Anthropogenic and lithogenic sources of lead in Lower Silesia (Southwest Poland): An isotope study of soils,basement rocks and anthropogenic materials

To discriminate possible anthropogenic and lithogenic sources of Pb in Lower Silesia (SW Poland), the Pb isotope composition was investigated in a spectrum of rocks and anthropogenic materials as well as within 10 soil profiles. Silicate rocks in Lower Silesia have ²⁰⁶Pb/²⁰⁷Pb ratios that vary from 1.17 for serpentinites to 1.38 for gneisses, and this variability is reflected in the isotope composition of the mineral soil horizons. The Pb isotope composition of coals, ores and anthropogenic materials (slags and fly ashes) is rather uniform, with ²⁰⁶Pb/²⁰⁷Pb ratios ranging from 1.17 to 1.18. Similar ratios were observed in ore and coal samples from Upper Silesia. The O soil horizons also have uniform ²⁰⁶Pb/²⁰⁷Pb ratios of 1.17–1.18 and the heterogeneity of the ²⁰⁶Pb/²⁰⁷Pb ratios increases with depth in the soil profiles. Five soils, with varying Pb concentrations, analysed far from contamination centres, show consistent, approximately 2-fold enrichment in Pb concentration from the C to A horizons, which is consistent with natural re-distribution of Pb within the profiles. The increase in the Pb concentration is accompanied by a decrease in ²⁰⁶Pb/²⁰⁷Pb ratios, also attributed to natural Pb isotope fractionation. Four soil profiles from industrial areas show variable enrichments in Pb concentrations and these are attributed to anthropogenic input from air-borne pollutants or even slag particles at smelting sites. The implication is that a lithogenic Pb source can deviate from the basement rock composition, and detailed isotope characteristics of the geological background and natural enrichments in soils are often needed to determine the lithogenic/anthropogenic proportions of Pb in soils.     

Lead in sediments and suspended particulate matter of the German Bight: natural versus anthropogenic origin

Sediments (568) and suspended particulate matter (SPM, 302 samples) of the southern German Bight and the adjacent tidal flat areas were analysed for selected major elements (Al, Fe, K), trace metals (Mn, Pb), and ²⁰⁶Pb/²⁰⁷Pb ratios using XRF, ICP–OES, ICP–MS. For selected samples a leaching procedure with 1 M HCl was used to estimate the Pb fraction associated with labile phases (e.g. Mn/Fe-oxihydroxide coatings) in contrast to the resistant mineral matrix. Enrichment factors versus average shale (EFS) reveal elevated Pb contents for all investigated sediments and SPM in the following order: Holocene tidal flat sediments (HTF, human-unaffected) <recent tidal flat sediments (RTF) <Helgoland Island mud hole sediments (MH) <nearshore SPM (SPM concentration>5 mg l⁻¹) < offhore SPM (<5 mg l⁻¹). Besides pollution, RTF contain elevated amounts of natural Pb-rich materials (K-feldspars and heavy minerals) due to a man-made high-energy environment (dike building) in comparison to HTF. ²⁰⁶Pb/²⁰⁷Pb ratios of RTF (1.192±0.019) are similar to the local geogenic background, determined from HTF (1.207±0.008). In contrast, Pb isotope ratios of nearshore SPM (1.172±0.007) and offshore SPM (1.166±0.012) show a distinct shift towards the anthropogenic/atmospheric signal of 1.11–1.14. This difference between RTF and SPM supports the assumption of low deposition rates of fine material in the intertidal systems. As the ²⁰⁶Pb/²⁰⁷Pb ratios of SPM do not reach the pure anthropogenic signal, the adsorbed Pb fraction was examined (leaching). However, the leachates also contained large amounts of geogenic Pb (SPM ≈40%, recent sediments ≈60%). The authors assume that the uptake of natural Pb occurs in nearshore waters, presumably in the turbid intertidal systems. Possible sources for dissolved Pb are mobilisation during weathering (geogenic signal) and dissolution of oxihydroxide coatings with subsequent release from porewaters, and unspecific riverine input. Comparatively small parts of SPM leave the coastal water mass and reach the open North Sea. This process therefore leads to a decontamination of the tidal flat sediments. Due to more pronounced atmospheric input, the offshore SPM becomes enriched in anthropogenic Pb as indicated by decreasing ²⁰⁶Pb/²⁰⁷Pb ratios with increasing distance from the coast.     

Sources and chronology of atmospheric lead deposition to a Canadian Shield lake: Inferences from Pb isotopes and PAH profiles

The depth-distribution of lead and its stable isotope ratios were determined in a dated sediment core from a Canadian Shield lake receiving anthropogenic Pb inputs exclusively from atmospheric deposition. The results demonstrate that anthropogenic Pb deposited to the sediments of this lake since the preindustrial period can be modeled successfully using as little as two isotopically distinct Pb types. The first, whose flux was not detectable before 1850, reached a maximum value around 1950, and then decreased significantly thereafter; it was characterized by ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁶Pb/²⁰⁸Pb ratios of 1.222 and 0.495, respectively, and was derived mainly from coal combustion. The second, whose flux was not detectable before 1880, increased sharply to exceed that of the Pb type derived from coal combustion around 1930, and reached a maximum in the mid 1970s; it is characterized by ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁶Pb/²⁰⁸Pb ratios of 1.179 and 0.482, respectively, and was derived mainly from leaded gasoline combustion and industrial sources. The chronology of deposition of these two anthropogenic lead types agrees well with the historical records of fossil fuel uses in Canada and the USA, and also with the history of sediment-deposited polycyclic aromatic hydrocarbons (PAHs) originating from coal combustion. The inventory of Pb derived from coal combustion (0.09 μmol cm⁻²) is ∼30% of that derived mainly, but not exclusively, from leaded gasoline (0.31 μmol cm⁻²). Apportionment among source regions of lead deposited to the sediments during the period when leaded gasoline dominated Pb atmospheric emissions indicates that ∼50% of this lead originated in the USA.     

A 2400-year record of trace metal loading in lake sediments of Lagoa Vermelha, southeastern Brazil

Sediments of the Lagoa Vermelha (Red Lake), situated in the Ribeira Valley, southeastern Brazil, are made of a homogeneous, organic-rich, black clay with no visible sedimentary structures. The inorganic geochemical record (Al, As, Ba, Br, Co,Cs, Cr, Fe, Mn, Ni, Rb, Sc, Sb, V, Zn, Hg and Pb) of the lake sediments was analyzed in a core spanning 2430 years. The largest temporal changes in trace metal contents occurred approximately within the last 180 years. Recent sediments were found to be enriched in Pb, Zn, Hg, Ni, Mn, Br and Sb (more than 2-fold increase with respect to the “natural background level”). The enhanced accumulation of Br, Sb, and Mn was attributed to biogeochemical processes and diagenesis. On the other hand, the anomalous concentrations of Pb, Zn, Hg and Ni were attributed to pollution. As Lagoa Vermelha is located in a relatively pristine area, far removed from direct contamination sources, the increased metal contents of surface sediments most likely resulted from atmospheric fallout. Stable Pb isotopes provided additional evidence for anthropogenic contamination. The shift of ²⁰⁶Pb/²⁰⁷Pb ratios toward decreasing values in the increasingly younger sediments is consistent with an increasing contribution of airborne anthropogenic lead. In the uppermost sediments (0-10 cm), the lowest values of the ²⁰⁶Pb/²⁰⁷Pb ratios may reflect the influence of the less radiogenic Pb from the Ribeira Valley District ores (²⁰⁶Pb/²⁰⁷Pb between 1.04 and 1.10), emitted during the last 50 years.     

Pb concentrations and isotope ratios of soil O and C horizons in Nord-Trøndelag,central Norway: Anthropogenic or natural sources?

Soil O and C horizon samples (N = 752) were collected at a sample density of 1 site/36 km² in Nord-Trøndelag and parts of Sør-Trøndelag (c. 25,000 km²), and analysed for Pb and three of the four naturally occurring Pb isotopes (²⁰⁶Pb, ²⁰⁷Pb and ²⁰⁸Pb) in a HNO₃/HCl extraction. Soil O and C horizons are decoupled in terms of both Pb concentrations and Pb isotope ratios. In the soil C horizon the Grong-Olden Culmination, a continuous exposure of the Precambrian crystalline basement across the general grain of the Caledonian orogen, is marked by a distinct ²⁰⁶Pb/²⁰⁷Pb isotope ratio anomaly. No clear regional or even local patterns are detected when mapping the Pb isotope ratios in the soil O horizon samples. Variation in the isotope ratios declines significantly from the soil C to the O horizon. On average, Pb concentrations in the O horizon are four times higher and the ²⁰⁶Pb/²⁰⁷Pb isotope ratio is shifted towards a median of 1.15 in comparison to 1.27 in the C horizon. It is demonstrated that natural processes like weathering in combination with plant uptake need to be taken into account in order to distinguish anthropogenic input from natural influences on Pb concentration and the ²⁰⁶Pb/²⁰⁷Pb isotope ratio in the soil O horizon.     

Historical lead pollution in the central region of Guizhou province,China: A record of lead stable isotopes of lake sediments

Economic reform in China since 1978 has accelerated economic development nationwide hugely, but has also brought about some environmental pollution. In order to identify the primary Pb source to the atmosphere in the central Guizhou region, Pb isotopic ratios in the acid soluble fraction of sediment from Hongfeng Lake were investigated. Lead isotopes in the lake sediments record the history of regional atmospheric Pb pollution. Before the economic reform in 1978, the ²⁰⁸Pb/²⁰⁶Pb and ²⁰⁶Pb/²⁰⁷Pb ratios in the leachates of lake sediments were constant, with a range of 2.0060 to 2.0117 and of 1.2314 to 1.2355, respectively. In the early period of economic reform (1978 to 1988), with the rapid industrial growth in Guizhou province, the acid soluble Pb isotope ratios in the lake sediments changed sharply: the ²⁰⁸Pb/²⁰⁶Pb ratios increased from 2.0212 to about 2.05, while the ²⁰⁶Pb/²⁰⁷Pb ratios decreased from 1.2251 to 1.2060. Emissions from Pb-ore-related industries are suggested to be the major pollution source of Pb in this period. Due to output from a local power plant since 1988, the isotope ratios of the acid soluble Pb in sediments in 1990s are characterized by a little higher radiogenic Pb (²⁰⁸Pb/²⁰⁶Pb = 2.0340–2.0400; ²⁰⁶Pb/²⁰⁷Pb = 1.2122–1.2158) than for the 1980s.     

Influences on the extent and record of heavy metal pollution in sediment cores from Loch Tay in a mineralised area of Scotland

The distribution and Inventories of Pb in the sediments of Loch Tay have been strongly influenced by inputs from past Pb mining activity, as demonstrated by correlation with the characteristic ²⁰⁶Pb/²⁰⁷Ph signature of the Tyndrum ore deposit. A major depositional event, perhaps associated with the cessation of Pb mining in the area, has been dated at 1906–1928 by the ²¹⁰Pb method. Zinc and Cu have been influenced to a lesser extent by mining, as shown by comparison with inventories in Loch Lomond. Profiles of As, Mn and Fe have been affected by post-depositional diagenetic remobilisation processes. The results serve as a benchmark, with Au mining set to commence at Cononish, near Tyndrum, in 1996.     

Anthropogenic Pb accumulation in forest soils from Lake Clair watershed: Duchesnay experimental forest (Québec, Canada)

Mineral soil horizons (Ae, Bhf1, Bhf2, Bf, BC and C) were carefully collected from two podzolic soil profiles in the Lake Clair watershed (Québec) in order to assess anthropogenic trace metal accumulation. Petrographic and selective analyses were performed to establish the soil mineralogy and properties. Furthermore, a complete sequential extraction procedure has been applied to help understanding the complex chemical speciation of Pb in forest soils. Chemical speciation of Pb showed a strong vertical gradient: 85% of this metal is mainly partitioned in refractory minerals in the C-horizon whereas in the upper Bhf1 and Ae-horizons, less than 50% of Pb is associated with this fraction. In the Ae-horizon, for example, 35%, 30% and 12% of total Pb, respectively, is associated with the exchangeable, labile organic matter and amorphous Fe-Mn oxides fractions. The distribution of Pb and Cr in the studied forest soils mainly reflects progressive contamination of the watershed by anthropogenic atmospheric sources. The anthropogenic source is indicated by elevated Cr and Pb concentrations in the topsoil (Bhf and Ae) horizons and by strong negative correlation between ²⁰⁶Pb/²⁰⁷Pb ratios and total Pb concentrations. According to these isotopic values, penetration of anthropogenic Pb does not exceed 10 cm in both soil profiles. Below this depth, both Pb concentrations and isotopic ratios remain nearly constant and similar to values observed in pre-anthropogenic sediments from Lake Clair. These values are interpreted as the natural geochemical backgrounds of the watershed. Based on that behaviour, calculated anthropogenic Pb net inputs amounted to between 1.24 and 1.8 g/m².     

Tracing diffuse anthropogenic Pb sources in rural soils by means of Pb isotope analysis

Knowledge of the cause and source of Pb pollution is important to abate environmental Pb pollution by taking source-related actions. Lead isotope analysis is a potentially powerful tool to identify anthropogenic Pb and its sources in the environment. Spatial information on the variation of anthropogenic Pb content and anthropogenic Pb sources in rural topsoils is remarkably limited. This study presents results of a survey of approximately 350 topsoil samples from rural locations covering the entire Netherlands, for which the bulk geochemical and Pb isotope compositions were determined. The specific aim of this study is to determine the anthropogenic Pb sources in the topsoils from rural areas in The Netherlands. The spatial distribution of anthropogenic Pb in soils in The Netherlands will be explained in terms of land use and pollution sources.Nearly all studied topsoils display Pb contents that exceed the amount expected based on the soil lithology. The range in Pb isotope ratios of the additional Pb fraction in rural Dutch topsoils is established at 1.056–1.199, 2.336–2.486 and 0.452–0.490 for ²⁰⁶Pb/²⁰⁷Pb, ²⁰⁷Pb/²⁰⁸Pb and ²⁰⁶Pb/²⁰⁸Pb, respectively. Five land use types are distinguished (forest, open nature, moor, arable land and grassland) with distinct isotopic compositions for added Pb. Additional Pb in soils of natural areas (forest, open nature and moor) has on average lower ²⁰⁶Pb/²⁰⁷Pb, ²⁰⁸Pb/²⁰⁷Pb and ²⁰⁶Pb/²⁰⁸Pb ratios than the agricultural soils (arable land and grassland). Additional Pb in both natural area soils and agricultural soils is interpreted to be of anthropogenic origin: most likely a mixture of coal/galena, incinerator ashes and gasoline Pb. The dominant sources of additional Pb in the topsoil of open nature areas are most likely incinerator ash and gasoline Pb. In contrast, the on average higher ²⁰⁶Pb/²⁰⁷Pb, ²⁰⁸Pb/²⁰⁷Pb and ²⁰⁶Pb/²⁰⁸Pb ratios of additional Pb in agricultural soils are most likely caused by the presence of animal manure and N–P fertilizers.Several areas are observed with notably high additional Pb contents (26–211 mg/kg on an organic matter-free basis) in the topsoil. The largest area is the Randstad area, which has the highest population and traffic density, and hosts a considerable fraction of the Dutch chemical industry. Two other areas with high additional Pb contents in the topsoil are located near the Dutch borders and are most likely influenced by German and Belgian chemical industries. The topsoils in the coastal dunes and southern, central and northern forests are characterized by relatively low additional Pb contents (<10 mg/kg on an organic matter-free basis). The population, traffic and chemical industry density is low in these areas and no fertilizers are applied.     

Determination of the extent of anthropogenic Pb migration through fractured sandstone using Pb isotope tracing

The extent of vertical migration of anthropogenic Pb beneath a medieval smelting site in Derbyshire, U.K. has been estimated using the determination of total Pb concentrations and ²⁰⁶Pb/²⁰⁷Pb isotope ratio from samples taken down 6 m of drill core. Preliminary studies of total Pb concentrations established that the surface slag derived from the smelting contained up to 16% Pb and that the normal background levels in uncontaminated sandstone were 10±2 ppm. Sample analyses beneath the site revealed elevated Pb concentrations in fracture infill clays (270 ppm Pb) and sandstone (76–83 ppm Pb). Both are well above the background Pb concentration.Lead isotope analysis of the slag wastes, the underlying contaminated sandstone and fracture infill has shown that all 3 contain very similar isotope ratios for ²⁰⁶Pb/²⁰⁷Pb (1.1802–1.1820). However, matched control sandstone samples show that the background ²⁰⁶Pb/²⁰⁷Pb isotope ratio (1.1670 ± 0.003) is distinctly different. This would indicate that both the sandstone and fracture infill underlying the historical smelting site contain a substantial proportion of Pb that has been derived from the overlying contamination.The application of total Pb concentrations along the core and isotope analysis suggest that anthropogenically derived Pb from the smelting site (that was operated between 665 and 445 a BP) has migrated to a depth of 4.50 m. Assuming a uniform migration rate and a mean time of migration of 555 a, then the mean migration rate is estimated to be 8 ± 2 mm/a.The proportion of natural versus anthropogenic Pb in the samples has been estimated from small variations in the ²⁰⁶Pb/²⁰⁷Pb isotope ratio. If the slag is considered to contain 100% anthropogenic Pb and the uncontaminated sandstone considered to contain 100% natural Pb, the linear interpolation can be applied between the 2 end members of the isotope ratio. The use of this approach to the ²⁰⁶Pb/²⁰⁷Pb ratio measurements has shown that 88% of the Pb in the contaminated sandstone (i.e. 69 ppm from a mean total Pb concentration of 78.5 ppm) has been derived from the anthropogenic Pb at the surface. For the fracture infill sample taken at a depth of 4.50 m, and with a total Pb concentration of 270 ppm, the % of Pb that has been derived from the slag wastes is approximately 98% (equivalent to 265 ppm Pb). The remaining Pb in both these samples (9.4 and 5 ppm, respectively) is deduced to have originated from the natural background concentration of Pb in the sandstone.The closeness of these estimates to the measured background concentration, suggests that a simple two-source model of Pb contamination is valid for this site.     

Chronological variations in concentrations and isotopic compositions of anthropogenic atmospheric lead in sediments of a remote subalpine pond

Lead concentrations decrease 4-fold in going from the surface of sediments in a mountain pond to relatively small values in layers 130 yr old. There is a corresponding change in the $\text{Pb}{}^{206}\text{Pb}{}^{207}$ ratio in the sediments from industrial-like values of 1.18 near the surface to natural values of 1.24 at depth. Concentrations of Ca, Sr, and Ba remain relatively constant with depth. The excess Pb is shown to be of eolian anthropogenic origin, through isotopic, chemical, and mass balance relationships with metals in aerosols, dry deposition, and precipitation. This proves that inputs of contamination Pb were nearly absent centuries ago in a remote non-domesticated subalpine canyon, but are present today in that ecosystem in amounts more than 20 times the natural inputs and are irrefutably linked with industrial sources. As a consequence of these inputs, present Pb concentrations have been elevated 5-fold in plants and 50-fold in animals above natural levels. These Pb contamination effects are being caused by present-day atmospheric concentrations of ~10 ng Pb/m³. The ecosystem studied here characterizes the vast remote non-domesticated regions of North America, and these findings indicate that such regions are highly polluted by industrial Pb aerosols.     

High-resolution historical records from Pettaquamscutt River basin sediments: 2. Pb isotopes reveal a potential new stratigraphic marker

A high-resolution record of Pb deposition in Rhode Island over the past 250 yr was constructed using a sediment core from the anoxic Pettaquamscutt River basin. The sedimentary Pb concentration record shows the well-described maximum associated with leaded gasoline usage in the United States. Diminished Pb variability during recorded periods of local industrial activity (1735 to 1847) supports the greater importance of regional atmospheric lead transport vs. local inputs. The Pb isotopic composition at this site shows a clear maximum in anthropogenic ²⁰⁶Pb/²⁰⁷Pb in the mid-1800s. Similar peaks have also been observed in sediments from Chesapeake Bay and the Great Lakes, suggesting a common source. Possible causes for this event include mining and smelting of Pb ores in the Upper Mississippi Valley district, which accounted for almost all Pb production in the United States in that period. The timing of this event can provide an important stratigraphic marker for sediments deposited in the past 200 yr in the Northeastern United States. The downcore profile of anthropogenic ²⁰⁶Pb/²⁰⁷Pb provides a classic example of how changes in the mixture of ores for production of tetraethyl lead caused a regional-scale shift in the sedimentary record, and suggests that coal could have played a secondary role in Pb emissions after 1920.     

Isotopic evidence for the source of lead in the North Pacific abyssal water

The absence of accurate measurements of lead (Pb) isotopic composition in the North Pacific abyssal water has made it difficult to assess the relative importance of what are believed to be the two major Pb sources: the natural Pb introduced during preindustrial time and recent anthropogenic Pb resulting from leaded gasoline combustion and high temperature industrial activities. Here we report a vertical profile of seawater ²⁰⁶Pb/²⁰⁷Pb ratio and a meridional section of Pb concentration in the North Pacific Ocean. We observe 2-3-fold increases in Pb concentration along the deep-water flow path and a deep-water ²⁰⁶Pb/²⁰⁷Pb ratio (∼1.188) substantially lower than the pre-industrial value (∼1.210). These data suggest that anthropogenic Pb has invaded the North Pacific abyssal water and become the predominant Pb source there. A simple model calculation based on these data indicates that the anthropogenic Pb is transported to the deep ocean by sinking particles and that this Pb vertical flux has a ²⁰⁶Pb/²⁰⁷Pb ratio that decreased during the past two centuries.     

湘东南铜山岭铅锌多金属矿床成矿时代与成矿物质来源——Sm-Nd等时线年龄和Pb同位素证据

铜山岭铅锌多金属矿床位于扬子地块湘南-桂东北坳陷与华夏地块粤北坳陷的拼贴部位,是中国南岭多金属成矿区代表性矿床之一。为确定矿床成矿时代,挑选铜山岭铅锌多金属矿床中含矿矽卡岩的石榴子石进行Sm-Nd同位素定年,获得的等时线年龄为173±3Ma,指示成矿作用发生于燕山早期。对金属硫化物矿物进行了Pb同位素分析,其~(206)Pb/~(204)Pb、~(207)Pb/~(204)Pb、~(208)Pb/~(204)Pb平均值分别为18.602、15.701、38.729,表明成矿物质来源于相对富集铀铅、略微亏损钍铅的上地壳源区。从(~(207)Pb/~(204)Pb)i-(~(206)Pb/~(204)Pb)i铅同位素演化模式图可知,寄主花岗闪长岩是铜山岭铅锌多金属矿床的重要物质来源,且成矿物质中可能含有寄存在花岗闪长岩中的地幔组分。     

Stable lead isotope ratios and metals in freshwater mussels from a uranium mining environment in Australia’s wet-dry tropics

Concentrations of Fe, Mn, Cu, Zn, U and Pb, and stable Pb isotopes ²⁰⁶Pb, ²⁰⁷Pb and ²⁰⁸Pb were measured via inductively coupled plasma mass spectrometry in sediments, water and freshwater mussels (Velesunio angasi) from two catchments in the Alligator Rivers Region, Australia. Sediment U and Pb concentrations were higher in Magela Creek downstream than upstream of the Ranger U mine due to the mineralised nature of the catchment and potential local input of sediment from the mine site. Water metal concentrations were highest in Georgetown Creek, which is a tributary of Magela Creek and part drains the Ranger mine site, but there was little difference in concentrations between the Magela Creek upstream and downstream sites. Metal concentrations in mussels collected immediately upstream and downstream of the mine site also showed little difference, whereas Pb isotope ratios displayed a very distinct pattern. The ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb isotope ratios were more uranogenic downstream than upstream of the site and also more uranogenic than ratios measured in Sandy Billabong, a reference billabong in a catchment not influenced by U mineralisation. Isotope ratios were also more uranogenic in younger mussels, potentially due to the increasing footprint of the mine site over the past decade. The most uranogenic ratios were found in mussels from Georgetown Creek and at a site approximately 2 km downstream. At Mudginberri Billabong, approximately 12 km downstream of the Ranger mine, the relative contribution of uranogenic Pb to the total Pb concentration in mussels was small and overwhelmed by the input of industrial Pb with a Broken Hill type Pb signature. Whereas metal uptake by and thus concentrations in mussel flesh are influenced by water chemistry, mussel condition and metabolic rates, Pb isotope ratios are independent of these factors and provide a powerful means of source apportionment of contaminants in mussels and waterways, in particular in an U mining environment.     

Lead and stable Pb-isotope characteristics of tropical soils in north-eastern Brazil

Stable Pb-isotope ratios are widely used as tracers for Pb-sources in the environment. Recently, a few publications have challenged the predominating view of environmental applications of Pb-isotopes. Present applications of Pb-isotopic tracers in soils largely represent the northern hemisphere. This study focuses on tropical soils from Paraíba, north-eastern Brazil. Lead concentrations and Pb-isotopic signatures (both 7N HNO₃) were determined at 30 sites along a 327 km E–W-transect, from the Atlantic coast at João Pessoa to some kilometers west of Patos, to identify possible processes for the observed (and anticipated) distribution pattern. Thirty samples each of litter (ORG) and top mineral soil (TOP) were taken on pasture land at suitable distance from roads or other potential contamination sources. Lead-content was determined by inductively-coupled plasma atomic emission spectrometry (ICP-AES) and the ratios of ²⁰⁶Pb/²⁰⁷Pb, ²⁰⁶Pb/²⁰⁸Pb, and ²⁰⁸Pb/²⁰⁷Pb by ICP-sector field mass spectrometry (ICP-SFMS). Both sample materials show similarly low Pb-concentrations with a lower median in the ORG samples (ORG 3.4 mg kg⁻¹ versus TOP 6.9 mg kg⁻¹). The ²⁰⁶Pb/²⁰⁷Pb ratios revealed a large spread along the transect with median ²⁰⁶Pb/²⁰⁷Pb ratios of 1.160 (ORG) and 1.175 (TOP). The ²⁰⁶Pb/²⁰⁷Pb ratios differ noticeably between sample sites located in the Atlantic Forest biome along the coast and sample sites in the inland Caatinga biome. The “forest” sites were characterised by a significant lower median and a lower spread in the ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁶Pb/²⁰⁸Pb ratios compared to the Caatinga sites. Results indicate a very restricted influence of anthropogenic activities (individual sites only). The main process influencing the spatial variability of Pb-isotope ratios is supposed to be precipitation-dependent bioproductivity and weathering.     

Lead isotopes as tracers of anthropogenic pollution in urban topsoils of Mexico City

A survey was performed to trace the main source of anthropogenic Pb pollution in Mexico City through Pb isotopic signatures (²⁰⁸Pb/²⁰⁴Pb, ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁶Pb/²⁰⁷Pb, and ²⁰⁸Pb/²⁰⁷Pb) from 103 urban topsoil (0–5 cm) samples. Those were collected in the metropolitan area of Mexico City and compared with isotopic compositions of leaded gasoline (LG), domestic Pb ores (DLO) and parent rock (PR). The isotope ratios (IRs) of Pb were determined by inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) and total Pb concentration analyzed by wavelength dispersive X-ray fluorescence (WDXRF). The range of Pb concentrations levels in urban topsoil samples was 15–473 mg/kg. The IR values obtained for these samples were 37.965–39.718 (²⁰⁸Pb/²⁰⁴Pb), 18.375–19.204 (²⁰⁶Pb/²⁰⁴Pb), 1.177–1.218 (²⁰⁶Pb/²⁰⁷Pb) and 2.443–2.496 (²⁰⁸Pb/²⁰⁷Pb). Analyzed topsoil samples with low Pb content (<50 mg/kg) displayed high dispersion in ²⁰⁸Pb/²⁰⁴Pb values, which are determined by different natural sources. Samples with 51–200 mg/kg Pb content, shown low dispersion that revealed the mixing between the natural Pb and anthropogenic Pb. The assessment of the IR values shown that, as Pb concentration increases, a trend toward gasoline IR data has been observed. The results obtained by this research suggest that although the use of leaded petrol had been banned in Mexico since 1997, the Pb pollution in the urban topsoils due to the historical use of Pb in petrol is still significant.     

Plumbotectonic aspects of polymetallic vein mineralization in Paleozoic sediments and Proterozoic basement of Moravia (Czech Republic)

A regional isotopic study of Pb and S in hydrothermal galenas and U–Pb and S in potential source rocks was carried out for part of Moravia, Czech Republic. Two major generations of veins, (syn-) Variscan and post-Variscan, are defined based on the Pb-isotope system together with structural constraints (local structures and regional trends). The Pb-isotopic compositions of galena plot in two distinct populations with outliers in ²⁰⁶Pb/²⁰⁴Pb–²⁰⁷Pb/²⁰⁴Pb space. Galena from veins hosted in greywackes provides a cluster with the lowest Pb–Pb ratios: ²⁰⁶Pb/²⁰⁴Pb = 18.15–18.27, ²⁰⁷Pb/²⁰⁴Pb = 15.59–15.61, ²⁰⁸Pb/²⁰⁴Pb = 38.11–38.23. Those hosted in both limestones and greywackes provide the second cluster: ²⁰⁶Pb/²⁰⁴Pb = 18.37–18.44, ²⁰⁷Pb/²⁰⁴Pb = 15.60–15.63, ²⁰⁸Pb/²⁰⁴Pb = 38.14–38.32. These clusters suggest model Pb ages as Early Carboniferous and Triassic–Jurassic, the latter associated with MVT-like deposits. Two samples from veins hosted in Proterozoic rocks lie outside the two clusters: in metagranitoid (²⁰⁶Pb/²⁰⁴Pb = 18.55, ²⁰⁷Pb/²⁰⁴Pb = 15.64, ²⁰⁸Pb/²⁰⁴Pb = 38.29) and in orthogneiss (²⁰⁶Pb/²⁰⁴Pb = 18.79, ²⁰⁷Pb/²⁰⁴Pb = 15.73, ²⁰⁸Pb/²⁰⁴Pb = 38.54). The results from these two samples suggest an interaction of mineralizing fluids with the radiogenic Pb-rich source (basement?). The values of δ³⁴S suggest the Paleozoic host rocks (mostly ?6.7 to +5.2‰ CDT) as the source of S for hydrothermal sulfides (mostly ?4.8 to +2.5‰ CDT). U–Pb data and Pb isotope evolutionary curves indicate that Late Devonian and Early Carboniferous sediments, especially siliciclastics, are the general dominant contributor of Pb for galena mineralization developed in sedimentary rocks. Plumbotectonic mixing occurred, it is deduced, only between the lower and the upper crust (the latter involving Proterozoic basement containing heterogeneous radiogenic Pb), without any significant input from the mantle. It is concluded that in the Moravo–Silesian and Rhenohercynian zones (including proximal districts in Poland) lead and sulfur have been mobilized from the adjacent rocks during multiple hydrothermal events in processes that are remarkably comparable in timing, geochemistry of fluids and nature of sources.     

Heavy metal pollution of coastal river sediments, north-eastern New South Wales, Australia: lead isotope and chemical evidence

 Heavy metal and metalloid concentrations within stream-estuary sediments (<180-μm size fraction) in north-eastern New South Wales largely represent natural background values. However, element concentrations (Ag, As, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Zn) of Hunter River sediments within the heavily industrialized and urbanized Newcastle region exceed upstream background values by up to one order of magnitude. High element concentrations have been found within sediments of the Newcastle Harbour and Throsby Creek which drains into urbanized and light industry areas. Observed Pb enrichments and low ²⁰⁸Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁶Pb/²⁰⁴Pb ratios are likely caused by atmospheric deposition of Pb additives from petrol and subsequent Pb transport by road run-off waters into the local drainage system. Sediments of the Richmond River and lower Manning, Macleay, Clarence, Brunswick and Tweed River generally display no evidence for anthropogenic heavy metal and metalloid contamination (Ag, As, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Zn). However, the rivers and their tributaries possess localized sedimentary traps with elevated heavy metal concentrations (Cu, Pb, Zn). Lead isotope data indicate that anthropogenic Pb provides a detectable contribution to investigated sediments. Such contributions are evident at sample sites close to sewage outlets and in the vicinity of the Pacific Highway. In addition, As concentrations of Richmond River sediments gradually increase downstream. This geochemical trend may be the result of As mobilization from numerous cattle-dip sites within the region into the drainage system and subsequent accumulation of As in downstream river and estuary sediments. Received: 5 September 1997 · Accepted: 4 November 1997     

Lead and its isotopes in the sediment of three sites on the Lebanese coast: Identification of contamination sources and mobility

Lead concentrations and isotopic composition of sediment samples collected from three sites within the Lebanese coastal zones were measured: at Akkar, Dora and Selaata. Akkar is located far from any direct source of contamination, while Dora and Selaata receive urban and industrial wastes, respectively. Low Pb concentrations (6–16 μg g⁻¹) were detected in the Akkar sediments, and high concentrations of Pb (70–101 μg g⁻¹) were detected in the Dora sediments. Measuring stable isotope ratios of Pb makes it possible to identify the principal sources of Pb in the Akkar sediments as Pb emitted from gasoline combustion and Pb originating from natural sources. On the other hand, Pb stable isotopic ratios in Dora sediments indicate that they are more highly influenced by anthropogenic sources. Isotopic Pb ratios in the Selaata deposits, where Pb concentrations range between 5 and 35 μg g⁻¹, have an exceptional radiogenic signature for marine sediments 1.25 < ²⁰⁶Pb/²⁰⁷Pb < 1.6 and 0.5 < ²⁰⁶Pb/²⁰⁸Pb < 0.67, which shows the impact of the phosphogypsum discharged by Selaata’s chemical plant. Isotopic Pb analysis applied to EDTA extracts, to test the mobility of Pb, shows that that this mobility is high (>60%) after 24 h of extraction, and that the extracted Pb is less radiogenic than the residual Pb.