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.     

Applications of Anthropogenic Lead ArchaeoStratigraphy (ALAS Model) to Hydrocarbon Remediation

A model, which employs the use of high precision stable lead isotopic analyses, has been developed to estimate the age of hydrocarbon releases. The ALAS Model (Anthropogenic Lead ArchaeoStratigraphy) is based on calibrated, systematic increases in lead isotope ratios of gasolines caused by shifts in sources of lead ores used by the U.S. lead industry, including manufacturers of alkylleads, to more radiogenic Mississippi Valley Type (MVT) deposits. Acquisition of high quality samples (free product, gasoline-impacted soil and groundwater) of known age and subsequent analyses of the hydrocarbon component by high precision lead isotopic analyses by thermal ionization mass spectrometry (TIMS) have produced the ALAS Model calibration curve. Age uncertainties range from - 1 to 2 years for gasoline releases which occurred between 1965 and 1990, the major era of leaded gasoline usage. Analytical methods required to measure lead isotope ratios on ~5 nanograms of lead with precisions and accuracy of < - 0.1% (2 SEM ) are discussed in detail. Published lead isotopic measurements of gasoline-derived anthropogenic lead of samples throughout the United States are used to demonstrate the wide geographic range over which the ALAS Model may be applied. Two representative case studies involving an early 1970s free product release in California and the discrimination of a 1970s from modern unleaded gasoline release in Florida demonstrate the use of the model on single and multiple hydrocarbon releases, respectively, in different geographic regions of the United States. A third investigation focuses on the use of lead isotopes to correlate dissolved phase hydrocarbons with their source, in this case, unleaded (aka low lead) gasoline releases in New Jersey. Dissolved phase hydrocarbons (BTEX/MTBE) are shown to carry the lead isotopic signature of the unleaded gasoline into groundwater, allowing the specific source of the release to be identified. Investigations of lead isotopes as tracers of MTBE in groundwater are ongoing. However, both laboratory and field data indicate MTBE carries the lead isotopic signature of its unleaded gasoline source into groundwater, demonstrating the potential of the lead isotopic system as a discriminant of MTBE sources. Although developed to estimate the age of leaded gasoline releases, the ALAS Model has been successfully applied in studies requiring age dating of jet-A, diesel, kerosene, motor oil, and heating oil. These petroleum distillates are suspected of accidentally acquiring small, yet significant quantities of alkylleads during refining, allowing accurate ALAS Model ages to be determined. When lead levels in these petroleum distillates are within their normal range, typically tens to hundreds of ppb lead, it is possible to use lead isotopic ratios to correlate environmental releases of these products to their source or other releases.     

Applications of Anthropogenic Lead ArchaeoStratigraphy (ALAS Model) to Hydrocarbon Remediation

A model, which employs the use of high precision stable lead isotopic analyses, has been developed to estimate the age of hydrocarbon releases. The ALAS Model (Anthropogenic Lead ArchaeoStratigraphy) is based on calibrated, systematic increases in lead isotope ratios of gasolines caused by shifts in sources of lead ores used by the U.S. lead industry, including manufacturers of alkylleads, to more radiogenic Mississippi Valley Type (MVT) deposits. Acquisition of high quality samples (free product, gasoline-impacted soil and groundwater) of known age and subsequent analyses of the hydrocarbon component by high precision lead isotopic analyses by thermal ionization mass spectrometry (TIMS) have produced the ALAS Model calibration curve. Age uncertainties range from  ± 1 to 2 years for gasoline releases which occurred between 1965 and 1990, the major era of leaded gasoline usage. Analytical methods required to measure lead isotope ratios on ∼5 nanograms of lead with precisions and accuracy of < ± 0.1% (2_SEM) are discussed in detail. Published lead isotopic measurements of gasoline-derived anthropogenic lead of samples throughout the United States are used to demonstrate the wide geographic range over which the ALAS Model may be applied. Two representative case studies involving an early 1970s free product release in California and the discrimination of a 1970s from modern unleaded gasoline release in Florida demonstrate the use of the model on single and multiple hydrocarbon releases, respectively, in different geographic regions of the United States. A third investigation focuses on the use of lead isotopes to correlate dissolved phase hydrocarbons with their source, in this case, unleaded (aka low lead) gasoline releases in New Jersey. Dissolved phase hydrocarbons (BTEX/MTBE) are shown to carry the lead isotopic signature of the unleaded gasoline into groundwater, allowing the specific source of the release to be identified. Investigations of lead isotopes as tracers of MTBE in groundwater are ongoing. However, both laboratory and field data indicate MTBE carries the lead isotopic signature of its unleaded gasoline source into groundwater, demonstrating the potential of the lead isotopic system as a discriminant of MTBE sources. Although developed to estimate the age of leaded gasoline releases, the ALAS Model has been successfully applied in studies requiring age dating of jet-A, diesel, kerosene, motor oil, and heating oil. These petroleum distillates are suspected of accidentally acquiring small, yet significant quantities of alkylleads during refining, allowing accurate ALAS Model ages to be determined. When lead levels in these petroleum distillates are within their normal range, typically tens to hundreds of ppb lead, it is possible to use lead isotopic ratios to correlate environmental releases of these products to their source or other releases.     

Potential for childhood lead poisoning in the inner cities of Australia due to exposure to lead in soil dust

This article presents evidence demonstrating that the historical use of leaded gasoline and lead (Pb) in exterior paints in Australia has contaminated urban soils in the older inner suburbs of large cities such as Sydney and Melbourne. While significant attention has been focused on Pb poisoning in mining and smelting towns in Australia, relatively little research has focused on exposure to Pb originating from inner-city soil dust and its potential for childhood Pb exposures. Due to a lack of systematic blood lead (PbB) screening and geochemical soil Pb mapping in the inner cities of Australia, the risks from environmental Pb exposure remain unconstrained within urban population centres.     

Levels of dioxins, dibenzofurans and selected other chlorinated organic compounds in food from Russia

Food is considered to be the main source of dioxins (PCDDs) and dibenzofurans (PCDFs) for human intake, but there are relatively few publications reporting the levels of dioxins and furans in food samples.^(1–4) Food samples from western to eastern Russia were collected during three recent trips by one of us (AS), and tested for dioxins and dibenzofurans to provide some indication of environmental contamination. The results show that in specific food samples there are more dioxins present than dibenzofurans, but in fish samples the opposite is true. We compare the levels found in Russian food with levels found in samples from other countries, on both wet weight and lipid basis. These Russian samples show ranges similar to but slightly lower than those seen in other industrial countries.     

Origins of Manganese in Air Participates in California

The proportions of manganese to other metals in samples of airborne fine particles taken at some sites in California have increased greatly since the beginning of 1985. Here, data are presented which indicate that the addition of manganese to leaded gasoline is largely responsible for this increase. Concentrations of manganese, silicon, titanium, iron, lead and other elements in airborne particles were measured using energy-dispersive X-ray fluorescence analysis. Coefficients of correlation among levels of manganese, iron and lead measured at twenty sites in California were calculated. Levels of manganese and iron are generally highly correlated because of the presence of large amounts of these elements in the earth’s crust. Levels of airborne manganese and lead at sites In Southern California are often highly correlated, suggesting a vehicular source of manganese. Observed manganese concentrations are apportioned into two major sources: the earth’s crust and motor vehicles. The apportionment indicates that vehicular emissions of manganese may account for a significant part of the total at urban sites in Southern California. At most other sites, the contribution from vehicles is found to be far smaller than that from the earth’s crust.     

Characterization of atmospheric particulates, particle-bound transition metals and polycyclic aromatic hydrocarbons of urban air in the centre of Athens (Greece)

The concentrations of trace metals and polycyclic aromatic hydrocarbons (PAHs) adsorbed to total suspended particulate (TSP) and finer fractions of airborne particulate matter (PM) were determined from a site in the centre of Athens (Greece), which is characterized by heavy local traffic and is densely populated, during the winter and summer periods in 2003-2004. Also, we collected and analyzed samples of diesel and gasoline exhaust particles from local vehicles (buses, taxis and private cars) and from chimney exhaust of residential central heating appliances. A seasonal effect was observed for the size distribution of aerosol mass, with a shift to larger fine fractions in winter. The most commonly detected trace metals in the TSP and PM fractions were Fe, Pb, Zn, Cu, Cr, V, Ni and Cd and their concentrations were similar to levels observed in heavily polluted urban areas from local traffic and other anthropogenic emissions. Analysis of 16 PAHs bound to PM showed that they are mostly traffic related. In general, the fine particulate PAHs concentrations were higher than coarse particles. The most common PAHs in PM(10.2) and PM(2.1) were pyrene, phenanthrene, acenapthylene and fluoranthene, which are associated with diesel and gasoline exhaust particles. The results of this study underlined the importance of local emission sources, especially vehicular traffic, central heating and other local anthropogenic emissions. Compared with other big cities, Athens has much higher levels of airborne particles, especially of the finer fractions PM(10) and PM(2.5), correlated with traffic-related air pollution.     

Airborne lead in the Springfield, Missouri, area during a 19-year period (1975-1993)

Concentrations of airborne lead at Springfield, Missouri, in 1975-1993 have been determined by analysis of particulate material collected on glass-fiber filters during the 19-year period. Nitric acid-soluble lead in 1100 samples collected at a total of 19 monitoring stations was determined by atomic absorption spectroscopy and by differential pulse polarography. Ambient concentrations of airborne lead were found to decrease steadily (by more than 90%) during this period in spite of increases in area population and in automobile traffic. The decrease is significantly correlated with national trends in total emissions of lead to the atmosphere and with US ambient lead levels. Airborne lead from a coal-fired power plant was small compared with that from gasoline burning.     

The use of Pb isotopes to differentiate between contemporary and ancient sources of pollution in Greece

Stable lead isotopes are used to illustrate the relation source–receptor and to differentiate between sources of pollution in Greece. Air filters collected in the Kozani–Ptolemais lignite mining area, West Macedonia, point to an impact from gasoline lead as well as lead from the combustion of lignite. This is supported by lead isotope data of wheat grown on reclaimed land. Lead isotope analyses of contemporary teeth from the Lavrio sulphide mining area, southeast of Greece, show the imprint of previous mining activities as well as traffic emissions. Moreover, the Lavrio teeth can be distinguished from one tooth from Athens; the Athens tooth show a stronger impact of gasoline lead. Lead data also imply that the Greek top soil is contaminated by air pollution from earlier sulphide mining and smelting since Hellenic and Roman times.     

Blood lead levels among populations differentially exposed to vehicular exhaust in Rohtak, India

In the absence of local industrial sources of lead, leaded gasoline has been suggested as the major source of lead in the urban atmosphere of Rohtak town, situated near Delhi metropolitan city and with a high vehicular density. Blood lead levels were measured in 42 male volunteers from within the Rohtak area with varying degrees of exposure to vehicular exhaust. The occupationally exposed group with a daily exposure of 10-12 h in automobile workshops was found to have the highest levels of blood lead (mean value 21.26 microg dl(-1)) followed by roadside population (mean value 14.91 microg/dl(-1)). This group of people had a daily exposure of 8-10 h in their business establishments, situated at a distance of less than 5 to about 10 ft (< 1.5-c. 3.0 m) from the road with an average traffic density of 8000 vehicles day(-1). Urban residents were found to have higher blood lead levels (mean value 9.85 microg/dl(-1)) than the rural ones (mean value 3.34 microg/dl(-1)). The values were found to increase correspondingly with the increase in age and smoking habits within the particular categories of volunteers. The levels found in the present study are comparable to those reported from other major cities of India, but well within the tolerable limits as recommended by the European Economic Community.     

Chemical behavior of residential lead in urban yards in the United States

Long after federal regulations banned the use of lead-based paints and leaded gasoline, residential lead remains a persistent challenge. Soil lead is a significant contributor to this hazard and an improved understanding of physicochemical properties is likely to be useful for in situ abatement techniques such as phytoremediation and chemical stabilization. A laboratory characterization of high-lead soils collected from across the United States shows that the lead contaminants were concentrating in the silt and clay fractions, in the form of discrete particles of lead, as observed by scanning electron microscopy coupled with energy dispersive X-ray analysis. Soil lead varied widely in its solubility behavior as assessed by sequential and chelate extractions. Because site-specific factors (e.g., soil pH, texture, etc.) are believed to govern the solubility of the lead, understanding the variability in these characteristics at each site is necessary to optimize in situ remediation or abatement of these soils.     

The origin of atmospheric lead in Oslo,Norway, studied with the use of isotopic ratios

Application of the lead isotope method to differentiate between the local contribution of lead and its portion from long-range transport of air pollution from sources a few thousand kilometers away to the lead pollution level measured in the Oslo area in Norway is discussed. The ²⁰⁶Pb/²⁰⁴Pb ratio is of particular interest in this respect. The results of measurements presented in the paper show that phase-out of lead additives to gasoline in Northern Europe has not phased out the Pb contamination of the environment. The lead isotope method proved very useful to present a contribution of small local sources to the Pb contamination of the air in the Oslo area during the period when the combustion of gasoline, the major source of Pb contamination has been decreasing. Wood combustion is one of these sources in Norway. Lower impact of long-range transport of air pollutants emitted from sources in Eastern and Central Europe and transported with air masses to Scandinavia, during the recent 5 years, can also be traced utilizing isotopic ratios of lead. The application of tree-rings as environmental archives contributed significantly to elucidating the historical Pb pollution.     

Soviet and post-Soviet environmental management: lessons from a case study on lead pollution

Through a case study on lead pollution in the former Soviet Union, the linkage of policy, environmental science, and environmental management is explored, and compared with the US experience. Soviet bans on leaded gasoline and lead-based paint appear to have been effective. Regional governments, in cooperation with the petroleum industry, are taking the initiative in phasing out leaded gasoline, to some extent in defiance of federal policy. Problems with management of lead-acid batteries have been worsened by the collapse of the political system. Lack of reliable environmental data impedes reliable environmental assessment. The types of environmental measurements reflect an emphasis on multipollutant environmental contamination, rather than on human exposure to single pollutants.     

Airborne lead concentration levels on the Korean peninsula between 1991 and 2004

In this study, a comprehensive analysis was made to describe the environmental behavior and pollution status of lead (Pb) in 13 major cities in Korea in a 14-year time span (1991–2004). The results clearly indicate that spatial distribution of Pb is clearly distinguished between different city types and between different temporal intervals. The Pb concentration levels in the cities of strong industrial activities are found to be higher than those of relatively clean ones by approximately an order of magnitude. Examination of the seasonal patterns indicated a strong consistency in almost all cities so that Pb concentration peaked during spring and winter, while it dropped noticeably during summer. If the long-term trend of Pb pollution is examined for the entire study period (14 years), it appears to contrast between different city types in relation with the relative intensity of Pb pollution. In cities of strong industrial activities, the reduction of Pb seemed to occur more effectively due to the stringent measures implemented to ban metal emissions over the past decades. In contrast, such temporal patterns appear to be more complicated in cities with moderately or fairly clean environments. This is possibly due to the fact that the effect induced by the phase-out of the dominant source (i.e., leaded gasoline) became less significant, while other sources were further diversified and/or intensified through time. The overall results of this comprehensive study confirm the fact that the status of Pb pollution in most city areas can be reflected fairly sensitively by changes in social and environmental conditions.     

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.     

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.     

Tracking historical lead pollution in the coastal area adjacent to the Yangtze River Estuary using lead isotopic compositions

The rapid economic development in the Yangtze River Delta (YRD), China in the last three decades has had a significant impact on the environment of the East China Sea (ECS). Lead isotopic compositions of a ²¹⁰Pb dated sediment core collected from the coastal ECS adjacent to the Yangtze River Estuary were analyzed to track the Pb pollution in the region. The baseline Pb concentration in the coastal ECS sediments before the industrialization in China was 32 μg g⁻¹, and the corresponding ²⁰⁶Pb/²⁰⁷Pb ratio was 1.195. The high-resolution profiles of Pb flux and ²⁰⁶Pb/²⁰⁷Pb ratios had close relationships with the economic development and the history of the use of leaded gasoline in China, and they were clearly different from those of most European countries and United States.     

Environmental lead pollution threatens the children living in the Pearl River Delta region, China

Introduction and purpose

The objective of this study is to determine children??s blood lead levels and identify sources of lead exposure. Childhood lead exposure constitutes a major pediatric health problem today in China. A blood lead screening survey program for children in the age group of 2?C12?years residing in Pearl River Delta region, south of China, was carried out from Dec 2007 to Jan 2008.

Methods

Blood lead levels and lead isotope ratios of a total of 761 participants were assessed by inductively coupled plasma mass spectroscopy. Measurements of urban environmental samples for source identification of children lead exposure were also performed.

Results and conclusions

The geometric mean value of the children??s blood lead levels was 57.05???g/L, and 9.6% of them were higher than 100???g/L. The blood lead levels were still much higher than those in developed countries. Based on the data of environmental lead source inventories, lead isotopic tracing revealed that there is about 6.7% past used gasoline Pb embedded in Shenzhen residential dust and about 15.6% in Guangzhou dust, respectively.     

Lead contamination of the Seine River, France: geochemical implications of a historical perspective

Four sediment cores collected in the Seine River basin and dated between 1916 and 2003 were analyzed for lead concentrations and isotopic composition. In all four cores, the measured Pb concentration (up to 460 mg kg⁻¹) lies significantly above the natural background (27-40 mg kg⁻¹), although a significant decrease (down to 75 mg kg⁻¹) was observed during the second half of the 20th century which can be explained by the reduction of lead emissions. The ²⁰⁶Pb/²⁰⁷Pb ratio measured in these samples indicates that the main source of Pb used in the Paris conurbation is characterized by a “Rio Tinto” signature (defined as ²⁰⁶Pb/²⁰⁷Pb = 1.1634 ± 0.0001). A high contribution, up to 25%, from the leaded gasoline (characterized by ²⁰⁶Pb/²⁰⁷Pb = 1.08 ± 0.02) is revealed in the Seine River downstream Paris, indicating that lead from the leaded gasoline is preferentially released to the river.The dominating Pb signature in the Paris conurbation that is currently sampled through incinerators fumes (²⁰⁶Pb/²⁰⁷Pb = 1.1550 ± 0.0005) and waste water treatment plant (²⁰⁶Pb/²⁰⁷Pb = 1.154 ± 0.002), represents a mixture of highly recycled lead from the Rio Tinto mine and lead from leaded gasoline (imprinted by the low ²⁰⁶Pb/²⁰⁷Pb of the Broken Hill mine). This signature is called “urban” rather than “industrial”, because it is clearly distinct from the Pb that is found in areas contaminated by heavy industry, i.e. the heavy industries located on the Oise River which used lead from European ores characterized by high ²⁰⁶Pb/²⁰⁷Pb ratios (∼1.18-1.19) and possibly a minor amount of North American lead (²⁰⁶Pb/²⁰⁷Pb ratios > 1.20). The “urban” signature is also found in a rural area upstream of Paris in the 1970’s. At the Seine River mouth in 2003, Pb with an urban signature represents 70% of the total Pb sediment content, with the 30% remaining corresponding to natural Pb.     

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.