in the birds' life. Lead isotopic signatures (Pb (208/206); Pb (206/207)) in liver samples of the majority of kites were compatible with those found in lead shot extracted from regurgitated pellets. Lead isotope ratios found in the livers of kites with very low Pb concentrations were distinct from UK petrol Pb isotopic signatures, indicating that birds were exposed to little residual petrol Pb. We conclude that the primary source of Pb to which red kites are exposed is lead ammunition (shotgun pellets or rifle bullets), or fragments thereof, in their food sources; in some cases exposure appears sufficient to be fatal. We make recommendations to reduce Pb poisoning in both captive and wild red kites and other scavenging species.     

Pb and 206Pb/207Pb isotopic analysis of a tree bark pocket near Sheffield,UK recording historical change in airborne pollution during the 20th century

A section of tree trunk (beech, Fagus sylvatica) containing a bark pocket progressively enclosed at the junction of two branches was collected from a semi-rural location near Sheffield, UK. According to the annual growth rings, the bark pocket formed between ca. 1919 and 1998 (the date of felling). The bark pocket was divided into consecutive samples of differing radial depth (and thus age), that were analysed by ICP mass spectrometry. The Pb concentration varied from 7 to 78 mg kg (-1) and the 206Pb/207Pb isotope ratio from 1.11 to 1.15. In contrast, the current surface bark contained 46 mg kg(-1) Pb and recorded a 206Pb/207Pb ratio of 1.11. The changing elemental and isotopic composition of the bark pocket recorded historical change in the level and sources of airborne Pb pollution. An overall increase in Pb concentration with time was accompanied by a progressive reduction in 206Pb/207Pb from ca. 1935 to 1943. Mass balance calculations indicated that Pb additives in petrol contributed significantly to the rise in concentration, accounting for a maximum of 50% of the total Pb for ca. 1986-1998, but that other sources were generally dominant. The highest Pb concentrations were recorded from ca. 1951 to 1973, suggesting a high level of industrial pollution. A reduction in Pb concentration and reversal of the trend in 206Pb/207Pb was observed in the current bark.     

The identification of lead ammunition as a source of lead exposure in First Nations: the use of lead isotope ratios

The use of lead shotshell to hunt water birds has been associated with lead-contamination in game meat. However, evidence illustrating that lead shotshell is a source of lead exposure in subsistence hunting groups cannot be deemed definitive. This study seeks to determine whether lead shotshell constitutes a source of lead exposure using lead isotope ratios. We examined stable lead isotope ratios for lichens, lead shotshell and bullets, and blood from residents of Fort Albany and Kashechewan First Nations, and the City of Hamilton, Ontario, Canada. Data were analyzed using ANOVA and regression analyses. ANOVA of isotope ratios for blood revealed significant differences with respect to location, but not sex. Hamilton differed from both Kashechewan and Fort Albany; however, the First Nations did not differ from each other. ANOVA of the isotope ratios for lead ammunition and lichens revealed no significant differences between lichen groups (north and south) and for the lead ammunition sources (pellets and bullets). A plot of (206)Pb/(204)Pb and (206)Pb/(207)Pb values illustrated that lichens and lead ammunition were distinct groupings and only the 95% confidence ellipse of the First Nations group overlapped that of lead ammunition. In addition, partial correlations between blood-lead levels (adjusted for age) and isotope ratios revealed significant (p<0.05) positive correlations for (206)Pb/(204)Pb and (206)Pb/(207)Pb, and a significant negative correlation for (208)Pb/(206)Pb, as predicted if leaded ammunition were the source of lead exposure. In conclusion, lead ammunition was identified as a source of lead exposure for First Nations people; however, the isotope ratios for lead shotshell pellets and bullets were indistinguishable. Thus, lead-contaminated meat from game harvested with lead bullets may also be contributing to the lead body burden.     

REE characteristics and Pb, Sr and Nd isotopic compositions of steel plant emissions

A comprehensive Pb-Sr-Nd isotope and REE tracer study of atmospheric trace metal pollution by a steel plant situated to the north of the urban communities of Strasbourg (France) and Kehl (Germany) has been performed using tree barks as biomonitors. The 206Pb/207Pb and 208Pb/207Pb isotopic ratios of the steel plant's filter dust are similar to values found in dust of waste incinerators. The 87Sr/86Sr ratio is similar to present-day ratios of Phanerozoic or Precambrian granitic rocks. The 143Nd/144Nd isotopic composition is very low and corresponds to an (Nd) value of -17.5. Such a low value is characteristic of old Precambrian granitic rocks and banded iron formations. Thus, this low (Nd) value might point to the origin of the iron necessary for the steel production. The fact, that this isotopic composition does not occur in crustal rocks of Western Central Europe makes the Nd isotope ratio a powerful tool to trace steel plants atmospheric emissions. The rare earth element (REE) distribution pattern of the steel plant's filter dust shows very specific fractionations like La and Nd enrichments which are traceable in tree barks over a distance of 4 km. The Pb, Sr and Nd isotope ratios not only enable the steel plant's emissions to be traced in a north-easterly direction, along the principal wind pathway but also enables the interference of this emission at 4 km NE from the steel plant with another atmospheric component originating from the Strasbourg Rhine harbour to be identified.     

Lead isotopic signatures in Antarctic marine sediment cores: A comparison between 1 M HCl partial extraction and HF total digestion pre-treatments for discerning anthropogenic inputs

Sensitive analytical techniques are typically required when dealing with samples from Antarctica as even low concentrations of contaminants can have detrimental environmental effects. Magnetic Sector ICP-MS is an ideal technique for environmental assessment as it offers high sensitivity, multi-element capability and the opportunity to determine isotope ratios. Here we consider the Pb isotope record of five marine sediment cores collected from three sites in the Windmill Islands area of East Antarctica: Brown Bay adjacent to the current Australian station Casey, Wilkes near the abandoned US/Australian Station and McGrady Cove lying midway between the two. Two sediment pre-treatment approaches were considered, namely partial extraction with 1 M HCl and total dissolution involving HF. Lead isotope ratio measurements made following sediment partial extraction provided a more sensitive indication of Pb contamination than either Pb concentrations alone (irrespective of sample pre-treatment method) or isotope ratios made after HF digestion, offering greater opportunity for discrimination between impacted and natural/geogenic samples and sites. Over 90% of the easily extractable Pb from sediments near Casey was anthropogenic in origin, consisting of Pb from major Australian deposits. At Wilkes impact from discarded batteries with a unique isotopic signature was found to be a key source of Pb contamination to the marine environment with ~ 70-80% of Pb being anthropogenic in origin. The country and source of origin of these batteries remain unknown. Little evidence was found suggesting contamination at Wilkes by Pb originating from the major US source, Missouri. No definitive assessment could be made regarding Pb impact at McGrady Cove as the collected sediment core was of insufficient depth. Although Pb isotope ratio signatures may indicate anthropogenic input, spatial concentration gradients at nearby Brown Bay suggest contamination at McGrady Cove is unlikely. We recommend Pb isotopic analysis following 1 M HCl partial extraction pre-treatment as a powerful and sensitive method for tracing Pb contamination in marine sediments.     

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.