Using biochemical and isotope geochemistry to understand the environmental and public health implications of lead pollution in the lower Guadiana River, Iberia: a freshwater bivalve study

Lead is a natural component of aquatic ecosystems with no known biological role and is highly toxic. Its toxicity stems from its ability to mimic biologically important metals and to produce membrane damage through lipid peroxidation (LPO). Most lead poisoning symptoms are thought to occur by interfering with an essential enzyme, delta-aminolevulinic acid dehydratase (ALAD), the activity of which is markedly inhibited by lead. The purpose of this work was to study the levels and effects of lead pollution (responses of ALAD and oxidative stress biomarker LPO) in the freshwater bivalve Corbicula fluminea along the lower Guadiana River (Portugal and Spain); a major river system impacted by historic mining pollution and more recent anthropogenic inputs. The results show that the enzymatic activity of ALAD is negatively correlated with the total Pb concentration of the whole tissue suggesting that ALAD has considerable potential as a biomarker of lead exposure in C. fluminea. To identify the sources of lead to which bivalves have been exposed, high precision (206)Pb/(204)Pb, (207)Pb/(204)Pb, (208)Pb/(204)/Pb ratios for C. fluminea confirm that historical mining activities in the Iberian Pyrite Belt are the dominant source of lead pollution in the lower Guadiana River. The isotope patterns however exhibit marked seasonal and geographic variation in response to rainfall and river water management. Locally, other anthropogenic sources of lead have been detected in C. fluminea close to population centres, thus adding to its versatility as a freshwater bio-indicator. Overall, the study highlights the value of natural ecosystems as monitors of water quality and their importance for public health assessment and surveillance.     

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.     

Lead shot contribution to blood lead of First Nations people: the use of lead isotopes to identify the source of exposure

Although lead isotope ratios have been used to identify lead ammunition (lead shotshell pellets and bullets) as a source of exposure for First Nations people of Canada, the actual source of lead exposure needs to be further clarified. Whole blood samples for First Nations people of Ontario, Canada, were collected from participants prior to the traditional spring harvest of water birds, as well as post-harvest. Blood-lead levels and stable lead isotope ratios prior to, and after the harvest were determined by ICP-MS. Data were analyzed by paired t-tests and Wilcoxon Signed-Ranks tests. All participants consumed water birds harvested with lead shotshell during the period of study. For the group excluding six males who were potentially exposed to other sources of lead (as revealed through a questionnaire), paired t-tests and Wilcoxon Signed-Ranks tests showed consistent results: significant (p<0.05) increases in blood-lead concentrations and blood levels of (206)Pb/(204)Pb and (206)Pb/(207)Pb towards the mean values we previously reported for lead shotshell pellets; and a significant decrease in (208)Pb/(206)Pb values towards the mean for lead shotshell pellets. However, when we categorized the group further into a group that did not use firearms and did not eat any other traditional foods harvested with lead ammunition other than waterfowl, our predictions for (206)Pb/(204)Pb, (206)Pb/(207)Pb and (208)Pb/(206)Pb hold true, but there was not a significant increase in blood-lead level after the hunt. It appears that the activity of hunting (i.e., use of a shotgun) was also an important route of lead exposure. The banning of lead shotshell for all game hunting would eliminate a source of environmental lead for all people who use firearms and/or eat wild game.     

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.     

A stable lead isotopic investigation of the use of sycamore tree rings as a historical biomonitor of environmental lead contamination

The validity of the use of sycamore (Acer pseudoplatanus) tree-rings for the reconstruction of atmospheric lead pollution histories was investigated. Tree cores spanning 1892-2003 were collected from several sycamores from the eastern shore of Loch Lomond, Scotland, an area with no local point sources of lead emission. The lead concentration and 206Pb/207Pb profiles of the Loch Lomond region cores were compared with corresponding data for the 210Pb-dated loch sediment, and also with data for moss of known age from a Scottish herbarium collection. Two of the seven sycamore cores showed the same lead concentration trend as the lead flux to the loch, the rest having no similarity to either each other or the loch sediment record. Two further sycamore cores showed some similarity in their temporal 206Pb/207Pb trends to those seen in the sediment and moss records, but only in part of their profiles, whilst the 206Pb/207Pb ratios of the other sycamore cores remained relatively unchanged for the majority of the time covered, or exhibited an opposite trend. The 206Pb/207Pb ratios of the tree cores were also mostly higher than those of the previously established records for any given time period. Tree cores covering 1878-2002 were also collected along transects from Wanlockhead and Tyndrum, two areas of former lead mining and smelting associated with distinct 206Pb/207Pb ratios of 1.170 and 1.144, respectively. The Wanlockhead tree cores exhibited a generally decreasing trend in lead concentration with both time and distance from the lead mine. The characteristic 206Pb/207Pb ratio of 1.170 was observed in samples close to the mine but a decrease in the influence of the mine-derived lead was observed in more distant samples. The tree sampled at Tyndrum showed elevated lead concentrations, which decreased with time, and a fairly constant 206Pb/207Pb ratio of 1.15 reflecting input from the mine, features not observed in any other trees along the transect. Overall the data suggest that sycamore tree-ring analysis is an unsuitable method for obtaining records of historical lead deposition in areas with no large local lead input, although it can reveal some information about the temporal and spatial influence of point source emitters. The unsuitability probably arises from the number of active annual rings in a single year, the post-uptake radial translocation of elements, the relative importance of the different routes of uptake, and the soil depth(s) from which trees draw nutrients.     

The graphical presentation of lead isotope data for environmental source apportionment

Lead isotope ratios are widely used to identify original sources of Pb in the environment. Such source apportionment depends on the ability to distinguish potential sources on the basis of their isotopic composition. However, almost all terrestrial Pb is co-linear in some of the plots i.e. ²⁰⁶Pb/²⁰⁸Pb versus ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁶Pb/²⁰⁴Pb versus ²⁰⁶Pb/²⁰⁷Pb commonly presented in the literature. These diagrams are unable to distinguish more than two sources of environmental Pb. Linear trends in such plots are an inevitable consequence of the co-linearity of terrestrial leads and should not be taken necessarily to indicate simple binary mixing of sources. A more reliable test for multiple source mixing can be obtained from plots involving ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb and therefore requires measurements of the minor ²⁰⁴Pb isotope.     

长江中下游中（新）生代岩浆岩铅同位素地质信息探索

长江中下游地区中生代花岗闪长岩系列和石英正长岩系列及新生代玄武岩系列岩浆岩的铅同位素比值间具有良好的线性关系。基于作者的研究，得出了以下结论：１）铅同位素组成特征可用壳－幔混合作用解释；２）研究区的地幔铅具有单阶段演化历史；３）研究区地幔物质组成相对均匀；４）有限量物质脱离地幔不能明显影响地幔物质组成；５）各系列岩石的壳源铅分别来自不同的壳层；６）研究区地幔属正常地幔。     

Comparison of lead isotopes with source apportionment models, including SOM, for air particulates

We have measured high precision lead isotopes in PM(2.5) particulates from a highly-trafficked site (Mascot) and rural site (Richmond) in the Sydney Basin, New South Wales, Australia to compare with isotopic data from total suspended particulates (TSP) from other sites in the Sydney Basin and evaluate relationships with source fingerprints obtained from multi-element PM(2.5) data. The isotopic data for the period 1998 to 2004 show seasonal peaks and troughs that are more pronounced in the rural site for the PM(2.5).samples but are consistent with the TSP. The Self Organising Map (SOM) method has been applied to the multi-element PM(2.5) data to evaluate its use in obtaining fingerprints for comparison with standard statistical procedures (ANSTO model). As seasonal effects are also significant for the multi-element data, the SOM modelling is reported as site and season dependent. At the Mascot site, the ANSTO model exhibits decreasing (206)Pb/(204)Pb ratios with increasing contributions of fingerprints for "secondary smoke" (industry), "soil", "smoke" and "seaspray". Similar patterns were shown by SOM winter fingerprints for both sites. At the rural site, there are large isotopic variations but for the majority of samples these are not associated with increased contributions from the main sources with the ANSTO model. For two winter sampling times, there are increased contributions from "secondary industry", "smoke", "soil" and seaspray with one time having a source or sources of Pb similar to that of Mascot. The only positive relationship between increasing (206)Pb/(204)Pb ratio and source contributions is found at the rural site using the SOM summer fingerprints, both of which show a significant contribution from sulphur. Several of the fingerprints using either model have significant contributions from black carbon (BC) and/or sulphur (S) that probably derive from diesel fuels and industrial sources. Increased contributions from sources with the SOM summer fingerprints could explain the summer-time peaks in isotopic ratio at both sites and, at the rural site, be associated with meteorological influences. Nevertheless, the SOM results indicate that there are multiple overlapping 'weak' sources.     

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 reveal different sources of lead in balsamic and other vinegars

Fifty-eight brands of balsamic vinegars were analyzed for lead concentrations and isotopic compositions (²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb, and ²⁰⁸Pb) to test the findings of a previous study indicating relatively high levels of lead contamination in some of those vinegars — more than two thirds (70%) of them exceeded California's State Maximum Level (34 μg/L) based on consumption rates ≥ 0.5 μg Pb per day. The Lead isotopic fingerprints of all those vinegars with high lead concentrations were then found to be primarily anthropogenic. This isotopic analysis unquestionably reveals multiple contamination sources including atmospheric pollutant Pb and an unidentified contamination source, likely occurring after grape harvest. Organically grown grape vinegars display the same Pb content and isotopic signatures as other vinegars. This implies that pesticides might not be a significant source of pollutant Pb in vinegars. A significant post-harvest contamination would be inherited from chemicals added during production and/or material used during transport, processing or storage of these vinegars. This is consistent with the highest Pb levels being found in aged vinegars (112 ± 112 μg/L) in contrast to other vinegars (41.6 ± 28.9 μg/L) suggesting contamination during storage. It is, therefore, projected that lead levels in most vinegars, especially aged balsamic and wine vinegars, will decrease with improvements in their manufacture and storage processes consequential to recent concerns of elevated levels of lead in some vinegars.     

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.     

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.     

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.     

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 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.     

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.     

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.     

Investigation of mine and industry dumps in the FRG in relation to a possible release of natural radioactive elements

More than 350 dumps of mines and industries in two federal states of the FRG were recorded, measured radiometrically, evaluated, and some of them sampled. Most of the mine dumps belonged to old and smaller residues from lead/zinc and iron ore mining, while the largest depositions contain tailings of modern ore beneficiation of flyash disposal. All mine dumps from uranium exploration in Baden-Württemberg and Bavaria were investigated.The highest doses, up to 100 mSv/a, were found on the piles of the uranium exploration. These depositions, which are supervised and licensed, are followed, in terms of surface dose, by the old uncontroll mne dupms of silver/cobalt mining with doses up to 20 mSv/a. The numerous porphyry and granite quarries show doses between 1 and 2 mSv/a, as do flyash and slag dumps. The lowest doses were found on the dumps of the hydrothermal Pb/Zn and iron ore deposits, while the slag piles of iron ore processing showed higher thorium values.Assays for Ra-226 and Pb-210 of the materials deposited confirmed the radiometric results. Analyses of seepage waters and gallery waters showed only very few values exceeding the derived drinking water concentrations.     

Seasonal and long-term change in lead deposition in central Japan: evidence for atmospheric transport from continental Asia

Long-range transport of air pollution from continental Asia is currently an important issue concerning the Japanese environment, especially in regions susceptible to acidification due to low buffering capacity, such as Murakami, Niigata prefecture, located on the west coast of central Japan. Evidence for long-range transport was obtained through lead and lead isotopic analysis of 84 archived precipitation filters, showing seasonal changes in lead deposition from May 1999 to May 2002. Lead deposition was highest in winter and spring (November through May) each year and lowest in summer. Computed 72-h back trajectories showed that in winter air masses were predominantly transported from the northwest, passing over northern China and eastern Russia, whilst in summer air masses predominantly originated from the southeast passing over Japan. Lead isotopic analysis showed higher (208)Pb/(206)Pb during winter, indicating that lead originated from a different source. A plot of (207)Pb/(206)Pb vs. (208)Pb/(206)Pb identified a thorogenic component, which is excess (208)Pb compared to a standard lead growth curve, indicative of certain lead ores and coals in continental Asia. The data provided evidence of long-range transport of lead from continental Asia to Japan. Bark pockets included within the trunks of two Japanese cedar trees harvested near Murakami, dating between 1972 and 1982, exhibited lead isotope ratios indicative of Japanese-sourced lead. In contrast, current (2003) bark showed thorogenic ratios, consistent with a relative decline in Japanese-sourced and increase in continental-sourced lead.     

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.