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.     

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.     

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.     

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.     

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.     

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.     

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.     

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 comparison of the isotopic composition of lead in rainwater, surface vegetation and tree bark at the long-term monitoring site, Glensaugh, Scotland, in 2007

The lead concentrations and isotopic ratios (²⁰⁶Pb/²⁰⁷Pb, ²⁰⁸Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁷Pb) of 31 rainwater (September 2006-December 2007) and 11 surface vegetation (moss, lichen, heather) samples (October 2007) from the rural upland catchment of Glensaugh in northeast Scotland and of nine bark samples (October 2007) from trees, predominantly Scots pine, in or near Glensaugh were determined. The mean ²⁰⁶Pb/²⁰⁷Pb ratios for rainwater in 2006 and 2007 were similar to those previously determined for 2000 to 2003 at Glensaugh, yielding an average mean annual value of 1.151 ± 0.005 (± 1 SD) for the period from 2000, when an outright ban on leaded petrol came into force in the UK, to 2007. The mean ²⁰⁶Pb/²⁰⁷Pb ratio (1.146 ± 0.004; n = 7) for surface vegetation near the top (430-450 m) of the catchment was not significantly different (Student's t test) from that of rainwater (1.148 ± 0.017; n = 24) collected over the 12-month period prior to vegetation sampling, but both were significantly different, at the 0.1% (i.e. p < 0.001) and 1% (p < 0.01) level, respectively, from the corresponding mean value (1.134 ± 0.006; n = 9) for the outermost layer of tree bark. When considered in conjunction with similar direct evidence for 2002 and indirect evidence (e.g. grass, atmospheric particulates, dated peat) for recent decades in the Glensaugh area, these findings confirm that the lead isotopic composition of surface vegetation, including that of suitably located moss, reflects that of the atmosphere while that of the outermost layer of Scots pine bark is affected by non-contemporaneous lead. The nature and relative extent of the different contributory sources of lead to the current UK atmosphere in the era of unleaded petrol, however, are presently not well characterised on the basis of lead isotopic measurements.     

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

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

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

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

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

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

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.     

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.     

Stable lead isotopes ratios in major french rivers and estuaries

Lead isotopes ratios have been determined in suspended matter and water samples collected from major rivers and estuaries in France to assess their present level of Pb pollution.Most of the anthropogenic Pb found in the environment comes from Pb alkyls added to petrol. In France most petrol Pb comes from imported Pb ores which mainly have very characteristic Pb isotopes ratios (for example, a low ²⁰⁶Pb/²⁰⁷Pb ratio). Indeed, the ²⁰⁶Pb/²⁰⁷Pb ratio of aerosols sampled in France near a highway and a carpark was found to be very low (1.09-1.11). Despite not being so important with respect to atmospheric and water pollution, anthropogenic Pb produced by the iron, steel and copper production industries has also been considered and a slightly higher ²⁰⁶Pb/²⁰⁷Pb ratio (1.141) has been found from measurements made in the north of France near industrial plants.Conversely, higher ²⁰⁶Pb/²⁰⁷Pb ratios (1.197-1.206) were found in the pre-industrial sediments discharged by the rivers studied. These ratios are considered to be representative of local natural Pb during pre-industrial times.The measured Pb isotopes ratios in the suspended particulate matter compared with the two end-members show that the most polluted river is the Seine, followed by the Rhône and then the Garonne and the Loire. It is shown that anthropogenic Pb pollution is more easily detected when the solid discharge is low, such as in the Seine river. Conversely, a high particulate load can dilute the level of pollution by anthropogenic Pb and in this case Pb isotopes ratios are very similar to the natural level.As far as estuaries are concerned (the Seine estuary was not studied), variations of Pb isotopes ratios are generally observed and are attributed either to natural geochemical processes (Gironde estuary) or to man's influence (Loire and Rhône estuaries).     

Stable lead isotopic characterisation of the historical record of environmental lead contamination in dated freshwater lake sediment cores from northern and central Scotland

Sediment cores from three Scottish freshwater lakes, Loch Ness in the remote north and Loch Lomond and the Lake of Menteith, much closer to the heavily populated and industrialised central belt were analysed for 210Pb, 137Cs, Pb and stable Pb isotopic composition (206Pb/207Pb). The radionuclide data were used to establish chronologies for the Loch Ness and Loch Lomond cores, but a chronology could not be developed for the Lake of Menteith core, in which the surface sediment had been subject to intense mixing. Although Pb concentrations generally started increasing during the mid-17th Century, a small peak occurred for Loch Ness in the early 16th Century, perhaps attributable to the influence of medieval mining and smelting in mainland Europe. Temporal trends in the pattern of Pb accumulation were similar for Loch Ness and both sites in Loch Lomond, with 40-50% of the anthropogenic Pb deposited prior to the 20th Century. Fluxes of anthropogenic Pb to the lake sediments peaked during the 1950s at all locations where chronologies could be established. The 5-fold increase in anthropogenic Pb inventory for the southern basin of Loch Lomond relative to Loch Ness reflected geographical proximity to the main polluting sources. The 206Pb/207Pb data for anthropogenic Pb in the sediments from Loch Ness and Loch Lomond exhibited largely similar trends related to five different time periods. Pre-1820, the 206Pb/207Pb ratio was close to that for coal (1.181). From 1820 to 1900, a fairly constant 206Pb/207Pb ratio of approximately 1.17 probably resulted from a combination of emissions from the smelting of indigenous Pb ore (1.170) and coal burning (1.181) in Scotland, and industrial activity to the south in England, where Australian Pb of characteristically low 206Pb/207Pb ratio (1.04) was already in use. From 1901 to 1930, the 206Pb/207Pb ratio declined by <0.01, due to the increasing influence of Australian Pb. From 1931 to 1975/1985, the 206Pb/207Pb ratio of anthropogenic Pb declined by a further 0.03 to 0.04, to minimum values from approximately 1975 to 1985, primarily a consequence of car-exhaust emissions of Pb arising from the introduction of alkyl Pb petrol additives (206Pb/207Pb approximately 1.06-1.09). From 1975/1985 to the mid-1990s, the 206Pb/207Pb ratio of anthropogenic Pb increased by up to 0.015, a consequence of a reduction in car-exhaust emissions of Pb, resulting from reductions in the maximum permitted concentration of Pb in petrol, and the introduction and increasing uptake of unleaded petrol. Source apportionment calculations, on the basis of 206Pb/207Pb values in surface sediment, suggested that the contribution of Pb emissions from the use of leaded petrol was 27-40% of the atmospheric burden by the mid-1990s, in line with estimates from rainwater 206Pb/207Pb data.     

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.     

Atmospheric Pb deposition in Spain during the last 4600 years recorded by two ombrotrophic peat bogs and implications for the use of peat as archive

Two ombrotrophic peat bogs in Northwestern Spain provided a history of 4600 years of Pb accumulation. Highest Pb concentrations (84-87 microg g(-1)) were found near the bogs' surface, but there were also other significant peaks (6-14 microg g(-1)), indicating pre-industrial atmospheric pollution. The enrichment factors (EFs) in both cores show a remarkably similar record. Atmospheric Pb pollution dates back to at least approximately 2500 years ago, reaching a first maximum during the Roman period. For the last 300 years, Pb EFs significantly increased due to industrial development, but the uppermost samples of the bogs show decreasing Pb EFs, probably due to the phasing out of leaded gasoline. These results are also supported by 206Pb/207Pb isotope ratios, as they continuously decrease from ca. 3000 BP until 2000 BP (from 1.275 at 4070 14C years BP to 1.182), indicating the growing importance of nonradiogenic Pb released from Iberian ores by ancient mining. Peat samples at a 3-5-cm depth are even less radiogenic (206Pb/107Pb = 1.157), indicating the strong influence of leaded gasoline. Despite the common history shared by the two bogs, striking differences were found for Pb enrichment, whether this was calculated by normalising to the Pb/Ti ratio of the upper continental crust or to the Pb/Ti ratios of peats from pre-anthropogenic times. This effect seems to be related to differences in Ti accumulation in both bogs, possibly due to physical fractionation of the airborne dust during wind transport. Enrichment has to be carefully considered when comparing the results obtained for different bogs, since our results suggest that normalising to crustal proportions is meaningless when the bulk of the deposition in an area is strongly influenced by short- and medium-range dust transport.     

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.     

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.