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.     

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.     

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.     

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.     

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.     

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.     

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.     

Mobility of Pb in salt marshes recorded by total content and stable isotopic signature

Total lead and its stable isotopes were analysed in sediment cores, leaves, stem and roots of Sacorconia fruticosa and Spartina maritima sampled from Tagus (contaminated site) and Guadiana (low anthropogenic pressure) salt marshes. Lead concentration in vegetated sediments from the Tagus marsh largely exceeded the levels in non-vegetated sediments. Depth profiles of (206)Pb/(207)Pb and (206)Pb/(208)Pb showed a decrease towards the surface ((206)Pb/(207)Pb=1.160-1.167) as a result of a higher proportion of pollutant Pb components. In contrast, sediments from Guadiana marsh exhibited low Pb concentrations and an uniform isotopic signature ((206)Pb/(207)Pb=1.172+/-0.003) with depth. This suggests a homogeneous mixing of mine-derived particles and pre-industrial sediments with minor inputs of anthropogenic Pb. Lead concentrations in roots of plants from the two marshes were higher than in leaves and stems, indicating limited transfer of Pb to aerial parts. A similar Pb isotopic signature was found in roots and in vegetated sediments, indicating that Pb uptake by plants reflects the input in sediments as determined by a significant anthropogenic contribution of Pb at Tagus and by mineralogical Pb phases at Guadiana. The accumulation in roots from Tagus marsh (max. 2870 microg g(-1) in S. fruticosa and max. 1755 microg g(-1) in S. maritima) clearly points to the dominant role of belowground biomass in the cycling of anthropogenic Pb. The fraction of anthropogenic Pb in belowground biomass was estimated based on the signature of anthropogenic Pb components in sediments ((206)Pb/(207)Pb=1.154). Since no differences exist between Pb signature in roots and upper sediments, the background and anthropogenic levels of Pb in roots were estimated. Interestingly, both background and anthropogenic Pb in roots exhibited a maximum at the same depth, although the proportion of anthropogenic Pb was relatively constant with depth (83+/-4% for S. fruticosa and 74+/-8% for S. maritima).     

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.     

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.     

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.     

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.     

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.     

Isotopic characterisation of the historical lead deposition record at Glensaugh, an organic-rich, upland catchment in rural N.E. Scotland

As part of a wider investigation of the biogeochemistry and fate of Pb deposited from the atmosphere at Glensaugh, a rural upland catchment in N.E. Scotland, the concentration and isotopic composition of Pb were determined in four thinly sectioned monolith cores (25 cm) of peat collected at altitudes of 426--434 m from different faces of Thorter Hill and in a series of 21 10-cm unsectioned cores of peat and organic-rich soil along a transect from near the top (434 m) to the bottom (224 m) of the catchment. Depth profiles of Pb concentration and (206)Pb/(207)Pb ratio were similar for the longer cores. Subsurface Pb maxima (238--489 mg kg(-1)) typically occurred below (206)Pb/(207)Pb minima (1.123-1.134). One core was (210)Pb-dated and had a fairly constant (206)Pb/(207)Pb value of 1.170 from mid-19th century to ca. 1930, followed by a decline (attributable to the increasing influence of Australian Pb of much lower (206)Pb/(207)Pb ratio) to 1.134 by the early 1990s, and then a rapid increase to 1.160 by 2002, after the phased withdrawal of leaded petrol. The fluxes of Pb increased from 15 mg m(-2) year(-1) in the late 19th century to a peak of 60 mg m(-2) year(-1) ca. 1960, before declining steadily to 3.6 mg m(-2) year(-1) by the beginning of the 21st century. Some 40% of the anthropogenic Pb in the core had been deposited prior to 1900. The mean anthropogenic Pb inventory of the four longer cores was 7.4+/-1.5 g m(-2), of which approximately 70% occurred in the top 10 cm, in good agreement with the inventories of the shorter cores collected above 400 m. These inventories are higher than those of the industrial central belt of Scotland, probably because of enhanced deposition at altitude. This is consistent with the derived average (210)Pb flux of 198+/-11 Bq m(-2) year(-1), which is twice that of typical UK (210)Pb deposition and the rainfall for the site. The past deposition of Pb at Glensaugh, including that from sources (e.g., smelting, coal combustion) other than leaded petrol, has clearly been considerable. Even since the introduction of leaded petrol ca. 1930, car-exhaust emissions may have accounted for no more than 35% of the Pb deposited.     

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.     

A lead isotopic study of the human bioaccessibility of lead in urban soils from Glasgow, Scotland

The human bioaccessibility of lead (Pb) in Pb-contaminated soils from the Glasgow area was determined by the Unified Bioaccessibility Research Group of Europe (BARGE) Method (UBM), an in vitro physiologically based extraction scheme that mimics the chemical environment of the human gastrointestinal system and contains both stomach and intestine compartments. For 27 soils ranging in total Pb concentration from 126 to 2160 mg kg^− 1 (median 539 mg kg^− 1), bioaccessibility as determined by the ‘stomach’ simulation (pH ~ 1.5) was 46-1580 mg kg^− 1, equivalent to 23-77% (mean 52%) of soil total Pb concentration. The corresponding bioaccessibility data for the ‘stomach + intestine’ simulation (pH ~ 6.3) were 6-623 mg kg^− 1 and 2-42% (mean 22%) of soil Pb concentration. The soil ²⁰⁶Pb/²⁰⁷Pb ratios ranged from 1.057 to 1.175. Three-isotope plots of ²⁰⁸Pb/²⁰⁶Pb against ²⁰⁶Pb/²⁰⁷Pb demonstrated that ²⁰⁶Pb/²⁰⁷Pb ratios were intermediate between values for source end-member extremes of imported Australian Pb ore (1.04) - used in the manufacture of alkyl Pb compounds (1.06-1.10) formerly added to petrol - and indigenous Pb ores/coal (1.17-1.19). The ²⁰⁶Pb/²⁰⁷Pb ratios of the UBM ‘stomach’ extracts were similar (< 0.01 difference) to those of the soil for 26 of the 27 samples (r = 0.993, p < 0.001) and lower in 24 of them. A slight preference for lower ²⁰⁶Pb/²⁰⁷Pb ratio was discernible in the UBM. However, the source of Pb appeared to be less important in determining the extent of UBM-bioaccessible Pb than the overall soil total Pb concentration and the soil phases with which the Pb was associated. The significant phases identified in a subset of samples were carbonates, manganese oxides, iron-aluminium oxyhydroxides and clays.     

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.     

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.     

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.