Determination of the bioaccessibility of chromium in Glasgow soil and the implications for human health risk assessment

The Unified Bioaccessibility Method (UBM), which simulates the fluids of the human gastrointestinal tract, was used to assess the oral bioaccessibility of Cr in 27 Glasgow soils. These included several contaminated with Cr(VI), the most toxic form of Cr, from the past disposal of chromite ore processing residue (COPR). The extraction was employed in conjunction with the subsequent determination of the bioaccessible Cr by ICP-OES and Cr(VI) by the diphenylcarbazide complexation colorimetric procedure. In addition, Cr(III)-containing species were determined by (i) HPLC-ICP-MS and (ii) ICP-OES analysis of gel electrophoretically separated components of colloidal and dissolved fractions from centrifugal ultrafiltration of extracts. Similar analytical procedures were applied to the determination of Cr and its species in extracts of the < 10 μm fraction of soils subjected to a simulated lung fluid test to assess the inhalation bioaccessibility of Cr.The oral bioaccessibility of Cr was typically greater by a factor of 1.5 in the ‘stomach’ (pH ~ 1.2) compared with the ‘stomach + intestine’ (pH ~ 6.3) simulation. On average, excluding two COPR-contaminated soil samples, the oral bioaccessibility (‘stomach’) was 5% of total soil Cr and, overall, similar to the soil Cr(VI) concentration. Chromium(VI) was not detected in the extracts, a consequence of pH- and soil organic matter-mediated reduction in the ‘stomach’ to Cr(III)-containing species, identified as predominantly Cr(III)-humic complexes. Insertion of oral bioaccessible fraction data into the SNIFFER human health risk assessment model identified site-specific assessment criteria (for residential land without plant uptake) that were exceeded by the soil total Cr (3680 mg kg^-1) and Cr(VI) (1485 mg kg^-1) concentration at only the most COPR-Cr(VI)-contaminated location. However, the presence of measurable Cr(VI) in the < 10 μm fraction of the two most highly Cr(VI)-contaminated soils demonstrated that inhalation of Cr(VI)-containing dust remains the most potentially harmful exposure route.     

The intake of lead and associated metals by sheep grazing mining-contaminated floodplain pastures in mid-Wales, UK: II. Metal concentrations in blood and wool

Sheep grazing metal-contaminated floodplain pastures across mid-Wales ingest high concentrations of lead (Pb) in vegetation and directly in the form of soil. Sheep whole blood analysis indicated that Pb concentrations can be significantly elevated for animals grazing contaminated sites: in winter/spring, a median blood concentration of 147 µg Pb l^− 1 was found at the location with the highest soil enrichment of this metal compared to only 26 µg Pb l^− 1 for the control flock. There was within-flock variability in blood-Pb concentration, and overlap between blood-Pb ranges in animals grazing control and contaminated sites, although use of the Kruskal-Wallis H test established a number of significant (P < 0.05) differences between the blood-Pb content of flocks grazing the various study locations. Despite total daily intakes of up to 723 mg Pb d^− 1, only one individual sheep showed a blood-Pb content above the ‘normal safe’ concentration of 250 µg l^− 1. Blood and wool analyses were found to have limited value for the diagnosis of environmental exposure to Pb, and further consideration of metal accumulation in offal, bone and muscle tissue is recommended.     

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

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

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

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

Influence of soil properties on trace element availability and plant accumulation in a Mediterranean salt marsh polluted by mining wastes: implications for phytomanagement

The aims of this study were to determine the factors which control metal and As phytoavailability in the different microenvironments (Sand Dunes, Salt Flat, Dry River and Shrubs) present at a Mediterranean salt marsh polluted by mining wastes. We performed a field study following a plot sampling survey. The analyses of soil parameters (pH, electrical conductivity (EC), organic carbon contents, etc.), total metal and As concentrations and their phytoavailability assessed with EDTA were related to each microenvironment and the corresponding plant species uptake. The averages of pH and EC were slightly alkaline (pH ≈ 7.5) and saline (≈ 2.2 to 17.1 dS m⁻¹) respectively. The soil samples from the Salt Flat subzone showed the highest metal concentrations (e.g. 51 mg kg⁻¹ Cd, 11,600 mg kg⁻¹ Pb) while for As, the highest concentrations occurred in the Dry River (380 mg kg⁻¹ As). The total metal and EDTA-extractable concentrations occurred as it follows: Salt Flat > Dry River > Degraded Dunes > Shrubs. In relation to plant metal and As accumulation, the highest root concentrations were obtained in the species from the Salt Flat subzone: ~ 17 mg kg⁻¹ As, ~ 620 mg kg⁻¹ Pb, for both, Juncus maritimus and Arthrocnemum macrostachyum. However the highest metal and As shoot concentrations occurred in species from the Sand Dunes: ~ 23 mg kg⁻¹ As ~ 270 mg kg⁻¹ Pb for Dittrichia viscosa; ~ 23 mg kg⁻¹ As, ~ 390 mg kg⁻¹ Zn for Crucianella maritima. The occurrence of edaphic gradients including salinity and texture determined the vegetation distribution. However, it cannot be concluded that there was a disturbance due to metal(loid)s soil concentrations in terms of vegetation composition except in the Degraded Dunes and Dry River. The higher EDTA-extractable concentrations were coincidental with the most saline soils but this did not result in higher metal(loid)s plant accumulation.     

Significance and interspecific variability of accumulated trace metal concentrations in Antarctic benthic polychaetes

Trace metals were analysed in polychaetes collected on Polarstern cruise ANT XXI/2 (2003/04) to the Weddell Sea. Pb concentrations were largely less than 1.3 mg kg⁻¹ DW in all samples analysed. Statistical results indicate that the accumulated Cd, Cu and Zn concentrations are related to the feeding guild to which the animals are belonging. Relatively low Cd and Cu concentrations are found in macrophagous carnivores and relatively high concentrations in microphagous detritus feeders. The relationship between Zn concentrations and the feeding guilds of polychaetes is reverse. Cd concentrations range from (median values and interquantile ranges in brackets) 2.6 (1.5-3.2) mg kg⁻¹ DW in the carnivorous Trypanosyllis gigantea to 133 (37-176) mg kg⁻¹ in the microphagous detritus feeder Lanicides bilobata; Cu concentrations from 16 (11-19) mg kg⁻¹ in the carnivorous Antarctinoe spicoides to 40 (23-68) mg kg⁻¹ in the microphagous detritus feeder Phyllocomus crocea and Zn from 89 (69-97) mg kg⁻¹ in the microphagous detritus feeder Isocirrus yungi to 396 (372-404) mg kg⁻¹ in the carnivorous Aglaophamus trissophyllus. Ni is ranging from 3.7 (1.8-6.0) mg kg⁻¹ in Polyeunoa laevis to 34 (20-41) mg kg⁻¹ in A. spicoides, but no significant differences are obvious regarding the feeding guilds. Since information on metals in Antarctic polychaetes is almost completely lacking, our results suggest further studies to clarify the role of feeding in the bioaccumulation of metals in this ecologically important taxonomic group.     

EXAFS speciation and phytoavailability of Pb in a contaminated soil amended with compost and gypsum

Due to unregulated uses of lead pellets for hunting purposes in Japan, soils and sediments in some river basins and wetlands have become highly contaminated with Pb. Deterioration of natural vegetation has occurred sporadically in these areas, and therefore revegetation is needed for ecological restoration. The objectives of the present study were to assess the effects of surface applications of compost and gypsum amendments on Pb availability to a watercress plant (Nasturtium officinale W.T. Aiton) and molecular-scale speciation of Pb in soil solid phases. The compost and gypsum amendments significantly decreased dissolved Pb and Sb in pore water. The concentration of Pb in aboveground plant tissues was 190 mg kg^− 1 in the control soil and was reduced to < 20 mg kg^− 1 in the compost and gypsum-amended soils. The concentration of Sb in plants grown in the control soil was 13 mg kg^− 1, whereas that in the soils receiving compost and gypsum decreased below detectable levels. Redox potential was higher in vegetated soils (ave. 349 mV) than in the unvegetated soils (ave. 99 mV) due to oxygen introduced by plant roots. Extended X-ray absorption fine structure (EXAFS) spectroscopy illustrated that Pb occurred as Pb sorbed on birnessite and/or ferrihydrite (Pb-Mn/Fe, ~ 60%) and Pb sorbed on organic matter (Pb-org, ~ 15%), and galena (PbS, ~ 10%) in the vegetated and unvegetated control soils. The compost amendment increased the proportion of Pb-org by 2-fold than in the control soils. The amended soils with plant growth decreased the proportion of Pb-Mn/Fe phases by half of that without plant growth. Galena and anglesite (PbSO₄) were not detected in compost-amended soils and even in gypsum-amended soils since a significant soil reduction to anoxic levels did not occur in the entire soil. The present study indicated that, under flooded conditions, surface applications of compost and gypsum amendments reduced plant Pb uptake from the Pb contaminated soil.     

Environmental impact of mining activities in the Lousal area (Portugal): chemical and diatom characterization of metal-contaminated stream sediments and surface water of Corona stream

Lousal mine is a typical “abandoned mine” with all sorts of problems as consequence of the cessation of the mining activity and lack of infrastructure maintenance. The mine is closed at present, but the heavy metal enriched tailings remain at the surface in oxidizing conditions. Surface water and stream sediments revealed much higher concentrations than the local geochemical background values, which the “Contaminated Sediment Standing Team” classifies as very toxic. High concentrations of Cu, Pb, Zn, As, Cd and Hg occurred within the stream sediments downstream of the tailings sites (up to: 817 mg kg⁻¹ As, 6.7 mg kg⁻¹ Cd, 1568 mg kg⁻¹ Cu, 1059 mg kg⁻¹ Pb, 82.4 mg kg⁻¹ Sb, 4373 mg kg⁻¹ Zn). The AMD waters showed values of pH ranging from 1.9 to 2.9 and concentrations of 9249 to 20,700 mg L⁻¹ SO₄⁻², 959 to 4830 mg L⁻¹ Fe and 136 to 624 mg L⁻¹ Al. Meanwhile, the acid effluents and mixed stream waters also carried high contents of SO₄^2−, Fe, Al, Cu, Pb, Zn, Cd, and As, generally exceeding the Fresh Water Aquatic Life Acute Criteria. Negative impacts in the diatom communities growing at different sites along a strong metal pollution gradient were shown through Canonical Correspondence Analysis: in the sites influenced by Acid Mine Drainage (AMD), the dominant taxon was Achnanthidium minutissimum. However, Pinnularia acoricola was the dominant species when the environmental conditions were extremely adverse: very low pH and high metal concentrations (sites 2 and 3). Teratological forms of Achnanthidium minutissimum (Kützing) Czarnecki, Brachysira vitrea (Grunow) Ross in Hartley, Fragilaria rumpens (Kützing) G. W. F. Carlson and Nitzschia hantzschiana Rabenhorst were found. A morphometric study of B. vitrea showed that a decrease in size was evident at the most contaminated sites. These results are evidence of metal and acidic pollution.     

Selenium concentrations of common weeds and agricultural crops grown in the seleniferous soils of northwestern India

The plants grown in seleniferous soils constitute a major source of toxic selenium levels in the food chain of animals and human beings. Greenhouse and field experiments were conducted to study selenium concentrations of weeds, forages and cereals grown on seleniferous soils located between 31.0417° to 31.2175° N and 76.1363° to 76.4147° E in northwestern India. Eleven winter season (November-April) weed plants were grown in the greenhouse in a soil treated with different levels of selenate-Se. Selenium concentrations of weed plants increased progressively with the levels of selenate-Se in soil. The highest Se concentration was recorded by Silene gallica (246 mg kg^− 1) and the lowest by Avena ludoviciana (47 mg kg^− 1) at 2.5 mg Se kg^− 1 soil. A.ludoviciana and Spergula arvensis proved highly tolerant to the presence of 1.25 and 2.5 mg selenate-Se kg^− 1 soil and the remaining weeds were sensitive to Se. Dry matter yield of Se-sensitive weed plants was 25 to 62% of the yield in the no-Se control at 1.25 mg selenate-Se kg^− 1 and 6 to 40% at 2.5 mg selenate-Se kg^− 1 soil. Other symptoms like change in leaf colour and size, burning of leaf tips and margins, and delayed flowering were also observed due to Se. Dry matter yield of Se-sensitive weed plants expressed as percentage of yield in the no-Se control at both the Se levels was inversely correlated with their Se content (r = − 0.731, p < 0.01, N = 17). Among the weed plants grown in seleniferous soils under field situations, Mentha longifolia accumulated the highest Se (365 mg kg^− 1) and Phalaris minor the lowest (34 mg kg^− 1). Among agricultural crops grown on a naturally contaminated soil in the greenhouse, Se concentrations were the highest for oilseed crops (19-29 mg kg^− 1), followed by legumes (6-13 mg kg^− 1) and cereals (2-18 mg kg^− 1). Helianthus annuus among the oilseed crops, A.ludoviciana among the winter season weeds, M.longifolia among the summer season (May-October) weeds and Cirsium arvense among the perennial weeds can be used for phytoremediation of seleniferous soils as these accumulate the highest amounts of Se.     

Bone lead levels and lead isotope ratios in red grouse from Scottish and Yorkshire moors

Leg and foot bones of adult and juvenile red grouse (Lagopus lagopus scoticus) were collected from hunter-shot birds on two Scottish estates (Glendye and Invermark) and one Yorkshire estate in September, 2003. The lead content of bones was measured by atomic absorption spectrophotometry, and corresponding stable lead isotopes (Pb^{204, 206, 207, 208}) by inductively coupled plasma mass spectrometry. At the Glendye (N = 111) and Invermark (N = 85) estates, relatively few birds (5.4% and 3.5%, respectively) had highly elevated bone lead concentrations (> 20 µg/g dry weight). In bones of these highly exposed birds, a combination of Pb²⁰⁶:Pb²⁰⁷ and Pb²⁰⁸:Pb²⁰⁷ratios was consistent with ingestion of lead gunshot available in Europe. By contrast, Yorkshire grouse experienced a high incidence (65.8%) of bone lead > 20 µg/g. The Pb²⁰⁶:Pb²⁰⁷ and Pb²⁰⁸:Pb²⁰⁷ratios in bones of these highly exposed birds were consistent with a combined exposure to ingested lead gunshot and lead from galena mining in the region. Lead isotope ratios also indicated that lead from UK gasoline combustion and fallout from atmospheric particles was not a likely source of elevated lead in bones of either Scottish or Yorkshire grouse. Suggested management options for the three moors include adopting nontoxic shot for all game shooting on the estates, allowing heather (Calluna vulgaris) vegetation to grow tall in lead shot fall-out zones to reduce physical access to high densities of lead shot already present, and provision of calcareous grit across moors to reduce lead assimilation from all ingested sources of lead.     

Bioaccumulation of silver in ectomycorrhizal and saprobic macrofungi from pristine and polluted areas

Macrofungi are effective accumulators of Ag. This study provides a comprehensive review of this phenomenon supported by original data on the Ag concentrations of macrofungi from pristine and Ag-polluted areas. In pristine areas, the median Ag concentrations of ectomycorrhizal (ECM) and saprobic (SAP) macrofungi were 0.79 and 2.94 mg kg^− 1, respectively. In these areas, hyperaccumulation thresholds for Ag in ECM and SAP macrofungi are proposed as 100 and 300 mg kg^− 1, respectively. In a Ag-polluted area, the Ag concentrations in macrofungi (ECM and SAP) were significantly elevated with the median value of 24.7 mg kg^− 1 and the highest concentrations in Amanita spp. of the section Vaginatae (304-692 mg kg^− 1). The intracellular speciation of Ag in fruit-bodies of the Ag-accumulator Amanita submembranacea was inspected by size exclusion chromatography followed by sulfhydryl-specific fluorimetric assays of ligands using reverse phase high-performance liquid chromatography and improved polyacrylamide gel electrophoresis. Virtually all Ag was found to be intracellular and sequestered in the major 7 kDa and minor 3.3 kDa complexes. The lack of glutathione and phytochelatins and the presence of a single 3 kDa sulfhydryl-containing peptide in the isolated Ag-complexes suggest that detoxification of Ag in A. submembranacea may rely on metallothionein. Vertical distribution of Ag in a polluted forest soil profile has shown substantial enrichment in organic horizons; in polluted technosol, the highest Ag concentrations were found in surface layers. Standardized EDTA extraction of Ag in both the investigated soil profiles showed relatively low Ag extractibility, generally within the range of 2.2-7.7% of total Ag content.     

The graphical presentation of lead isotope data for environmental source apportionment

Lead isotope ratios are widely used to identify original sources of Pb in the environment. Such source apportionment depends on the ability to distinguish potential sources on the basis of their isotopic composition. However, almost all terrestrial Pb is co-linear in some of the plots i.e. ²⁰⁶Pb/²⁰⁸Pb versus ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁶Pb/²⁰⁴Pb versus ²⁰⁶Pb/²⁰⁷Pb commonly presented in the literature. These diagrams are unable to distinguish more than two sources of environmental Pb. Linear trends in such plots are an inevitable consequence of the co-linearity of terrestrial leads and should not be taken necessarily to indicate simple binary mixing of sources. A more reliable test for multiple source mixing can be obtained from plots involving ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb and therefore requires measurements of the minor ²⁰⁴Pb isotope.     

Impact of model uncertainty on soil quality standards for cadmium in rice paddy fields

At present, soil quality standards used for agriculture do not consider the influence of pH and CEC on the uptake of pollutants by crops. A database with 750 selected paired samples of cadmium (Cd) in soil and paddy rice was used to calibrate soil to plant transfer models using the soil metal content, pH, and CEC or soil Cd and Zn extracted by 0.01 M CaCl₂ as explanatory variables. The models were validated against a set of 2300 data points not used in the calibration. These models were then used inversely to derive soil quality standards for Japonica and Indica rice cultivars based on the food quality standards for rice. To account for model uncertainty, strict soil quality standards were derived considering a maximum probability that rice exceeds the food quality standard equal to 10 or 5%. Model derived soil standards based on Aqua Regia ranged from less than 0.3 mg kg^− 1 for Indica at pH 4.5 to more than 6 mg kg^− 1 for Japonica-type cultivars in clay soils at pH 7. Based on the CaCl₂ extract, standards ranged from 0.03 mg kg^− 1 Cd for Indica cultivars to 0.1 mg kg^− 1 Cd for Japonica cultivars. For both Japonica and Indica-type cultivars, the soil quality standards must be reduced by a factor of 2 to 3 to obtain the strict standards. The strong impact of pH and CEC on soil quality standards implies that it is essential to correct for soil type when deriving national or local standards. Validation on the remaining 2300 samples indicated that both types of models were able to accurately predict (> 92%) whether rice grown on a specific soil will meet the food quality standard used in Taiwan.     

The isotopic record of atmospheric lead fall-out on an Icelandic salt marsh since AD 50

We report a record of atmospheric Pb deposition at a coastal site in western Iceland that spans the last two millennia. The elemental concentrations of Pb, Al, Li and Ti are determined using ICP-MS from a sediment monolith collected from a salt marsh. Multicollector (MC) ICP-MS analysis is used to obtain isotopic ratios of stable Pb. The Pb/Ti and Pb/Li ratios are used to separate natural Pb background concentrations from Pb derived from remote anthropogenic sources. The pollution record in western Iceland is subdued in comparison with Pb records from the European mainland, but the isotopic character, profile and timing of Pb deposition show good agreement with the atmospheric Pb fall-out reported from sites in Scandinavia and northwestern Europe. At the bottom of the sequence we isolate a low-level (0.1-0.4 mg kg^− 1) Pb enrichment signal dated to AD 50-150. The isotopic signature and timing of this signal suggest Roman metal working industries as the source. In the subsequent millennium there was no significant or very low (i.e. elemental concentrations < 0.01 mg kg^− 1) anthropogenic Pb deposition at the site up to, and including, the early Medieval period. Above a pumice layer, dated to AD 1226-1227, a small increase in Pb deposition is found. This trend is maintained until a more substantive and progressive increase is signalled during the late 1700s and early 1800s. This is followed by a substantial enrichment signal in the sediments (> 3.0 mg kg^− 1) that is interpreted as derived from industrial coal burning and metal working during the 19th and 20th centuries in northern Europe. During the late 20th century, significant fall-out from European fuel additives reached Iceland.     

Health risk from heavy metals via consumption of food crops in the vicinity of Dabaoshan mine, South China

Heavy metal contamination of soils resulting from mining and smelting is causing major concern due to the potential risk involved. This study was designed to investigate the heavy metal (Cu, Zn, Pb and Cd) concentrations in soils and food crops and estimate the potential health risks of metals to humans via consumption of polluted food crops grown at four villages around the Dabaoshan mine, South China. The heavy metal concentrations in paddy and garden soils exceeded the maximum allowable concentrations for Chinese agricultural soil. The paddy soil at Fandong village was heavily contaminated with Cu (703 mg kg^− 1), Zn (1100 mg kg^− 1), Pb (386 mg kg^− 1) and Cd (5.5 mg kg^− 1). Rice tended to accumulated higher Cd and Pb concentration in grain parts. The concentrations of Cd, Pb and Zn in vegetables exceeded the maximum permissible concentration in China. Taro grown at the four sampled villages accumulated high concentrations of Zn, Pb and Cd. Bio-accumulation factors for heavy metals in different vegetables showed a trend in the order: Cd > Zn > Cu > Pb. Bio-accumulation factors of heavy metals were significantly higher for leafy than for non-leafy vegetable. The target hazard quotient (THQ) of rice at four sites varied from 0.66-0.89 for Cu, 0.48-0.60 for Zn, 1.43-1.99 for Pb, and 2.61-6.25 for Cd. Estimated daily intake (EDI) and THQs for Cd and Pb of rice and vegetables exceeded the FAO/WHO permissible limit. Heavy metal contamination of food crops grown around the mine posed a great health risk to the local population through consumption of rice and vegetables.     

Manganese and lead in children's blood and airborne particulate matter in Durban, South Africa

Despite the toxicity and widespread use of manganese (Mn) and lead (Pb) as additives to motor fuels and for other purposes, information regarding human exposure in Africa is very limited. This study investigates the environmental exposures of Mn and Pb in Durban, South Africa, a region that has utilized both metals in gasoline. Airborne metals were sampled as PM_2.5 and PM₁₀ at three sites, and blood samples were obtained from a population-based sample of 408 school children attending seven schools. In PM_2.5, Mn and Pb concentrations averaged 17 ± 27 ng m^− 3 and 77 ± 91 ng m^− 3, respectively; Mn concentrations in PM₁₀ were higher (49 ± 44 ng m^− 3). In blood, Mn concentrations averaged 10.1 ± 3.4 μg L^− 1 and 8% of children exceeded 15 μg L^− 1, the normal range. Mn concentrations fit a lognormal distribution. Heavier and Indian children had elevated levels. Pb in blood averaged 5.3 ± 2.1 μg dL^− 1, and 3.4% of children exceeded 10 μg dL^− 1, the guideline level. Pb levels were best fit by a mixed (extreme value) distribution, and boys and children living in industrialized areas of Durban had elevated levels. Although airborne Mn and Pb concentrations were correlated, blood levels were not. A trend analysis shows dramatic decreases of Pb levels in air and children's blood in South Africa, although a sizable fraction of children still exceeds guideline levels. The study's findings suggest that while vehicle exhaust may contribute to exposures of both metals, other sources currently dominate Pb exposures.     

Multiple site study of recent atmospheric metal (Pb, Zn and Cu) deposition in the NW Iberian Peninsula using peat cores

In order to estimate atmospheric metal deposition in Southern Europe since the beginning of the Industrial Period (~ 1850 AD), concentration profiles of Pb, Zn and Cu were determined in four ²¹⁰Pb-dated peat cores from ombrotrophic bogs in Serra do Xistral (Galicia, NW Iberian Peninsula). Maximum metal concentrations varied by a factor of 1.8 for Pb and Zn (70 to 128 μg g⁻¹ and 128 to 231 μg g⁻¹, respectively) and 3.5 for Cu (11 to 37 μg g⁻¹). The cumulative metal inventories of each core varied by a factor of 3 for all analysed metals (132 to 329 μg cm⁻² for Pb, 198 to 625 μg cm⁻² for Zn and 22 to 69 μg cm⁻² for Cu), suggesting differences in net accumulation rates among peatlands. Although results suggest that mean deposition rates vary within the studied area, the enhanced ²¹⁰Pb accumulation and the interpretation of the inventory ratios (²¹⁰Pb/Pb, Zn/Pb and Cu/Pb) in two bogs indicated that either a record perturbation or post-depositional redistribution effects must be considered. After correction, Pb, Zn and Cu profiles showed increasing concentrations and atmospheric fluxes since the mid-XX^th century to maximum values in the second half of the XX^th century. For Pb, maximum fluxes were observed in 1955-1962 and ranged from 16 to 22 mg m⁻² yr⁻¹ (mean of 18 ± 1 mg m⁻² yr⁻¹), two orders of magnitude higher than in the pre-industrial period. Peaks in Pb fluxes in Serra do Xistral before the period of maximum consumption of leaded petrol in Europe (1970s-1980s) suggest the dominance of local pollutant sources in the area (i.e. coal mining and burning). More recent peaks were observed for Zn and Cu, with fluxes ranging from 32 to 52 mg m⁻² yr⁻¹ in 1989-1996, and from 4 to 9 mg m⁻² yr⁻¹ in 1994-2001, respectively. Our results underline the importance of multi-core studies to assess both the integrity and reliability of peat records, and the degree of homogeneity in bog accumulation. We show the usefulness of using the excess ²¹⁰Pb inventory to distinguish between differential metal deposition, accumulation or anomalous peat records.     

Accumulation of oxytetracycline and norfloxacin from saline soil by soybeans

Soil of former shrimp aquaculture facilities in Thailand may be contaminated by antibiotics (e.g. oxytetracycline and norfloxacin) and have elevated salinity. Therefore, reuse of this land can be problematic. The utility of soybean (Glycine max (L.) Merr.) for phytoremediation was investigated. The rate of germination and seedling emergence in prepared contaminated soil (conductivity 17.7 dS m^− 1 from adding 70 mg sodium chloride g^− 1 dry weight, 105 mg kg^− 1 dry weight oxytetracycline and 55 mg kg^− 1 dry weight norfloxacin) in sunlight was approximately 80% that of uncontaminated soil. This reduction was largely due to the high salinity. The antibiotics of interest degraded relatively rapidly in soil (half-life < 10 h for both) but loss was slower in deionised water. Accumulation of the antibiotics from deionised water by soybean resulted in little effect on growth rate and maximum levels in plants were observed after two days exposure, followed by declining concentrations. For soybean plants grown in saline soil, 90% removal of NaCl from soil adjacent to plant roots was observed, most within two days. Wilting and defoliation occurred, but plants recovered after 10 days and maximum salt levels in plants exceeded 20,000 mg g^− 1 dry weight with translocation from root to shoot tissue noted. Soybean plants also accumulated the antibiotics from prepared contaminated saline soil, but translocation from the roots was not observed. The results showed that soybean can be valuable for phytoremediation in these situations.     

Distribution of (210)Pb and (210)Po in boreal forest soil

Vertical distribution and activity contents of ²¹⁰Pb and ²¹⁰Po were investigated in forest soils of Scots pine-dominated (Pinus sylvestris L.) stands from seven different locations in Finland. The mean total inventory in the soil profile, up to 20 cm, of ²¹⁰Pb was 4.0 kBq m^− 2 (range 3.1-5.0 kBq m^− 2) and ²¹⁰Po 5.5 kBq m^− 2 (range 4.0-7.4 kBq m^− 2), the organic soil layer containing 45% of the total inventory of both nuclides. In both the organic and the mineral layers the ²¹⁰Po/²¹⁰Pb ratio was close to unity indicating a radioactive equilibrium between them. In the litter layer there was, however, a clear excess of ²¹⁰Po suggesting that polonium is recycled via root uptake from the root zone to the ground surface. The activity concentration (Bq kg^− 1) of ²¹⁰Pb clearly correlated with organic matter and the Fe, Al and Mn concentrations in soil indicating that radioactive lead is associated both with humic substances and the oxides of iron, aluminium and manganese. Radioactive lead was also seen to follow the behavior of stable lead. No systematic correlation between polonium and soil properties was seen.     

In vitro digestion and DGT techniques for estimating cadmium and lead bioavailability in contaminated soils: influence of gastric juice pH

A sensitivity analysis was conducted on an in vitro gastrointestinal digestion test (i) to investigate the influence of a low variation of gastric juice pH on the bioaccessibility of Cd and Pb in smelter-contaminated soils (F_B, using the unified bioaccessibility method UBM) and fractions of metals that may be transported across the intestinal epithelium (F_A, using the diffusive gradient in thin film technique), and (ii) to provide a better understanding of the significance of pH in health risk assessment through ingestion of soil by children. The risk of metal exposure to children (hazard quotient, HQ) was determined for conditions that represent a worst-case scenario (i.e., ingestion rate of 200 mg day^− 1) using three separate calculations of metal daily intake: estimated daily intake (EDI), bioaccessible EDI (EDI-F_B), and oral bioavailable EDI (EDI-F_A). The increasing pH from 1.2 to 1.7 resulted in: (i) no significant variation in Cd-F_B in the gastric phase but a decrease in the gastrointestinal phase; (ii) a decrease in soluble Pb in the gastric phase and a significant variation in Pb-F_B in the gastrointestinal phase; (iii) a significant decrease in Cd-F_A and no variation in Pb-F_A; (iv) no change in EDI-F_B and EDI-F_A HQs for Cd; (v) a significant decrease in EDI-F_B HQs and no significant variation in EDI-F_A HQ for Pb. In the analytical conditions, these results show that risk to children decreases when the bioavailability of Pb in soils is taken into account and that the studied pH values do not affect the EDI-F_A HQs. The present results provide evidence that the inclusion of bioavailability analysis during health risk assessment could provide a more realistic estimate of Cd and Pb exposure, and opens a wide field of practical research on this topic (e.g., in contaminated site management).