Interactions between endogenous and dietary antioxidants against Pb-induced oxidative stress in wild ungulates from a Pb polluted mining area

Certain physiologic disorders, attributed to lead (Pb) exposure are related to the generation of oxidative stress. Organisms rely on a complex antioxidant system, composed of endogenously produced compounds such as glutathione (GSH), superoxide dismutase (SOD) and GSH peroxidase (GPX); and dietary antioxidants such as vitamins A and E. The aim of this work was to study the interactions between both groups of antioxidants and to evaluate their role in fighting Pb-induced oxidative stress in wild ungulates living in a Pb mining area. We studied red deer (n = 54) and wild boar (n = 60) from mining and control sites. Liver Pb, copper (Cu) and selenium (Se) levels were measured in liver and bone. Levels of GSH, oxidized GSH (GSSG), lipid peroxidation (TBARS), α-tocopherol, free retinol and retinyl esters, and the activities of SOD and GPX were measured in liver. Wild boar and red deer from the mining sites had higher bone (geometric means: 7.36 vs. 1.23 μg/g dw for boar; and 0.46 vs. 0.11 μg/g dw for deer) and liver Pb levels (0.81 vs. 0.24 μg/g dw for boar; and 0.35 vs. 0.11 μg/g dw for deer) than the controls. Pb exposure in deer was associated with lower GSH, α-tocopherol and retinyl esters, and higher free retinol and TBARS. A similar effect on vitamin A balance was observed in wild boar, but this was accompanied with an increase in GSH and α-tocopherol. GPX activity and Se levels were higher in wild boar (mean in controls: 670 IU/mg protein and 1.3 μg/g dw, respectively) than in red deer (150 IU/mg protein and 0.3 μg/g). These differences may indicate that red deer is more sensitive to Pb-induced oxidative stress than wild boar. Both endogenous and nutritional antioxidants may be negatively affected by Pb exposure, and their interactions are essential to fight against Pb-mediated oxidative damage.     

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.     

An evaluation of the reactivity of synthetic and natural apatites in the presence of aqueous metals

Metal removal from contaminated effluents was examined following reaction with natural apatites of biological and geological origin or a synthetic hydroxylapatite (HAP). Mammalian meat and bone meal (MBM), a by-product from meat industry, was the biological apatite source. The effect of incineration on metal removal capacity of MBM and HAP was also examined. The reactivity of apatites for all tested metals (Pb, Cd, Cu and Zn) followed the general order: synthetic > biological > mineral. For all apatites tested, Pb was removed best and preferentially from multi-metal solutions. MBM and HAP (0.5 g solid) removed Pb completely from both highly concentrated single metal solutions (50 ml, 1000 mg/L Pb) and from multi-metal solutions (50 ml) with 100 mg/L each of Cd, Cu and Zn in addition to Pb. The incineration of MBM (725 °C and 850 °C) reduced significantly its capacity for removal of Zn (by 47%, from 56 mg/g to 9 mg/g) and Cd (by 38%, from 53 mg/g to 13 mg/g) in particular and to a lesser extent for Cu (by 14%, from 61 mg/g to 46 mg/g) while the removal of Pb was not affected (100 mg/g). The same pattern was observed for incinerated HAP. SEM and XRD analysis indicated that HAP reacted with the metals by precipitation of pure metal phosphates—Pb hydroxylapatite, Zn phosphate (hopeite), a Cd phosphate (identified only by ED-SEM) and Cu phosphate (libenthenite).     

Biomonitoring of Cd, Cr, Hg and Pb in the Baluarte River basin associated to a mining area (NW Mexico)

With the purpose of knowing seasonal variations of Cd, Cr, Hg and Pb in a river basin with past and present mining activities, elemental concentrations were measured in six fish species and four crustacean species in Baluarte River, from some of the mining sites to the mouth of the river in the Pacific Ocean between May 2005 and March 2006. In fish, highest levels of Cd (0.06 μg g^− 1 dry weight) and Cr (0.01 μg g^− 1) were detected during the dry season in Gobiesox fluviatilis and Agonostomus monticola, respectively; the highest levels of Hg (0.56 μg g^− 1) were detected during the dry season in Guavina guavina and Mugil curema. In relation to Pb, the highest level (1.65 μg g^− 1) was detected in A. monticola during the dry season. In crustaceans, highest levels of Cd (0.05 μg g^− 1) occurred in Macrobrachium occidentale during both seasons; highest concentration of Cr (0.09 μg g^− 1) was also detected in M. occidentale during the dry season. With respect to Hg, highest level (0.20 μg g^− 1) was detected during the rainy season in Macrobrachium americanum; for Pb, the highest concentration (2.4 μg g^− 1) corresponded to Macrobrachium digueti collected in the dry season. Considering average concentrations of trace metals in surficial sediments from all sites, Cd (p < 0.025), Cr (p < 0.10) and Hg (p < 0.15) were significantly higher during the rainy season. Biota sediment accumulation factors above unity were detected mostly in the case of Hg in fish during both seasons. On the basis of the metal levels in fish and crustacean and the provisional tolerable weekly intake of studied elements, people can eat up to 13.99, 0.79 and 2.34 kg of fish in relation to Cd, Hg and Pb, respectively; regarding crustaceans, maximum amounts were 11.33, 2.49 and 2.68 kg of prawns relative to levels of Cd, Hg and Pb, respectively.     

Metals contained and leached from rubber granulates used in synthetic turf areas

The aim of this study was to quantify metals contained in and leached from different types of rubber granulates used in synthetic turf areas. To investigate the total content of metals, ca 0.5 g of material was added with HNO₃, HF and HClO₄ and microwave digested with power increasing from 250 W to 600 W. Leachates were prepared by extraction of about 5.0 g of material at room temperature for 24 h in an acidic environment (pH 5). Leaching with deionized water was also performed for comparison. Aluminium, As, Ba, Be, Cd, Co, Cr, Cu, Hg, Fe, Li, Mg, Mn, Mo, Ni, Pb, Rb, Sb, Se, Sn, Sr, Tl, V, W and Zn were quantified by high-resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) and ICP optical emission spectrometry (ICP-OES).Results indicated that the developed method was accurate and precise for the multi-element characterization of rubber granulates and leachates. The total amount and the amount leached during the acidic test varied from metal to metal and from granulate to granulate. The highest median values were found for Zn (10,229 mg/kg), Al (755 mg/kg), Mg (456 mg/kg), Fe (305 mg/kg), followed by Pb, Ba, Co, Cu and Sr. The other elements were present at few units of mg/kg. The highest leaching was observed for Zn (2300 μg/l) and Mg (2500 μg/l), followed by Fe, Sr, Al, Mn and Ba. Little As, Cd, Co, Cr, Cu, Li, Mo, Ni, Pb, Rb, Sb and V leached, and Be, Hg, Se, Sn, Tl and W were below quantification limits. Data obtained were compared with the maximum tolerable amounts reported for similar materials, and only the concentration of Zn (total and leached) exceeded the expected values.     

Lead contamination and associated disease in captive and reintroduced red kites Milvus milvus in England

Since 1989, a red kite Milvus milvus reintroduction programme has been underway in the United Kingdom, with 4-6 week old nestlings brought into captivity and held for 6-8 weeks before reintroduction. As scavengers, red kites may consume unretrieved game, and ingest shot or lead (Pb) fragments in their prey's flesh. We evaluated exposure to Pb in captive and wild red kites by taking blood samples from 125 captive young red kites prior to release, through analysing 264 pellets (regurgitated by wild birds) collected from under a roost site, and analysing Pb concentrations in livers and/or bones of 87 red kites found dead between 1995 and 2003. Lead isotope analyses of livers were also conducted in an effort to identify Pb exposure routes. Forty-six (36.8%) kites sampled prior to release had elevated blood Pb concentrations (201-3340 microg l(-1)). The source of this Pb was probably small fragments of lead ammunition in the carcasses of birds or mammals either fed to the nestlings by their parents or, more likely, subsequently whilst in captivity. Once released, kites were also exposed to lead shot in their food, and a minimum of 1.5-2.3% of regurgitated pellets contained Pb gunshot. Seven of 44 red kites found dead or that were captured sick and died within a few days had elevated (>6 mg kg(-1) dry weight [d.w.]) liver Pb concentrations, and six of these (14%) had concentrations of >15 mg kg(-1) d.w., compatible with fatal Pb poisoning. Post-mortem analyses indicated that two of these birds had died of other causes (poisoning by rodenticide and a banned agricultural pesticide); the remaining four (9%) probably died of Pb poisoning. Bone samples from 86 red kites showed a skewed distribution of Pb concentration, and 18 samples (21%) had Pb concentrations >20 mg kg(-1) d.w., indicating elevated exposure to Pb at some stage in the birds' life. Lead isotopic signatures (Pb (208/206); Pb (206/207)) in liver samples of the majority of kites were compatible with those found in lead shot extracted from regurgitated pellets. Lead isotope ratios found in the livers of kites with very low Pb concentrations were distinct from UK petrol Pb isotopic signatures, indicating that birds were exposed to little residual petrol Pb. We conclude that the primary source of Pb to which red kites are exposed is lead ammunition (shotgun pellets or rifle bullets), or fragments thereof, in their food sources; in some cases exposure appears sufficient to be fatal. We make recommendations to reduce Pb poisoning in both captive and wild red kites and other scavenging species.     

Remediation measures and displacement of pollutants in soils affected by the spill of a pyrite mine

The soils affected by the spill of a pyrite mine were analysed in 100 sampling points at three depths (0-10, 10-30, and 30-50 cm) in 1998 (after the tailings were removed), 1999 (after the cleaning of the highly contaminated areas), and 2004 (after the tilling of the upper 20-25 cm). The comparative study reveals that the removal of the tailings left a heterogeneous distribution pattern of the contaminants, with highly polluted spots alternating with less contaminated areas. The cleanup did not substantially lower the concentration in the highly polluted soils, and the spread of the pollutants increased the concentration in As and Pb in the uppermost 10 cm of 60% of the soils, while the Zn and Cd concentrations increased in only 30% of the soils. Given the high concentration of pollutants in the topsoil (especially As), the tilling of the upper 20-25 cm, despite reducing the average concentration of pollutants in the uppermost 10 cm, did not substantially lower the percentage of soils that exceeded the concentration of 40 mg As kg^− 1 dry soil and almost doubled the percentage of soils that surpassed this concentration between 10 and 30 cm. Meanwhile, the displacement of Zn and Cd within the soil supported the reduction in the percentage of soils that in the upper 10 cm exceeded the reference concentrations of these elements (900 mg Zn kg^− 1 dry soil and 2 mg Cd kg^− 1 dry soil), and the percentage of soils exceeding these concentrations between 10 and 50 cm in depth did not increase. Six years after the spill and at the end of all remediation measures, the intervention levels defined by the Environmental Agency of the Regional Government of Andalusia for natural parks were exceeded in the uppermost 10 cm in 35% of the soils.     

Speciation of lead, copper, zinc and antimony in water draining a shooting range—Time dependant metal accumulation and biomarker responses in brown trout (Salmo trutta L.)

The speciation of Pb, Cu, Zn and Sb in a shooting range run-off stream were studied during a period of 23 days. In addition, metal accumulation in gills and liver, red blood cell ALA-D activity, hepatic metallothionine (Cd/Zn-MT) and oxidative stress index (GSSG/ tGSH levels) in brown trout (Salmo trutta L.) exposed to the stream were investigated. Fish, contained in cages, were exposed and sampled after 0, 2, 4, 7, 9, 11 and 23 days of exposure. Trace metals in the water were fractionated in situ according to size (nominal molecular mass) and charge properties. During the experimental period an episode with higher runoff occurred resulting in increased levels of metals in the stream. Pb and Cu were mainly found as high molecular mass species, while Zn and Sb were mostly present as low molecular mass species. Pb, Cu and Sb accumulated on gills, in addition to Al origination from natural sources in the catchment. Pb, Cu and Sb were also detected at elevated concentration in the liver. Blood glucose and plasma Na and Cl levels were significantly altered during the exposure period, and are attributed to elevated concentrations of Pb, Cu and Al. A significant suppression of ALA-D was detected after 11 days. Significant differences were detected in Cd/Zn-MT and oxidative stress (tGSH/GSSG) responses at Day 4. For Pb the results show a clear link between the HMM (high molecular mass) positively charged Pb species, followed by accumulation on gills and liver and a suppression in ALA-D. Thus, high flow episodes can remobilise metals from the catchment, inducing stress to aquatic organisms.     

Evaluation of zinc, cadmium and lead isotope fractionation during smelting and refining

To evaluate metallurgical processing as a source of Zn and Cd isotopic fractionation and to potentially trace their distribution in the environment, high-precision MC-ICP-MS Zn, Cd and Pb isotope ratio measurements were made for samples from the integrated Zn-Pb smelting and refining complex in Trail, B.C., Canada. Significant fractionation of Zn and Cd isotopes during processing of ZnS and PbS ore concentrates is demonstrated by the total variation in δ^66/64Zn and δ^114/110Cd values of 0.42‰ and 1.04‰, respectively, among all smelter samples.No significant difference is observed between the isotopic compositions of the Zn ore concentrates (δ^66/64Zn = 0.09 to 0.17‰; δ^114/110Cd = − 0.13 to 0.18‰) and the roasting product, calcine (δ^66/64Zn = 0.17‰; δ^114/110Cd = 0.05‰), due to ∼ 100% recovery from roasting. The overall Zn recovery from metallurgical processing is ∼ 98%, thus the refined Zn metal (δ^66/64Zn = 0.22‰) is not significantly fractionated relative to the starting materials despite significantly fractionated fume (δ^66/64Zn = 0.43‰) and effluent (δ^66/64Zn = 0.41 to 0.51‰). Calculated Cd recovery from metallurgical processing is 72-92%, with the majority of the unrecovered Cd lost during Pb operations (δ^114/110Cd = − 0.38‰). The refined Cd metal is heavy (δ^114/110Cd = 0.39 to 0.52‰) relative to the starting materials. In addition, significant fractionation of Cd isotopes is evidenced by the relatively light and heavy isotopic compositions of the fume (δ^114/110Cd = − 0.52‰) and effluent (δ^114/110Cd = 0.31 to 0.46‰). In contrast to Zn and Cd, Pb isotopes are homogenized by mixing during processing. The total variation observed in the Pb isotopic compositions of smelter samples is attributed to mixing of ore sources with different radiogenic signatures.     

Historical biomonitoring of fluoride pollution by determining fluoride contents in roe deer (Capreolus capreolus L.) antlers and mandibles in the vicinity of the largest Slovene thermal power plant

Roe deer antlers/mandibles are a useful tool for determination of ambient fluoride pollution. Antlers have a well-defined annual cycle of growth, therefore they represent a natural standardisation of samples during winter months. On the contrary, mandibles accumulate fluorides during the whole life of an organism, thus they reflect aggregated effect of fluoride pollution trough the life-span of an organism. Both tissues are easily available; mandibles are often systematically collected with the purpose of cognitive management and control, and antlers could be gathered from private well-dated hunters' collections.Considering these benefits, fluoride contents were measured in 141 antlers (period 1960-2007) and 220 mandibles (period 1997-2009) of roe deer, shot in the vicinity of the largest Slovene Thermal Power Plant of Šoštanj (ŠTPP) as one of the major sources of fluorides in Slovenia. Fluoride contents in antlers significantly differed among age categories, and ranged from 110 to 1210 mg/kg in yearlings, 130 to 2340 mg/kg in young adults, and 250 to 2590 mg/kg in older adults, respectively. Fluoride levels in mandibles were also significantly different among age categories, and ranged from 30.0 to 227 mg/kg in fawns, 33.8 to 383 mg/kg in yearlings, and 61.5 to 1020 mg/kg in adults, respectively.Comparison of these results with previously reported fluoride contents in antlers and mandibles of roe deer from different areas of Europe revealed that the study area has never been extensively contaminated with fluorides. Moreover, trends of fluoride contents in both tissues confirmed a significant decrease of fluoride pollution in the area after the years 1995 and 2000, when flue-gas cleaning devices were constructed on the ŠTPP. Indeed, highly positive correlations between annual emissions from the ŠTPP and mean annual fluoride contents in antlers/mandibles confirmed that both tissues may be a useful tool for assessing temporal trends in ambient fluoride pollution.     

Metals and selenium in the liver and bone of three dolphin species from South Australia, 1988-2004

Metal and selenium concentrations (wet weight) were determined in the liver (Cd, Hg, Pb, Zn, Cu and Se) and bone (Pb and Cd) of common dolphins (Delphinus delphis, N=71) and bottlenose dolphins (Tursiops truncatus, N=12, and Tursiops aduncus, N=71) stranded or by-caught in South Australia from 1988 to 2004. Differences in metal burdens existed between species, stranding location, and relative age. T. aduncus had the greatest mean tissue burdens of liver Pb (0.45 mg/kg), Cd (6.45 mg/kg), Hg (475.78 mg/kg), Se (178.85 mg/kg) and Zn (93.88 mg/kg) and bone Pb (2.78 mg/kg), probably reflecting their coastal habitat and benthic prey. Mean Cu was highest in T. truncatus (21.18 mg/kg). Bone Cd was measured only in T. aduncus and averaged 0.05 mg/kg. Stranding location impacted metal burdens. Dolphins from Spencer Gulf had higher mean levels of liver Pb (0.39 mg/kg) while Gulf St Vincent dolphins had greater liver Hg (444.64 mg/kg), liver Se (163.12 mg/kg), and bone Pb (2.85 mg/kg). This may be due to high anthropogenic inputs of Pb and Hg into Spencer Gulf and Gulf St Vincent respectively. Liver Cd, Hg, Se and Pb increased with age in all species while Cu decreased with age, in keeping with previous studies. Se and Hg were positively correlated. The possibility that metallothioneins are driving observed correlations between Zn, Cd, Hg and Cu are discussed. Future research must investigate the toxicological consequences of the metal concentrations reported.     

Distribution of Pb and Po concentrations in wild berries and mushrooms in boreal forest ecosystems

The activity concentrations and distribution of ²¹⁰Pb and ²¹⁰Po in wild berries and edible mushrooms were investigated in Finnish forests. The main study areas were located in Scots pine (Pinus sylvestris L.) forests in southern and northern Finland. The activity concentrations of ²¹⁰Pb and ²¹⁰Po in blueberry (Vaccinium myrtillus L.) and lingonberry (Vaccinium vitis-idaea L.) samples decreased in the order: stems > leaves > berries (i.e. fruits). The activity ratios of ²¹⁰Po/²¹⁰Pb in the wild berry samples were mainly higher than one, indicating elevated activity concentrations of polonium in the samples. In mushrooms the activity concentrations of ²¹⁰Pb and especially ²¹⁰Po were higher than in fruits of the wild berries. The highest activity concentration of ²¹⁰Pb was detected in Cortinarius armillatus L. (16.2 Bq kg^− 1 d.w.) and the lowest in Leccinum vulpinum L. (1.38 Bq kg^− 1 d.w.). The ²¹⁰Po activity concentrations of the whole fruiting bodies ranged from 7.14 Bq kg^− 1 d.w. (Russula paludosa L.) to 1174 Bq kg^− 1 d.w. (L. vulpinum L.). In general, the highest activity concentrations of ²¹⁰Po were recorded in boletes. The caps of mushrooms of the Boletaceae family showed higher activity concentrations of ²¹⁰Po compared to the stipes. In most of the mushrooms analyzed, the activity concentrations of ²¹⁰Po were higher than those of ²¹⁰Pb. ²¹⁰Po and ²¹⁰Pb dominate the radiation doses received via ingestion of wild berries and mushrooms in northern Finland, while in southern Finland the ingested dose is dominated by ¹³⁷Cs from the Chernobyl fallout.     

Lead toxicity to wildlife: Derivation of a critical blood concentration for wildlife monitoring based on literature data

Generic risk assessments of lead (Pb) toxicity to wildlife puts soil Pb limits below the natural background. The Tissue Residue Approach (TRA) is an alternative method by which the current risk of Pb to wildlife can be assessed and avoids uncertainties about Pb exposure routes or bioavailability of environmental Pb. About 80 toxicity studies were reviewed of which 19 experimental and 6 field studies with mammals and birds were selected. Blood lead concentration (Pb-B, µg Pb/dL) was used as the index of exposure. The highest No Observed Effect Concentrations (NOECs) varied about 1600-fold among species and tests when expressed as external doses (mg Pb/kg body weight/day) whereas this range reduced to 50-fold when expressed as Pb-B. This illustrates that variation in Pb absorption from diet largely contributes to the variation in critical doses. A critical Pb-B concentration protecting mammals and birds from Pb toxicity was calculated with the HC₅ approach, i.e. the 5th percentile of species NOEC values with data of 15 different species and using growth, reproduction or hematology as endpoints. The HC₅ was significantly lower for mammals than that for birds (p < 0.05), suggesting that the association between blood lead concentration and systemic toxicity was different between the two groups. The HC₅ was 18 µg/dL for mammals and was 71 µg/dL for birds. The dose-response relationship between hematological effects (hemoglobin concentration, hematocrit) and Pb-B was aggregated for different species. These relationships were highly significant and significantly different between mammals and birds. The relationships predict that the % inhibitions of hematological endpoints at the calculated HC₅ values are only 1.5% in mammals and 2% in birds, clearly within the natural variation.     

Comparison of chlorine and chloramine in the release of mercury from dental amalgam

The purpose of this project was to compare the ability of chlorine (HOCl/OCl⁻) and monochloramine (NH₂Cl) to mobilize mercury from dental amalgam. Two types of amalgam were used in this investigation: laboratory-prepared amalgam and samples obtained from dental-unit wastewater. For disinfectant exposure simulations, 0.5 g of either the laboratory-generated or clinically obtained amalgam waste was added to 250 mL amber bottles. The amalgam samples were agitated by end-over-end rotation at 30 rpm in the presence of 1 mg/L chlorine, 10 mg/L chlorine, 1 mg/L monochloramine, 10 mg/L monochloramine, or deionized water for intervals of 0 h, 2 h, 4 h, 8 h, and 24 h for the clinically obtained amalgam waste samples and 4 h and 24 h for the laboratory-prepared samples. Chlorine and monochloramine concentrations were measured with a spectrophotometer. Samples were filtered through a 0.45 µm membrane filter and analyzed for mercury with USEPA standard method 245.7. When the two sample types were combined, the mean mercury level in the 1 mg/L chlorine group was 0.020 mg/L (n = 25, SD = 0.008). The 10 mg/L chlorine group had a mean mercury concentration of 0.59 mg/L (n = 25, SD = 1.06). The 1 mg/L chloramine group had a mean mercury level of 0.023 mg/L (n = 25, SD = 0.010). The 10 mg/L chloramine group had a mean mercury level of 0.024 mg/L (n = 25, SD = 0.011). Independent samples t-tests showed that there was a significant difference between the natural log mercury measurements of 10 mg/L chlorine compared to those of 1 mg/L and 10 mg/L chloramine. Changing from chlorine to chloramine disinfection at water treatment plants would not be expected to produce substantial increases in dissolved mercury levels in dental-unit wastewater.     

Delineation of Pb contamination pathways in two Pectinidae: The variegated scallop Chlamys varia and the king scallop Pecten maximus

Bioaccumulation of Pb was determined in Chlamys varia and Pecten maximus exposed to ²¹⁰Pb via seawater, food and sediment. Both scallops readily concentrated dissolved Pb with whole-body 7-d concentration factors of 250 ± 40 and 170 ± 70, respectively. In both species, more than 70% of Pb taken up from seawater was strongly retained within tissues (biological half-life > 1.5 month) whereas Pb ingested with phytoplankton was poorly assimilated (< 20%). As P. maximus lives buried in the sediment, this exposure pathway was assessed and showed low bioaccumulation efficiency for sediment-bound Pb (transfer factor < 0.015). Despite the poor transfer efficiency of Pb from food and sediment, the use of a global bioaccumulation model indicated that the particulate pathway (food and/or sediment) constituted the major bioaccumulation route of Pb in both scallops. Whatever the exposure pathway, the digestive gland and kidneys always played a major role in Pb accumulation. In scallop tissues, Pb was predominantly associated with the insoluble subcellular fraction, suggesting a low bioavailability of Pb for scallop consumers.     

Prevalence and predictors of exposure to multiple metals in preschool children from Montevideo, Uruguay

The extent of children's exposure to multiple toxic metals is not well described in many developing countries. We examined metal exposures in young children (6-37 months) from Montevideo, Uruguay and their mothers (15-47 years) participating in a community-based study. Hair samples collected from 180 children and their mothers were analyzed for: lead (Pb), cadmium (Cd), manganese (Mn), and arsenic (As) concentration using inductively coupled plasma-mass spectrometry (ICP-MS). Median metal levels (μg/g) were: Pb 13.69, Mn 1.45, Cd 0.17, and As 0.09 for children and Pb 4.27, Mn 1.42, Cd 0.08, and As 0.02 for mothers. Of the child and maternal samples, 1.7% and 2.9% were below the limit of detection (LOD) for Cd, and 21.3% and 38.5% were below the LOD for As, respectively. Correlations between maternal and child levels ranged 0.38-0.55 (p < 0.01). Maternal hair metal levels were the strongest predictors of metal concentrations in children's hair. Girls had significantly lower As levels than boys (p < 0.01) but did not differ on other metals. In addition, in bivariate logistic regressions predicting the likelihood that the child would be exposed to multiple metals, hemoglobin < 10.5 g/dL (OR = 2.12, p < 0.05), blood lead (OR = 1.17, p < 0.01), and the mother being exposed to two or more metals (OR = 3.34, p < 0.01) were identified as significant predictors of increased likelihood of multiple metal exposure. Older child age (OR = 0.96, p < 0.05), higher maternal education (OR = 0.35, p < 0.01), and higher number of household possessions (OR = 0.83, p < 0.01) were significantly associated with decreased likelihood of multiple metal exposure. Preschool children in Uruguay are exposed to multiple metals at levels that in other studies have been associated with cognitive and behavioral deficits. Sources of exposure, as well as cognitive and behavioral consequences of multiple metal exposure, should be investigated in this population.     

Dietary exposure and biomarkers of arsenic in consumers of fish and shellfish from France

Seafood, especially fish, is considered as a major dietary source of arsenic (As). Seafood consumption is recommended for nutritional properties but contaminant exposure should be considered. The objectives were to assess As intake of frequent French seafood consumers and exposure via biomarkers. Consumptions of 996 high consumers (18 and over) of 4 coastal areas were assessed using a validated food frequency questionnaire. Seafood samples were collected according to a total diet study (TDS) sampling method and analyzed for total As, arsenite (AsIII), arsenate (AsV), arsenobetaïne (AsB), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA). The average As dietary exposure is 94.7 ± 67.5 μg/kg bw/week in females and 77.3 ± 54.6 μg/kg bw/week in males (p < 0.001) and the inorganic As dietary exposure is respectively 3.34 ± 2.06 μg/kg bw/week and 3.04 ± 1.86 μg/kg bw/week (p < 0.05).Urine samples were collected from 382 of the subjects. The average urinary As concentration is 94.8 ± 250 μg/g creatinine for females and 59.7 ± 81.8 μg/g for males (p < 0.001). Samples having an As concentration above 75 μg/g creatinine (n = 101) were analyzed for inorganic As (As(III), As(V), MMA(V) and DMA(V)) which was 24.6 ± 27.9 μg/g creatinine for males and 27.1 ±20.6 μg/g for females. Analyses do not show any correlation between dietary exposure and urinary As.These results show that biological results should be interpreted cautiously. Diet recording seems to be the best way to assess dietary As exposure. Seafood is a high source of As exposure but even among high consumers it is not the main source of toxic As. From a public health point of view these results should be interpreted carefully in the absence of international consensus on the health-based guidance value.     

Effects of local point source polychlorinated biphenyl (PCB) contamination on bone mineral density in deer mice (Peromyscus maniculatus)

A former local source of PCBs has contaminated soil and the terrestrial food web at Saglek, Labrador. The relationship between PCB exposure and bone mineral density as an osteoporosis biomarker in deer mice (Peromyscus maniculatus) was investigated at two sites at Saglek: a contaminated Beach and a reference area. Bone mineral density was measured on the femur of twenty-six deer mice using dual-energy X-ray absorptiometry (DXA) technology. Bone mineral density was significantly lower in deer mice from the high exposure site (average whole body ∑PCB = 5769 ng/g wet weight, n = 20) than at the reference site (average whole body ∑PCB = 79.8 ng/g wet weight, n = 7). We used T-scores from the World Health Organization to determine the degree of decreased bone mineral density in exposed mice. Assuming the same biomechanical forces apply as for humans, and using a conservative factor of 1.5 (fracture risk increases 1.5 to 3 fold for every standard deviation decrease in bone mineral density), mice from the contaminated Beach are up to five folds more susceptible to fracture risk than mice from the reference area. Therefore, the PCB concentrations found locally at contaminated military sites such as Saglek are high enough to affect local wildlife.     

Displacement mechanism of binary competitive adsorption for aqueous divalent metal ions onto a novel IDA-chelating resin: isotherm and kinetic modeling

Adsorptive properties for Cu (II), Pb (II) and Cd (II) onto an iminodiacetic acid (IDA) chelating resin were systematically investigated at the optimal pH-value in both single and binary solutions using batch experiments. The Langmuir isotherm model and the pseudo second-order rate equation could explain respectively the isotherm and kinetic experimental data for sole-component system with much satisfaction. The maximum adsorption capacity in single system for Cu (II), Pb (II) and Cd (II) was calculated to be 2.27 mmol/g, 1.27 mmol/g and 0.65 mmol/g individually. The initial adsorption rate followed the order as Cu (II) > Pb (II) > Cd (II) at the fixed initial concentration, and for each metal the initial sorption rate increased as the initial concentration increased. In addition, the modified Langmuir model could describe the binary competitive adsorption behavior successfully, with which the interaction coefficient was obtained to follow the order as Cu (II) < Pb (II) < Cd (II). Furthermore, in every case of the investigated three binary systems, the reduction in both the uptake amounts and distribution coefficients testified the antagonistic competitive phenomena. Obviously, this novel IDA-chelating resin possessed of a good selectivity toward Cu (II) over Pb (II) and Cd (II) for the obtained highest separation factor values were up to 21.30 and 133.91 in the range of tested. This interaction mechanism between the favorable component and other metal ions could mainly contribute to the direct displacement impact which be herewith illustrated schematically.     

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.