Pb isotope ratios of lake sediments in West Greenland: inferences on pollution sources

Lead (Pb), like many other pollutants, is carried into the Arctic by long-range atmospheric transport from industrial centers at lower latitudes. Unlike other pollutants, Pb can be used to assess emission source regions through the use of stable Pb isotope analyses. Using sediment cores from 17 lakes (three profiles and 14 top/bottom sample pairs) in the Søndre Strømfjord (Kangerlussuaq) region, West Greenland (67°N), this study assesses the extent and origin of Pb pollution along a 150 km transect between the Inland Ice and Davis Strait. Like ice core analyses from the interior of Greenland, the isotope analyses suggest pre-industrial contamination, although significant concentration changes in the lake sediments do not occur until the 18th/19th centuries, with the maximum concentrations occurring about 1970. Compared to the background, the Pb concentrations in recent sediments have increased about 2.5-fold, with slightly higher enrichments towards the coast, where annual precipitation is highest. For all of the lakes, there is a major decline in the ²⁰⁶Pb/²⁰⁷Pb ratio in the recent sediments (mean 1.218±0.030) as compared to deeper sediments (mean 1.365±0.084). Using a Pb isotope mixing model, we calculated an excess Pb isotope ratio, i.e. the isotope ratio necessary to produce the observed declines in recent sediments. While studies of atmospheric aerosols in the high Arctic (²⁰⁶Pb/²⁰⁷Pb ratio ∼1.16) have indicated that Russian emissions (²⁰⁶Pb/²⁰⁷Pb ratio ∼1.15–1.16) are a dominant source of arctic pollution, the excess Pb ratios of the lake sediments in the Søndre Strømfjord region (²⁰⁶Pb/²⁰⁷Pb ratio ∼1.14–1.15), in the low Arctic, suggest that W Europe (²⁰⁶Pb/²⁰⁷Pb ratio ∼1.14) is also a major emission source for this region.     

The Pb pollution fingerprint at Lochnagar: the historical record and current status of Pb isotopes

Ratios of 206Pb/207Pb in a Lochnagar sediment core slowly decline from c. 1.32 at 140 cm to c. 1.23 at 9 cm, and then rapidly decline to c. 1.15 at the surface. Ninety percent of the Pb in the surface sediments can be attributed to anthropogenic sources. The 206Pb/207Pb ratio data imply that catchment peat surface contains a higher fraction of anthropogenic Pb than the sediment surface. The 206Pb/207Pb ratios in the surface of the sediment core are consistent with ratios in trapped sediments collected annually between 1998 and 2003. However, there is no significant decline in these recent samples suggesting that the reduction in atmospheric Pb emissions has not yet been recorded by the sediments due to Pb inputs from the catchment. As catchment peats store about 840 kg previously deposited anthropogenic Pb since 1860, it is likely that catchment inputs will continue to affect future 206Pb/207Pb ratios.     

The quantification and distribution of pollution Pb at a woodland in rural south central Ontario, Canada

Lead concentrations and Pb isotope ratios were measured in the forest floor, mineral soil and vegetation at a white pine and a sugar maple stand in a woodland in south central Ontario. Lead concentrations decreased and 206Pb/207Pb ratios increased with mineral soil depth reflecting the mixing of pollution and natural Pb sources. Lead concentrations and 206Pb/207Pb ratios at 20-30 cm depth were approximately 6-7 mg/kg and 1.31-1.32, respectively. Assuming an integrated 206Pb/207Pb ratio in deposition over time of 1.18, estimated from lichen measurements and published data for the region, approximately 65% of Pb in the surface (0-1 cm) mineral soil is from anthropogenic sources. Approximately 90% of pollution Pb is found in the 0-10 cm soil layer (Ah) and less than 3% of the pollution Pb is present in the forest biomass and mull-type forest floor combined. Despite low Pb concentrations in vegetation (<2.5 mg/kg), we estimate that between 65 and 100% of the Pb in vegetation and approximately 75% of the Pb in the forest floor is from pollution sources. In total, the pollution Pb burdens at the pine and maple stands are estimated to be 860 and 750 mg/m2, respectively.     

Sequential extraction combined with isotope analysis as a tool for the investigation of lead mobilisation in soils: application to organic-rich soils in an upland catchment in Scotland

Sequential extraction (modified BCR procedure) combined with isotope analysis has been investigated as a tool for assessing mobilisation of lead into streams at an upland catchment in NE Scotland. The maximum lead concentrations (up to 110 mg kg(-1) in air-dried soil) occurred not at the surface but at about 10 cm depth. The lowest (206)Pb/(207)Pb ratios in any profile occurred, with one exception, at 2.5-5 cm depth. In the one exception, closest to the only road in the area, significantly lower (206)Pb/(207)Pb ratios in the surface soil together with much increased chloride concentrations (in comparison to other surface waters) indicated the possible mobilisation of roadside lead and transfer to the stream. The (206)Pb/(207)Pb ratios in extractable fractions tended at depth towards the ratio measured in the residual phase but the ratios in the oxidizable fraction increased to a value higher than that of the residual phase.     

Isotopic characterisation of lead in contaminated soils from the vicinity of a non-ferrous metal smelter near Plovdiv, Bulgaria

Soil samples from the vicinity of a non-ferrous metal smelter near Plovdiv, Bulgaria contained very high concentrations of cadmium, lead and zinc (up to 140, 4900 and 5900 mg kg(-1), respectively). A roadside soil in a relatively uncontaminated area also contained high concentrations of the same metals (24, 1550 and 1870 mg kg(-1), respectively) indicating that the transport of ores could be a source of contamination. Even though the lead isotope ratios in all the samples fell within a very narrow range (for example, 1.186-1.195 for (206)Pb/(207)Pb), the samples could be differentiated into three distinct groups: ores ((206)Pb/(207)Pb and (208)Pb/(207)Pb ratios of 1.1874-1.1884 and 2.4755-2.4807, respectively), current deposition (1.1864 and 2.4704-2.4711, respectively) and local background (1.1927-1.1951 and 2.4772-2.4809, respectively). Although most of the current deposition has its origin in the ores used at the smelter, up to 12% could be from other sources such as petrol lead.     

Atmospheric lead deposition to Okefenokee Swamp, Georgia, USA

Contamination of the environment from atmospheric deposition during the twentieth century is pervasive even in areas ostensibly considered pristine or remote from point sources. In this study, Pb concentrations in a 210Pb-dated peat core collected from the Okefenokee Swamp, GA were used to assess historical contaminant input via atmospheric deposition. Lead isotope ratios were determined by dynamic reaction cell ICP-MS (DRC-ICP-MS). Increases in Pb concentration occurred in the late nineteenth century and a marked rise in Pb concentrations pre-dated the widespread use of leaded gasoline within the US. The 206Pb/207Pb ratios of 1.19 during this period were consistent with coal combustion emissions. A later increase in Pb concentration, concurrent with a trend toward more radiogenic 206Pb/207Pb ratios in gasoline is consistent with an increased input of Pb from leaded gasoline emissions. However, it appears that coal combustion emissions remain a major source of Pb to the Okefenokee.     

Historical reconstruction of atmospheric lead pollution in central Yunnan province, southwest China: an analysis based on lacustrine sedimentary records

Atmospheric lead (Pb) pollution during the last century in central Yunnan province, one of the largest non-ferrous metal production centers in China, was reconstructed using sediment cores collected from Fuxian and Qingshui Lakes. Lead concentrations and isotopic ratios (²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb) were measured in sediment cores from both lakes. The operationally defined chemical fractions of Pb in sediment core from Fuxian Lake were determined by the optimized BCR procedure. The chronology of the cores was reconstructed using ²¹⁰Pb and ¹³⁷Cs dating methods. Similar three-phase variations in isotopic ratios and enrichment factors of Pb were observed in the sediment cores from both lakes. Before the 1950s, the sediment data showed low ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios and enrichment factors (EFs?=?~1), indicating that the sedimentary Pb was predominantly of lithogenic origin. However, these indices were increased gradually between the 1950s and the mid-1980s, implying an atmospheric Pb deposition. The EFs and isotopic ratios of Pb reached their peak during recent years, indicating aggravating atmospheric Pb pollution. The average anthropogenic Pb fluxes since the mid-1980s were estimated to be 0.032 and 0.053 g m^?2 year^?1 recorded in Fuxian and Qingshui cores, respectively. The anthropogenic Pb was primarily concentrated in the reducible fraction. Combining the results of Pb isotopic compositions and chemical speciations in the sediment cores and in potential sources, we deduced that recent aggravating atmospheric Pb pollution in central Yunnan province should primarily be attributed to regional emissions from non-ferrous metal production industries.     

Metal contamination in the lichen Alectoria sarmentosa near the copper smelter of Murdochville, Québec

Lichens were used to evaluate the metal pollution in a forest ecosystem around the smelter of Murdochville, Canada. As reached values 5.8 times higher in the smelter vicinity than in the 'background' sites. This enrichment was 2 times higher for 3 metals (Cu, Cd and Pb). The highest As, Ba, Cd, Cu, and Pb concentrations in lichens were 4, 112, 1, 23, 50 and 952mg/kg respectively. Contamination declined exponentially with increasing distance from the smelter and was related to elevation and slope exposition to the smelter flux. (206)Pb/(207)Pb and (206)Pb/(204)Pb ratios were low close to the smelter (1.16 and 18), but increased with distance to constant values (1.19 and 18.7) and showed an inverse correlation with lead concentrations. Forest contamination was detectable up to 30km from the smelter.     

Trace metal contamination of sediments in an e-waste processing village in China

This study examined trace metal contamination of sediments in Guiyu, China where primitive e-waste processing activities have been carried out. It was found that some river sediments in Guiyu were contaminated with Cd (n.d.-10.3mg/kg), Cu (17.0-4540mg/kg), Ni (12.4-543mg/kg), Pb (28.6-590mg/kg), and Zn (51.3-324mg/kg). The (206)Pb/(207)Pb and (208)Pb/(207)Pb ratios of the Pb-contaminated sediments of Lianjiang (1.1787+/-0.0057 and 2.4531+/-0.0095, respectively) were lower than those of Nanyang River (1.1996+/-0.0059 and 2.4855+/-0.0082, respectively), indicating a significant input of non-indigenous Pb with low (206)Pb/(207)Pb and (208)Pb/(207)Pb ratios. Copper, Pb and Zn in the non-residual fractions noticeably increased in the contaminated sediments compared to those in the uncontaminated sediments. A genuine concern is associated with potential transport of the contaminated sediments downstream and enhanced solubility and mobility of trace metals in the non-residual fractions.     

Pb isotopes as tracers of mining-related Pb in lichens, seaweed and mussels near a former Pb-Zn mine in West Greenland

Identification of mining-related contaminants is important in order to assess the spreading of contaminants from mining as well as for site remediation purposes. This study focuses on lead (Pb) contamination in biota near the abandoned ‘Black Angel Mine’ in West Greenland in the period 1988-2008. Stable Pb isotope ratios and total Pb concentrations were determined in lichens, seaweed and mussels as well as in marine sediments. The results show that natural background Pb (²⁰⁷Pb/²⁰⁶Pb: 0.704-0.767) and Pb originating from the mine ore (²⁰⁷Pb/²⁰⁶Pb: 0.955) have distinct isotopic fingerprints. Total Pb in lichens, seaweed, and mussels was measured at values up to 633, 19 and 1536 mg kg⁻¹ dry weight, respectively, and is shown to be a mixture of natural Pb and ore-Pb. This enables quantification of mining-related Pb and shows that application of Pb isotope data is a valuable tool for monitoring mining pollution.     

Accumulation and quantitative estimates of airborne lead for a wild plant (Aster subulatus)

Foliar uptake of airborne lead is one of the pathways for Pb accumulation in plant organs. However, the approximate contributions of airborne Pb to plant organs are still unclear. In the present study, aerosols (nine-stage size-segregated aerosols and total suspended particulates), a wild plant species (Aster subulatus) and the corresponding soils were collected and Pb contents and isotopic ratios in these samples were analyzed. Average concentration of Pb was 96.5 ± 63.5 ng m⁻³ in total suspended particulates (TSP) and 20.4 ± 5.5 ng m⁻³ in the fine fractions of size-segregated aerosols (SSA) (<2.1 μm), higher than that in the coarser fractions (>2.1 μm) (6.38 ± 3.71 ng m⁻³). Enrichment factors show that aerosols and soils suffered from anthropogenic inputs and the fine fractions of the size-segregated aerosols enriched more Pb than the coarse fractions. The order of Pb contents in A. subulatus was roots > leaves > stems. The linear relationship of Pb isotope ratios (²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb) among soil, plant and aerosol samples were found. Based on the simple binary Pb isotopic model using the mean ²⁰⁶Pb/²⁰⁷Pb ratios in TSP and in SSA, the approximate contributions of airborne Pb into plant leaves were 72.2% and 65.1%, respectively, suggesting that airborne Pb is the most important source for the Pb accumulation in leaves. So the combination of Pb isotope tracing and the simple binary Pb isotope model can assess the contribution of airborne Pb into plant leaves and may be of interest for risk assessment of the exposure to airborne Pb contamination.     

Using stable lead isotopes to trace heavy metal contamination sources in sediments of Xiangjiang and Lishui Rivers in China

Lead isotopes and heavy metal concentrations were measured in two sediment cores sampled in estuaries of Xiangjiang and Lishui Rivers in Hunan province, China. The presence of anthropogenic contribution was observed in both sediments, especially in Xiangjiang sediment. In the Xiangjiang sediment, the lower ²⁰⁶Pb/²⁰⁷Pb and higher ²⁰⁸Pb/²⁰⁶Pb ratio, than natural Pb isotope signature (1.198 and 2.075 for ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb, respectively), indicated a significant input of non-indigenous Pb with low ²⁰⁶Pb/²⁰⁷Pb and high ²⁰⁸Pb/²⁰⁶Pb. The corresponding concentrations of heavy metals (As, Cd, Zn, Mn and Pb) were much higher than natural values, suggesting the contaminations of heavy metals from extensive ore-mining activities in the region.     

Sphagnum mosses as archives of recent and past atmospheric lead deposition in Switzerland

Sphagnum mosses received from a herbarium and collected recently from a peat bog surface, were used to assess the isotopic character of past and recent atmospheric Pb deposition in Switzerland and to constrain possible Pb sources. Lead removed from the moss surface was isotopically similar to that measured in the corresponding solid plant, suggesting that neither preservative actions for the herbarium samples nor dust had affected the isotopic composition of the samples. The addition of HCl to aqueous extracts to remove surface particles from the plants released more Pb compared to H₂O alone. The changes in isotope ratios between Sphagnum collected during the past c. 130 yr were significantly greater than the small fluctuations between and among species collected at any one time. Three isotope ratio plots and emission inventories indicated that the most likely source of atmospheric Pb was coal-burning at the turn of the century, fly ash from waste incineration until approximately 1950, and gasoline combustion after that. The pollution record derived from the Sphagnum plants is in good agreement with other archives from Switzerland (peat, sediment, ice) and with other herbarium records in Europe.     

Metal contamination and solid phase partitioning of metals in urban roadside sediments

This study was undertaken to assess the anthropogenic impact on metal concentrations of urban roadside sediments (N = 633) in Seoul city, Korea and to estimate the potential mobility of selected metals (Zn, Cu, Pb, Cr, Ni, and Cd) using sequential extraction. Comparison of metal concentrations in roadside sediments with mean background values in sediments collected from first- or second-order streams in Korea shows that Zn, Cu and Pb are most affected by anthropogenic inputs. The 206Pb/207Pb ratios of roadside sediments (range = 1.1419-1.1681; mean 1.1576 +/- 0.0068) suggest that Pb is mainly derived from industrial sources rather than from leaded gasoline. A five-step sequential extraction of roadside sediments showed that Zn, Cd and to a lesser degree Ni occur predominantly in the carbonate bound fraction, while Pb is highest in the reducible fraction, Cu in the organic fraction, and Cr in the residual fraction. It was found that the concentrations in the readily available exchangeable fraction were generally low for most metals examined, except for Ni whose exchangeable fraction was appreciable (average 15.2%). Considering the proportion of metals bound to the exchangeable and carbonate fractions, the comparative mobility of metals probably decreases in the order of Zn > Ni > Cd > Pb > Cu > Cr. As potential changes of redox state and pH may remobilize the metals bound to carbonates, reducible, and/or organic matter, and may release and flush them through drain networks into streams, careful monitoring of environmental conditions appears to be very important. With respect to ecotoxicity, it is apparent the Zn and Cu pollution is of particular concern in Seoul city.     

Heavy metals and Pb isotopic composition of aerosols in urban and suburban areas of Hong Kong and Guangzhou,South China—Evidence of the long-range transport of air contaminants

Rapid urbanization and industrialization in South China has placed great strain on the environment and on human health. In the present study, the total suspended particulate matter (TSP) in the urban and suburban areas of Hong Kong and Guangzhou, the two largest urban centres in South China, was sampled from December 2003 to January 2005. The samples were analysed for the concentrations of major elements (Al, Fe, Mg and Mn) and trace metals (Cd, Cr, Cu, Pb, V and Zn), and for Pb isotopic composition. Elevated concentrations of metals, especially Cd, Pb, V and Zn, were observed in the urban and suburban areas of Guangzhou, showing significant atmospheric trace element pollution. Distinct seasonal patterns were observed in the heavy metal concentrations of aerosols in Hong Kong, with higher metal concentrations during the winter monsoon period, and lower concentrations during summertime. The seasonal variations in the metal concentrations of the aerosols in Guangzhou were less distinct, suggesting the dominance of local sources of pollution around the city. The Pb isotopic composition in the aerosols of Hong Kong had higher ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb ratios in winter, showing the influence of Pb from the northern inland areas of China and the Pearl River Delta (PRD) region, and lower ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb ratios in summer, indicating the influence of Pb from the South Asian region and from marine sources. The back trajectory analysis showed that the enrichment of heavy metals in Hong Kong and Guangzhou was closely associated with the air mass from the north and northeast that originated from northern China, reflecting the long-range transport of heavy metal contaminants from the northern inland areas of China to the South China coast.     

Contamination and source differentiation of Pb in park soils along an urban-rural gradient in Shanghai

Urban soil Pb contamination is a great human health risk. Lead distribution and source in topsoils from 14 parks in Shanghai, China were investigated along an urban-rural gradient. Topsoils were contaminated averagely with 65 mg Pb kg⁻¹, 2.5 times higher than local soil background concentrations. HCl-extracts contained more anthropogenic Pb signatures than total sample digests as revealed by the higher ^207/206Pb and ^208/206Pb ratios in extracts (0.8613 ± 0.0094 and 2.1085 ± 0.0121 versus total digests 0.8575 ± 0.0098 and 2.0959 ± 0.0116). This suggests a higher sensitivity of HCl-extraction than total digestion in identifying anthropogenic Pb sources. Coal combustion emission was identified as the major anthropogenic Pb source (averagely 47%) while leaded gasoline emission contributed 12% overall. Urbanization effects were observed by total Pb content and anthropogenic Pb contribution. This study suggests that to reduce Pb contamination, Shanghai might have to change its energy composition to clean energy.     

<Emphasis Type="Bold">Tracing lead contamination in foods in the city of Kolkata,India</Emphasis>

Lead isotopic ratios (LIR) of eight common food items, street dust, coal, diesel, sediments, lead ore and rainwater from India have been reported for the first time in this paper. This study characterized the source and extent of lead pollution in the different foodstuff consumed in Kolkata, a major metropolis of eastern India. The atmospheric lead input to the food items, sold openly in busy roadside markets of the city, has been quantified. The mean 207/206 and 208/206 LIRs of the eight food items ranged from 0.8847 to 0.8924 and 2.145 to 2.167, respectively. Diesel had the highest mean 207/206 and 208/206 values of 0.9015 and 2.1869, respectively, apart from the lead ore. The food items had a mean lead concentration between 3.78 and 43.35 mg kg^?1. The two ratio scatter plots of all the different environmental matrices were spread linearly between the uncontaminated Ichapur sediment and diesel. The 207/206 LIRs of the coal with a mean of 0.8777 did not fall in the linear trend, while the street dust and food samples overlapped strongly. The rainwater sample had a 207/206 LIR of 0.9007. Contaminated sediments in Dhapa, the repository of the city’s municipal garbage, had a mean 207/206 LIR of 0.8658. The corresponding value obtained from the sewage-fed vegetable grown there was 0.8058. The present study indicated that diesel was one of the main contributor to Pb pollution. The atmospheric lead contribution to the food items was in the range of 68.48–86.66 %.     

Isotopic evidence of pollutant lead sources in Northwestern France

Ratios of stable lead isotopes (²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb, ²⁰⁸Pb) are used to characterize both spatial and temporal variations in anthropogenic emissions of industrial lead aerosols to the atmosphere of northwestern France. Differences in isotopic compositions of aerosols collected from a rural area (Wimereux) in the Nord-Pas de Calais region along the English Channel in 1982–1983 (²⁰⁶Pb/²⁰⁷Pb=1.108±0.005) and 1994 (²⁰⁶Pb/²⁰⁷Pb=1.148±0.003) are paralleled by similar variations in urban aerosols within France during the same period (e.g., ²⁰⁶Pb/²⁰⁷Pb=1.115±0.008 from 1981–1989 and 1.143±0.006 from 1992–1995). These results correlate well with recent findings in the Mediterranean basin (Alleman, 1997) where this radiogenicity increase is clearly associated with industrial sources other than leaded gasoline that has remained relatively constant during its phasing out (²⁰⁶Pb/²⁰⁷Pb=1.08–1.11). Here we used archived data, air mass trajectories and aerosol diameters combined with isotopic signatures to confirm this trend at a regional scale. Indeed, the main industrial signatures from lead smelting (²⁰⁶Pb/²⁰⁷Pb=1.133±0.001) and steel metallurgy (²⁰⁶Pb/²⁰⁷Pb=1.196±0.015) in northwestern France appear more radiogenic than that of leaded gasoline. The shift in isotopic compositions also conform with the systematic change in the mean size (diameter) of aerosols at Wimereux, which ranged from 0.30 to 0.61 μm in 1982–1984 and from 0.70 to 0.89 μm in 1994.     

Remanence of lead pollution in an urban river system: a multi-scale temporal and spatial study in the Seine River basin,France

Total lead (Pb) concentration and Pb isotopic ratio (²⁰⁶Pb/²⁰7Pb) were determined in 140 samples from the Seine River basin (France), covering a period of time from 1945 to 2011 and including bed sediments (bulk and size fractionated samples), suspended particulate matter (SPM), sediment cores, and combined sewer overflow (CSO) particulate matter to constrain the spatial and temporal variability of the lead sources at the scale of the contaminated Seine River basin. A focus on the Orge River subcatchment, which exhibits a contrasted land-use pattern, allows documenting the relation between hydrodynamics, urbanization, and contamination sources. The study reveals that the Pb contamination due to leaded gasoline that peaked in the 1980s has a very limited impact in the river nowadays. In the upstream Seine River, the isotopic ratio analysis suggests a pervasive contamination which origin (coal combustion and/or gasoline lead) should be clarified. The current SPM contamination trend follows the urbanization/industrialization spatial trend. Downstream of Paris, the lead from historical use originating from the Rio Tinto mine, Spain (²⁰⁶Pb/²⁰⁷Pb?=?1.1634?±?0.0001) is the major Pb source. The analysis of the bed sediments (bulk and grain size fractionated) highlights the diversity of the anthropogenic lead sources in relation with the diversity of the human activities that occurred in this basin over the years. The “urban” source, defined by waste waters including the CSO samples (²⁰⁶Pb/²⁰⁷Pb?=?1.157?±?0.003), results of a thorough mixing of leaded gasoline with “historical” lead over the years. Finally, a contamination mixing scheme related to hydrodynamics is proposed.