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Shooting activities is an important source of Pb in contaminated soils. Lead accumulates in superficial soil horizons because of its low mobility, favouring its uptake by plants and representing a high transference risk to the trophic chain. A combination of phytoremediation with nanoremediation techniques can be used to recover firing range soils and decrease the mobility, bioavailability and toxicity of Pb. This study examines in depth the changes in Pb behaviour in firing range soils by adding hydroxyapatite nanoparticles (HANPs). These nanoparticles (NPs) may immobilise Pb and improve the quality of these areas. The use of HANPs and the Pb effects were assessed in three different species (Sinapis alba L., Lactuca sativa L. and Festuca ovina L.), focusing on their germination and early growth, through phytotoxicity assays. Single extractions with CaCl 2 (0.01 M) in soils treated with HANPs show that these NPs retained Pb and reduced highly its availability and mobility. HR-TEM and TOF-SIMS were used to determine the interactions between HANPs and Pb, as well as with soil components. According to TOF-SIMS and HR-TEM/EDS analysis, Pb was mainly retained by HANPs but also associated lightly to organic matter, Fe compounds and silicates. Phytotoxicity assays exposed that S. alba , L. sativa and F. ovina were able to germinate and develop in the firing range soils despite the high available Pb contents before adding HANPs. After adding HANPs, Pb retention increased, favouring the germination and the growth of roots in the three species. These results suggest that HANPs can be used to decrease the availability and the toxicity of Pb without negative effects in the species growth. Accordingly, the combination of phytoremediation and nanoremediation techniques can be a great tool to stabilise these soils, avoiding the Pb transfer to nearby areas and its entry in the trophic chain. Unlabelled Image • HANPs reduce efficiently the available Pb contents in firing range soils. • HANPs favour the germination and root growth of S. alba , L. sativa and F. ovina. • TOF-SIMS/HR-TEM allow to assess the interactions among HANPs, Pb and soil components. • Pb mobility, availability and toxicity decrease greatly after treatment with HANPs. • Nanoremediation and phytoremediation can be effective to recover firing range soils. [ABSTRACT FROM AUTHOR]

Chalcophile (Ag, Cd, Co, Cu, Mo, Ni, Pb, Se, Tl, Zn) and lithophile (Al, Ba, Ce, Cr, Cs, Fe, La, Li, Mn, Nd, Rb, Sr, V, Y) trace elements (TEs) were determined in kidney, liver and muscle of beaver (Castor canadensis) from a rural watershed in southern Ontario, Canada. To estimate the relative bioavailability of TEs in the landscape, they were also determined in the dissolved (<0.45 μm) fraction of water from the river where the animals were harvested. Concentration ratios (tissue/water) always showed the greatest enrichments for Cd (kidney, 1.1 × 107; liver, 2.4 × 106; muscle, 7.2 × 105), most likely due to the metal binding properties of metallothioneins. Despite its potential toxicity, Tl also showed considerable enrichment: kidney, 4.2 × 104; liver 1.2 × 104; muscle 1.5 × 104. Enrichments of Cs and Rb exceeded those of Tl in all three tissues, suggesting that the chemical similarity of their ionic species (Cs+, Rb+, Tl+) to K+ may be the key to their uptake. Lithophile elements of limited solubility in natural waters (Al, Ce, La, Nd) show moderate enrichments, despite the lack of physiological role. The smallest enrichments were found for Sr and Ba, the two TEs which are most abundant in the river. Of the TEs considered essential for animal nutrition, V was the least enriched in tissue relative to water (liver 19×, kidney, 33× and muscle 28×). Despite the lack of physiological function and absence of any known sources of contamination, Al, Ag, Cd, Ce, Cs, La, Pb, Rb, and Tl, are all enriched in beaver tissue, relative to water, by at least three orders of magnitude, due to natural processes. The widespread abundance of beaver in Canada combined with the growing need to manage their numbers in populated regions offer a unique opportunity for monitoring environmental quality in the riparian zone. Unlabelled Image • beaver (Castor canadensis) were taken from a small, rural watershed in S. Ontario. • 10 chalcophile and 12 lithophile elements were determined using ICP-MS in a clean lab. • liver, kidney and muscle were compared with the dissolved fraction of the river. • Cd showed the greatest concentration ratios (105 – 107) and Sr the lowest ratios (tissue/water) • Ag, Ce, Cs, Pb, Rb, and Tl all yielded concentration ratios > 103 [ABSTRACT FROM AUTHOR]

Historical mining has a millennial scale history on the globe often leaving a long-lasting imprint on the environment. Previous results on trace metal concentrations in the Pyrenees, where extensive mining (Ag, Fe) occurred from the Antiquity to the 19th century, suggest that ≥600 tons of anthropogenic lead (Pb) is stored in soils in the Haut-Vicdessos area (France). Yet the potential bioavailability of this legacy contamination to contemporary biota remains unclear. We therefore asked if previously reported high-levels of legacy Pb can be seen in other environmental compartments including aquatic biota, and how these are distributed within the biota. Based on Pb-isotopic data, we also assessed if any Pb contamination found in contemporary biota can be linked to local/regional mining. Samples of sphagnum, soil, sediment, biofilm, and fish (Salmo trutta and Phoxinus phoxinus) were collected from three adjacent valleys in the Haut-Vicdessos area. Pb concentrations varied both between sites (i.e. decreasing concentrations with increasing distance from the former mine) and between within-site environmental compartments (i.e. soil > biofilm ≥ sediment > sphagnum > fish) as well as within organisms (i.e. entire organism > liver > muscle). Further, Pb-isotopic ratios (206Pb/207Pb, 208Pb/207Pb and 208Pb/206Pb) measured in soil, biofilm, and fish indicated both natural (weathering bedrock) and anthropogenic (industrial, transportation and/or former mining activities) sources of Pb-deposition to the area. Generally, body Pb-concentrations were within regulatory guidelines, yet contemporary biota in the upper Haut-Vicdessos area, and their prey, still showed a large range of Pb isotopic signatures, of which former mining activities appeared to have a strong influence. Our study showed that mining derived legacy Pb continues to affect onsite biota even if mining activities ceased >100 years ago, thus reflecting the long-lasting impact of human-environment interaction, suggesting that ecosystem conditions may remain impaired centuries after activities have ceased. Unlabelled Image • Historical mining is still a major source of Pb to contemporary aquatic ecosystems. • Concentrations of Pb decreases with increasing distance from a former Ag-Pb mine. • Pb concentrations were in the order soil > biofilm > sediment > sphagnum > fish. • Soils and biofilm prevents further dispersal and increased loadings of Pb to biota. • Fish Pb concentrations were in the order minnow > trout & whole fish > liver > muscle. [ABSTRACT FROM AUTHOR]

Metal mining activities have resulted in the widespread metal pollution of soils and sediments and are a worldwide health concern. Pb is often prolific in metal-mining impacted systems and has acute and chronic toxic effects. Environmental factors controlling diffuse pollution from contaminated riverbank sediment are currently seen as a “black box” from a process perspective. This limits our ability to accurately predict and model releases of dissolved Pb. Previous work by the authors uncovered key mechanisms responsible for the mobilisation of dissolved Zn. The current study identifies key mechanisms controlling the mobilisation of dissolved Pb, and the environmental risk these releases pose, in response to various sequences of “riverbank” inundation/drainage. Mesocosm experiments designed to mimic the riverbank environment were run using sediment severely contaminated with Pb, from a mining-impacted site. Results indicated that, although Pb is generally reported as less mobile than Zn, high concentrations of dissolved Pb are released in response to longer or more frequent flood events. Furthermore, the geochemical mechanisms of release for Zn and Pb were different. For Zn, mechanisms were related to reductive dissolution of Mn (hydr)oxides with higher concentrations released, at depth, over prolonged flood periods. For Pb, key mechanisms of release were related to the solubility of anglesite and the oxidation of primary mineral galena, where periodic drainage events serve to keep sediments oxic, particularly at the surface. The results are concerning because climate projections for the UK indicate a rise in the occurrence of localized heavy rainfall events that could increase flood frequency and/or duration. This study is unique in that it is the first to uncover key mechanisms responsible for dissolved Pb mobilisation from riverbank sediments. The mineralogy at the mining-impacted site is common to many sites worldwide and it is likely the mechanisms identified in this study are widespread. [ABSTRACT FROM AUTHOR]

Chronic exposure to heavy metals could affect cell-mediated immunity. The aim of this study was to explore the status of memory T cell development in preschool children from an e-waste recycling area. Blood lead (Pb) levels, peripheral T cell subpopulations, and serum levels of cytokines (IL-2/IL-7/IL-15), relevant to generation and homeostasis of memory T cells were evaluated in preschool children from Guiyu (e-waste-exposed group) and Haojiang (reference group). The correlations between blood Pb levels and percentages of memory T cell subpopulations were also evaluated. Guiyu children had higher blood Pb levels and increased percentages of CD4 + central memory T cells and CD8 + central memory T cells than in the Haojiang group. Moreover, blood Pb levels were positively associated with the percentages of CD4 + central memory T cells. In contrast, Pb exposure contributed marginally in the change of percentages of CD8 + central memory T cells in children. There was no significant difference in the serum cytokine levels between the e-waste-exposed and reference children. Taken together, preschool children from an e-waste recycling area suffer from relatively higher levels of Pb exposure, which might facilitate the development of CD4 + central memory T cells in these children. [ABSTRACT FROM AUTHOR]

Shooting activities are a very important source of contamination as they are commonly detected high concentrations of Pb in the soils from these facilities. Different remediation methods imply the immobilization of the pollutants by decreasing their mobility and availability and nanotechnology is a promising technique in this field. The effectiveness of calcium phosphate nanoparticles (CPNs) in the remediation of small-arms firing range and trap shooting range soils is evaluated in this work. The operationally defined extractable content of Pb, Cu and Zn is determined together with the interaction of the pollutants with the nanomaterials. Soil samples were treated with the CPNs and after the treatment the extractable contents of Cu, Pb and Zn decrease. To check the retention by the nanoparticles TOF-SIMS (Time of Flight Secondary Ion Mass Spectrometry) and HR-TEM-EDS (High Resolution Transmission Electron Microscopy with Energy Dispersive X-ray Spectroscopy) techniques were applied. The association of Pb and Cu to the CPNs was demonstrated by TOF-SIMS although it also indicated that not all the Pb and Cu contents are linked to the nanoparticles. By means of HR-TEM/EDS it was made out the filamentous shape and the size (50–150 nm long and 20–40 nm wide) of the CPNs together with their elemental composition (Ca, P and O). The CPNs were identified in treated soil samples together with signals of metals. The decrease on metal extractability detected is, in part, due to the association with CPNs but still more investigation is needed regarding mobility and availability of potentially hazardous elements in soils treated with nanoparticles. [ABSTRACT FROM AUTHOR]

Some 644 individual soil horizons from 169 sites in Scotland were analyzed for Pb concentration and isotopic composition. There were three scenarios: (i) 36 sites where both top and bottom (i.e. lowest sampled) soil horizons were classified as organic in nature, (ii) 67 with an organic top but mineral bottom soil horizon, and (iii) 66 where both top and bottom soil horizons were mineral. Lead concentrations were greater in the top horizon relative to the bottom horizon in all but a few cases. The top horizon 206 Pb/ 207 Pb ratio was lesser (outside analytical error) than the corresponding bottom horizon 206 Pb/ 207 Pb ratio at (i) 64%, (ii) 94% and (iii) 73% of sites, and greater at only (i) 8%, (ii) 3% and (iii) 8% of sites. A plot of 208 Pb/ 207 Pb vs. 208 Pb/ 206 Pb ratios showed that the Pb in organic top (i, ii) and bottom (i) horizons was consistent with atmospherically deposited Pb of anthropogenic origin. The 206 Pb/ 207 Pb ratio of the organic top horizon in (ii) was unrelated to the 206 Pb/ 207 Pb ratio of the mineral bottom horizon as demonstrated by the geographical variation in the negative shift in the ratio, a result of differences in the mineral horizon values arising from the greater influence of radiogenic Pb in the north. In (iii), the lesser values of the 206 Pb/ 207 Pb ratio for the mineral top horizon relative to the mineral bottom horizon were consistent with the presence of anthropogenic Pb, in addition to indigenous Pb, in the former. Mean anthropogenic Pb inventories of 1.5 and 4.5 g m − 2 were obtained for the northern and southern halves of Scotland, respectively, consistent with long-range atmospheric transport of anthropogenic Pb (mean 206 Pb/ 207 Pb ratio ~ 1.16). For cultivated agricultural soils (Ap), this corresponded to about half of the total Pb inventory in the top 30 cm of the soil column. [ABSTRACT FROM AUTHOR]

In the present study, the residual toxicity and impact of aged nZVI after a leaching experiment on heavy metal (Pb, Zn) polluted soils was evaluated. No negative effects on physico-chemical soil properties were observed after aged nZVI exposure. The application of nZVI to soil produced a significant increase in Fe availability. The impact on soil biodiversity was assessed by fluorescence in situ hybridization (FISH). A significant effect of nZVI application on microbial structure has been recorded in the Pb-polluted soil nZVI-treated. Soil bacteria molecular response, evaluated by RT-qPCR using exposure biomarkers (pykA, katB) showed a decrease in the cellular activity (pykA) due to enhanced intracellular oxidative stress (katB). Moreover, ecotoxicological standardised test on Caenorhabditis elegans ( C. elegans ) showed a decrease in the growth endpoint in the Pb-polluted soil, and particularly in the nZVI-treated. A different pattern has been observed in Zn-polluted soils: no changes in soil biodiversity, an increase in biological activity and a significant decrease of Zn toxicity on C. elegans growth were observed after aged nZVI exposure. The results reported indicated that the pollutant and its nZVI interaction should be considered to design soil nanoremediation strategies to immobilise heavy metals. [ABSTRACT FROM AUTHOR]

The effects of shooting-derived lead (Pb) on the structure and functioning of a forest ecosystem, and the recovery of the ecosystem after range abandonment were studied at an active shotgun shooting range, an abandoned shooting range where shooting ceased 20 years earlier and an uncontaminated control site. Despite numerous lead-induced changes in the soil food web, soil processes were only weakly related to soil food web composition. However, decomposition of Scots pine ( Pinus sylvestris ) needle litter was retarded at the active shooting range, and microbial activity, microbial biomass and the rate of decomposition of Pb-contaminated grass litter decreased with increasing soil Pb concentrations. Tree ( P. sylvestris ) radial growth was suppressed at the active shooting range right after shooting activities started. In contrast, the growth of pines improved at the abandoned shooting range after the cessation of shooting, despite reduced nitrogen and phosphorus contents of the needles. Higher litter degradation rates and lower Pb concentrations in the topmost soil layer at the abandoned shooting range suggest gradual recovery after range abandonment. Our findings suggest that functions in lead-contaminated coniferous forest ecosystems depend on the successional stage of the forest as well as the time since the contamination source has been eliminated, which affects, e.g., the vertical distribution of the contaminant in the soil. However, despite multiple lead-induced changes throughout the ecosystem, the effects were rather weak, indicating high resistance of coniferous forest ecosystems to this type of stress. [ABSTRACT FROM AUTHOR]

Abstract: In urban areas with high fallout of airborne particles, metal uptake by plants mainly occurs by foliar pathways and can strongly impact crop quality. However, there is a lack of knowledge on metal localization and speciation in plants after pollution exposure, especially in the case of foliar uptake. In this study, two contrasting crops, lettuce (Lactuca sativa L.) and rye-grass (Lolium perenne L.), were exposed to Pb-rich particles emitted by a Pb-recycling factory via either atmospheric or soil application. Pb accumulation in plant leaves was observed for both ways of exposure. The mechanisms involved in Pb uptake were investigated using a combination of microscopic and spectroscopic techniques (electron microscopy, laser ablation, Raman microspectroscopy, and X-ray absorption spectroscopy). The results show that Pb localization and speciation are strongly influenced by the type of exposure (root or shoot pathway) and the plant species. Foliar exposure is the main pathway of uptake, involving the highest concentrations in plant tissues. Under atmospheric fallouts, Pb-rich particles were strongly adsorbed on the leaf surface of both plant species. In lettuce, stomata contained Pb-rich particles in their apertures, with some deformations of guard cells. In addition to PbO and PbSO4, chemical forms that were also observed in pristine particles, new species were identified: organic compounds (minimum 20%) and hexagonal platy crystals of PbCO3. In rye-grass, the changes in Pb speciation were even more egregious: Pb–cell wall and Pb–organic acid complexes were the major species observed. For root exposure, identified here as a minor pathway of Pb transfer compared to foliar uptake, another secondary species, pyromorphite, was identified in rye-grass leaves. Finally, combining bulk and spatially resolved spectroscopic techniques permitted both the overall speciation and the minor but possibly highly reactive lead species to be determined in order to better assess the health risks involved. [Copyright &y& Elsevier]

Abstract: The effect of lead (Pb) toxicity on bone mineralization was investigated in a wild population of red-legged partridge (Alectoris rufa) inhabiting a farmland area contaminated with Pb-shot from recreational hunting activities in Albacete, a southeastern province of Spain. Femora from 40 specimens of red-legged partridge were analyzed for Pb by graphite furnace atomic absorption spectroscopy (GF-AAS), and for bone composition by Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD). The FTIR and DRX data of bone were analyzed in detail to determine possible alterations in bone mineral chemistry and crystallinity due to Pb toxicity. Results showed a marked decrease in the degree of mineralization as Pb concentrations in bone tissue increased while XRD analyses showed that the crystallinity of apatite crystals increased with the Pb load in bone. These load-dependent effects are indicative that Pb contamination altered bone remodeling by reducing new bone mineral formation and demonstrate that bone quality is a sensitive indicator of adverse effects on wild bird populations exposed to Pb pollution. [Copyright &y& Elsevier]

Abstract: The natural radionuclide 210Pb is commonly used to establish accurate and precise chronologies for the recent (past 100–150years) layers of peat deposits. The most widely used 210Pb-dating model, Constant Rate of Supply (CRS), was applied using data from three peat cores from Chao de Lamoso, an ombrotrophic mire in Galicia (NW Spain). On the basis of the CRS-chronologies, maximum Pb concentrations and enrichment factors (EFs) occurred in the 1960s and late 1970s, consistent with the historical use of Pb. However, maximum Pb fluxes were dated in the 1940s and the late 1960s, 10 to 20 years earlier. Principal component analysis (PCA) showed that, although the 210Pb distribution was mainly (74%) controlled by radioactive decay, about 20% of the 210Pb flux variability was associated with atmospheric metal pollution, suggesting an extra 210Pb supply source and thus invalidating the main assumption of the CRS model. When the CRS-ages were recalculated after correcting for the extra input from the 210Pb inventory of the uppermost peat layers of each core, Pb flux variations were consistent with the historical atmospheric Pb deposition. Our results not only show the robustness of the CRS model to establish accurate chronologies of recent peat deposits but also provide evidence that there are confounding factors that might influence the calculation of reliable peat accumulation rates (and thus also element accumulation rates/fluxes). This study emphasizes the need to verify the hypotheses of 210Pb-dating models and the usefulness of a full geochemical interpretation of peat bog records. [Copyright &y& Elsevier]

Abstract: Results are presented for a study of spatial distributions and temporal trends in concentrations of lead (Pb) from different sources in soil and vegetation of an arable farm in central Scotland in the decade since the use of leaded petrol was terminated. Isotopic analyses revealed that in all of the samples analysed, the Pb conformed to a binary mixture of petrol Pb and Pb from industrial or indigenous geological sources and that locally enhanced levels of petrol Pb were restricted to within 10m of a motorway and 3m of a minor road. Overall, the dominant source of Pb was historical emissions from nearby industrial areas. There was no discernible change in concentration or isotopic composition of Pb in surface soil or vegetation over the decade since the ban on the sale of leaded petrol. There was an order of magnitude decrease in Pb concentrations in road dust over the study period, but petrol Pb persisted at up to 43% of the total Pb concentration in 2010. Similar concentrations and spatial distributions of petrol Pb and non petrol Pb in vegetation in both 2001 and 2010, with enhanced concentrations near roads, suggested that redistribution of previously deposited material has operated continuously over that period, maintaining a transfer pathway of Pb into the biosphere. The results for vegetation and soil transects near minor roads provided evidence of a non petrol Pb source associated with roads/traffic, but surface soil samples from the vicinity of a motorway failed to show evidence of such a source. [Copyright &y& Elsevier]

Abstract: Analyses of metal and organic contaminants were carried out on 41 sediment cores, dated using 210Pb and 137Cs, from the heavily industrialized region of Sydney Harbour, N.S. to evaluate the history of contamination and to predict the rates of natural containment of the harbour by sediment burial. Geochronologies for metals (eg. Pb, As) and polycyclic aromatic hydrocarbons (PAHs) are correlated with the development of the steel and coke industries in the Sydney region while polychlorinated biphenyl (PCB) geochronologies reflect the disposal of electrical equipment used in the steel mill/coking operations. Pb was derived mainly from atmospheric emissions and its concentration has declined exponentially with time in harbour sediments since the closure of the steel mill/coke ovens in the 1980s with a time constant of about 15 years. This represents the time scale for the circulation of this particle-associated contaminant in transient catchment basins prior to permanent deposition in the sediments. PAH and PCB sediment concentrations have also declined exponentially with time since the 1980s, but with a smaller time constant of 10 years owing to the fact that they enter the harbour directly with steel mill and coke oven effluent rather than through atmospheric pathways. Since the time dependence for the burial of metal and organic inventories can be modeled by first order processes, future contaminant levels can be predicted for surface sediments in Sydney Harbour. Mean sediment concentrations of metal and organic contaminants in the upper 5 cm throughout most of the harbour are predicted to decline to levels below the effects range-medium (above which organisms are very likely to be negatively affected by the presence of a contaminant) by 2030. [Copyright &y& Elsevier]

Abstract: Uptake studies have shown that chickens foraging on soils contaminated with environmental pollutants accumulate these compounds into their eggs. Home-produced eggs thereby show higher contamination levels than commercially produced eggs. It was the aim of this study to identify the major source of two environmental pollutants in home-produced eggs, i.e. dioxins and lead, to formulate preventive measures to reduce the contamination levels of such eggs, and to assess the feasibility of the formulated measures in terms of the perception and behavior of private egg producers towards such measures. The major source of dioxins and lead in eggs, i.e. the soil, was identified by transfer calculations of the pollutants from the feed and soil towards eggs. Preventive measures to reduce soil intake or geophagy and hence egg contamination levels, were formulated and their feasibility evaluated through interviews with private chicken owners. The results show that a paved surface inside the henhouse, an indoor feeding place and providing a sufficient surface area per chicken were considered the most appropriate in terms of feasibility and willingness to apply the measures by the private chicken owners. To enhance the effect of the measures, a combination of measures supported and promoted at policy level is considered as a good strategy to reduce contamination levels in home-produced eggs. [Copyright &y& Elsevier]

Pb-LIII edge XANES spectra of atmospheric particles are directly obtained by fluorescent XAFS spectroscopy using a 19-element solid state detector (SSD). Particulate sample was collected on a quartz fiber filter using a high-volume air sampler, and the filter was cut into small pieces (25×25 mm). Then, surface layer of the filter piece was scaled and accumulated in order to enhance the particle density per filter unit. Use of 10 pieces of the surface layer enables the measurement of Pb-LIII edge XANES spectra on beamline BL01B1 at SPring-8, Hyogo, Japan. The shape of the Pb-LIII edge XANES spectra of the particulate sample is similar to the shapes of the spectra for PbS, PbCO3, PbSO4 and/or PbCl2. Additionally, the filter sample is also divided into water-soluble, 0.1 M HCl-extractable, and residual fractions of Pb compounds by a simple acid extraction procedure. We discuss the possibility of Pb speciation in the particulate samples with combination of highly sensitive XANES spectroscopy and simple acid extraction. [Copyright &y& Elsevier]

Arsenic, cadmium, chromium, lead, manganese, mercury and selenium were analyzed in the feathers of pigeon guillemots (Cepphus columba) from breeding colonies in Prince William Sound and in the Aleutian Islands (Amchitka, Kiska) to test the null hypothesis that there were no differences in metal levels as a function of location, gender, or whether the birds were from oiled or unoiled areas in Prince William Sound. Birds from locations with oil from the Exxon Valdez Oil Spill in the environment had higher levels of cadmium and lead than those from unoiled places in Prince William Sound, but otherwise there were no differences in metal levels in feathers. The feathers of pigeon guillemots from Prince William Sound had significantly higher levels of cadmium and manganese, but significantly lower levels of mercury than those from Amchitka or Kiska in the Aleutians. Amchitka had the lowest levels of chromium, and Kiska had the highest levels of selenium. There were few gender-related differences, although females had higher levels of mercury and selenium in their feathers than did males. The levels of most metals are below the known effects levels, except for mercury and selenium, which are high enough to potentially pose a risk to pigeon guillemots and to their predators. [Copyright &y& Elsevier]

Leaching of toxic metals from slag waste produced during smelting of Pb–Zn ores is generally considered to be negligible. A 1.4 million tonne stockpile of slag containing up to 2.5% Pb and other contaminants has accumulated on a smelter site at North Lake Macquarie, New South Wales, Australia, and it has also been freely used within the community for landscaping and drainage projects. It had been suggested that Pb in fine particles derived from the slags may be a potential contributor to the blood Pb of some children in this community, although there is conflicting evidence in the literature for such a hypothesis. Bioaccessibility of lead and selected metals derived from nine slag samples collected from areas of public open space was examined using a relatively simple in vitro gastric dissolution technique. Size analyses of the slag samples demonstrate that finely-sized material was present in the slags which could be ingested, especially by children. The finer-sized particles contain high levels of Pb (6490–41,400 ppm), along with Cd and As. Pb bioaccessibility of the slags was high, averaging 45% for −250 μm material and 75% for particles in the size range −53+32 μm. Increasing bioaccessibility and Pb concentration showed an inverse relationship to particle size. Almost 100% of Pb would be bioaccessible in the smallest slag particles (<20 μm), which also contained very high Pb levels ranging from 50,000 to 80,000 ppm and thus constitute a potential health hazard for children. [Copyright &y& Elsevier]

The Driver–Pressures–State–Impact–Response approach is applied to heavy metals in the Seine River catchment (65 000 km2; 14 million people of which 10 million are aggregated within Paris megacity; 30% of French industrial and agricultural production). The contamination pattern at river mouth is established on the particulate material at different time scales: 1930–2000 for floodplain cores, 1980–2003 for suspended particulate matter (SPM) and bed-sediments, 1994–2003 for atmospheric fallout and annual flood deposits. The Seine has been among the most contaminated catchments with maximum contents recorded at 130 mg kg− 1 for Cd, 24 for Hg, 558 for Pb, 1620 for Zn, 347 for Cu, 275 for Cr and 150 for Ni. Today, the average levels for Cd (1. 8 mg kg−1), Hg (1. 08), Pb (108), Zn (370), Cu (99), Cr (123) and Ni (31) are much lower but still in the upper 90% of the global scale distribution (Cr and Ni excepted) and well above the natural background values determined on pre-historical deposits. All metal contents have decreased at least since 1955/65, well before metal emission regulations that started in the mid 1970''s and the metal monitoring in the catchment that started in the early 1980''s. In the last 20 y, major criteria changes for the management of contaminated particulates (treated urban sludge, agricultural soils, dredged sediments) have occurred. In the mid 1990''s, there was a complete shift in the contamination assessment scales, from sediment management and water usage criteria to the good ecological state, now required by the 2000 European Directive. When comparing excess metal outputs, associated to river SPM, to the average metal demand within the catchment from 1950 to 2000, the leakage ratios decrease exponentially from 1950 to 2000 for Cd, Cr, Cu, Pb and Zn, meanwhile, a general increase of the demand is observed: the rate of recycling and/or treatment of metals within the anthroposphere has been improved ten-fold. Hg environmental trajectory is very specific: there is a marked decontamination from 1970 to 2000, but the leakage ratio remains very high (10 to 20%) during this period. Drivers and Pressures are poorly known prior to 1985; State evolution since 1935 has been reconstructed from flood plain cores analysis; Impacts were maximum between 1950 and 1970 but remained unknown due to analytical limitation and lack of awareness. Some Responses are lagging 10 y behind monitoring and have much evolved in the past 10 y. [Copyright &y& Elsevier]

River basin metal pollution originates from heavy industries (plating, automobile) and from urban sources (Paris conurbation: 2740 km2, 9. 47 million inhabitants). The natural sources of metal have been found to be limited due to sedimentary nature of this catchment and to the very low river sediment transport (10 t km−2 y−1). Several types of data have been collected to build the metal budget within the whole Seine River basin: field surveys, economical statistics and environmental models. Environmental contamination and related fluxes have been measured on atmospheric fallout, rural streams particles, and Seine River particles upstream and downstream of Paris and at river mouth. Metal pathways and budgets have been set up for (i) a typical cultivated area, (ii) a Paris combined sewer system, (iii) Paris conurbation and (iv) the whole catchment metal retention effect in floodplain and dredged material. Metal fluxes to the estuary have been decomposed into natural, urban domestic and other sources. The latter are within 1–2 orders of magnitude larger than waste water fluxes directly released into rivers according to an industrial census. These fluxes have been further compared to the annual use (1994–2003) of these metals. Metal excess fluxes exported by the river are now a marginal leak of metal inputs to the catchment (i.e. “raw” metals, metals in goods, atmospheric fallout), generally from 0. 2 to 5‰. However, due to the very limited dilution power in this basin, the contamination of particles is still relatively high. The Seine River basin is gradually storing metals, mostly in manufactured products used in construction, but also in various waste dumps, industrial soils, agricultural and flood plain soils. [Copyright &y& Elsevier]

Abstract: A sample of 573 infants (aged 0 to 12 months) from the Moroccan city of Marrakech was studied in order to determine the level of Pb and Al contaminations. Mean values of Pb and Al in children''s hair were 6.6 and 9.5 μg/l, respectively. Age, gender, and parents'' occupation influenced significantly Pb content but not Al content. Larger mean values were measured for Al compared with Pb. This finding can be explained by a higher level of Al available in both the infant diet (complementary feeding) and the local environmental factors (soil and drinking water). During weaning, beverages like tea, widely used in Morocco, represent an important source of Pb and Al contamination. Al content in drinking water is above the international standard. [Copyright &y& Elsevier]

Abstract: The aim of this case study was to uncover the consequences of lead pellet-derived heavy lead contamination at a cast-off shooting range in southern Finland, covering aspects from soil chemistry and biology up to ecosystem level. The observed changes in the soil properties of the most contaminated areas suggest that the contamination may be disturbing processes of decomposition and nutrient mineralisation. Also two functionally important groups of soil organisms, microbes (as analysed using the PLFA analysis) and enchytraeid worms, were negatively affected by the contamination. Furthermore, there was an indication of reduced pine litter production at the contaminated areas. On the other hand, lead contamination appears not to have affected pine growth or soil-dwelling nematodes and microarthropods, and the general outlook of the whole ecosystem is that of a healthy forest. Thus, the boreal forest ecosystem studied as a whole appears to bear strong resistance to contamination, despite negative effects of lead on many of its components. This resistance may result from e.g. low bioavailability of lead, avoidance of the most contaminated soil horizons and microsites by the organisms, and functional redundancy and development of lead-tolerant populations amongst the organisms. The relative importance of these factors and the mechanisms behind them will be investigated in forthcoming studies. [Copyright &y& Elsevier]

Abstract: This paper presents a survey on soil Pb contamination around Paris (France) using the French soil monitoring network. The first aim of this study is to estimate the total amount of anthropogenic Pb inputs in soils and to distinguish Pb due to diffuse pollution from geochemical background Pb. Secondly, this study tries to find the main controlling factors of the spatial distribution of anthropogenic Pb. We used the technique of relative topsoil enhancement to evaluate the anthropogenic stock of Pb and we performed lognormal kriging to map Pb regional distribution. The results show a strong gradient of anthropogenic stock of Pb around the urban Paris area. We estimate a total amount of anthropogenic stock of Pb close to 143,000 metric tons, which corresponds to an average accumulation of 5.9 t km−2. Our study suggests that a grid-based survey can help to quantify diffuse Pb contamination by using robust techniques of calculation and that it might also be used to validate predictions of deposition models. [Copyright &y& Elsevier]

Abstract: This study was aimed at evaluating the lead (Pb) and cadmium (Cd) contamination status using resident pigeons from rural (island), central urban (Seoul), and four industrial complex areas in Korea with varying traffic density as well as atmospheric metal pollution records. We also discussed the results with respect to metal exposure trends in urban area after introduction of lead-free gasoline in Korea. Mean concentrations of Pb and Cd in bone and kidney of pigeons from Seoul were comparable to those from industrial complex areas and were about 15–20 times those at the reference site. This suggests that exposure to metals in the urban environment is as high as in the industrial areas. Lead and Cd concentrations in lungs of pigeons from Seoul were significantly higher by more than three times in 2000 than in 1991 (p <0.01), whereas the residues in liver, kidney, and bone remained at a similar level, despite the introduction of unleaded gasoline in 1993. The Pb and Cd concentrations in tissues of pigeons did not decrease as atmospheric metal levels decreased. Ingestion may be more important than inhalation in exposing pigeons to Pb and Cd in this study. [Copyright &y& Elsevier]

Abstract: The Ensenada de San Simón is the inner part of the Ría de Vigo, one of the major mesotidal rías of the Galician coast, NW Spain. The geochemistry of its bottom sediments can be accounted for in terms of both natural and anthropogenic sources. Mixture-modelling enables much of the Cr, Ni, V, Cu, Pb and Zn concentrations of the bottom and subaqueous sediments to be explained by sediment input from the river systems and faecal matter from manmade mussel rafts. The compositions and relative contributions of additional, unknown, sources of anomalous heavy-metal concentrations are quantified using constrained nonlinear optimization. The pattern of metal enrichment is attributed to: material carried in solution and suspension in marine water entering the Ensenada from the polluted industrial areas of the adjacent Ría de Vigo; wind-borne urban dusts and/or vehicular emissions from the surrounding network of roads and a motorway road-bridge over the Estrecho de Rande; industrial and agricultural pollution from the R. Redondela; and waste from a former ceramics factory near the mouth of the combined R. Oitabén and R. Verdugo. Using 137Cs dating, it is suggested that heavy metal build-up in the sediments since the late 1970s followed development of inshore fisheries and introduction of the mussel rafts (ca. 1960) and increasing industrialisation. [Copyright &y& Elsevier]

In order to predict metal bioavailability by microorganisms in natural waters, analytical speciation techniques such as the permeation liquid membrane (PLM) are required. A planar sheet PLM has been characterized by measuring Pb fluxes in the absence and presence of tiron and nitrilotriacetic, iminodiacetic, malonic, citric, polyacrylic and fulvic (Suwannee River fulvic, SRFA) acids. Important parameters such as the diffusion coefficient in the membrane phase and the effective distribution coefficient between the solution and membrane were evaluated in order to determine limiting conditions for the overall transport flux through the membrane. Subsequently, the PLM was tested for its ability to predict bioavailability by the freshwater alga, Chlorella kesslerii by comparing Pb PLM fluxes (JPLM) to Pb biouptake fluxes (Jint) in the absence and presence of the synthetic ligands and SRFA. The capability of the PLM to mimic transport across biological membranes was demonstrated, in particular, from the similarity between the accumulated (PLM, algal) Pb vs. time plots under the different conditions. Under membrane transport limiting conditions, fluxes across both the PLM and biological membranes were proportional to the free metal ion and directly correlated to each other in the zone below saturation of the biological metal uptake sites. The correlation between the different fluxes may be used to predict Pb uptake by C. kesslerii in the presence of the synthetic ligands. However, in the presence of SRFA, the observed Jint was much higher than predicted by results obtained either in the absence or presence of the synthetic ligands. [Copyright &y& Elsevier]

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. [Copyright &y& Elsevier]

This paper examines how fluxes in the aquatic environment reflect the reduced use of cadmium (Cd) and lead (Pb) in Stockholm, Sweden, between 1975 and 1995. The sediment deposition of Cd and Pb in the waters around Stockholm was investigated using laminated sediment cores, which facilitated reconstructions of historical annual metal deposition to the sediments. The resulting reconstructions were compared to independent estimations of the emissions to the aquatic environment during the phase-out period. The loads of Cd and Pb from sewage treatment plants, storm water and in atmospheric deposition were studied using literature data. The data set indicates a reduced load of Cd and Pb on the aquatic surroundings of Stockholm. The reduction is, however, not as pronounced in the sediment deposition as in the calculated emissions. This indicates that emissions may be delayed on their way to the sediments or that there are other sources, e.g. resuspension of older sediments. It is therefore argued that sediment investigations are an essential component in environmental monitoring, in order to get a complete picture of the metal fluxes to and in the environment in urban areas. [Copyright &y& Elsevier]

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. [Copyright &y& Elsevier]