Essential and non-essential trace metals in scalp hair of men chronically exposed to volcanogenic metals in the Azores, Portugal

Volcanoes produce and release large amounts of toxicants, and the concentration of metals in hair can be used as a biomarker of exposure to trace metals. In order to investigate whether humans exposed to volcanic emissions demonstrate higher concentrations of essential and non-essential trace metals, scalp hair of men (3-89 years) living in two areas of the Azores, one exposed to volcanic emissions and the other not, was sampled, and their content in Cd, Cu, Pb, Rb, Se, and Zn was quantified by using High Resolution Inductively Coupled Plasma Mass Spectrometry. In average, men exposed to volcanic emissions presented higher concentrations of Cd (96.9 ppb), Cu (16.2 ppm), Pb (3417.6 ppb), Rb (216.3 ppb), and Zn (242.8 ppm), but not Se (469.6 ppb). Also, strong and significant correlations were found between Cd-Rb and Pb-Rb in the exposed men. In conclusion, humans living chronically exposed to volcanic emissions show high concentrations of essential and non-essential trace metals in scalp hair, and is suggested that this type of exposure may be as harmful as living close to industrial facilities.     

Accumulation of Pb, Cd, Cu and Zn in plants and hyperaccumulator choice in Lanping lead-zinc mine area, China

A field survey of higher terrestrial plants growing on Lanping lead-zinc mine, China were conducted to identify species accumulating exceptionally large concentrations of Pb, Cd, Cu and Zn of 20 samples of 17 plant species. Concentrations of Pb and Zn in soil and in plant were higher than that of Cu and Cd. Significant difference was observed among the average concentrations of four heavy metals in plants (except Cd and Cu) and in soil (except Pb and Zn) (P<0.05). For the enrichment coefficient of the four heavy metals in plant, the order of average was Pbtree>herbaceous, and herbaceous grew in soil with the highest concentrations of four heavy metals. In different areas, the concentrations of Pb, Cd, Cu and Zn in plants and soils and enrichment coefficient were different. Plants in Paomaping had more accumulating ability to Pb, Cd and Zn, and plants in Jinfeng River had more accumulating ability to Cu. Six plant species, i.e. S. cathayana, Lithocarpus dealbatus, L. plyneura, Fargesia dura, Arundinella yunnanensis and R. annae in Paomaping, had high accumulation capacity. R. annae in Paomaping had hyperaccumulating capacity to Pb, Cd and Zn, L. plyneura to Pb and Cd, and S. cathayana to Cd, respectively.     

Trace elements in fish from the Savannah river near Savannah river nuclear plant

A survey of trace element residues in fish from the Savannah River near Savannah River Nuclear Plant was undertaken in 1982. Fish muscle tissue was incubated by the wet digestion method. Fifteen trace elements were determined by flame atomic absorption spectrophotometry analysi of the digests. It was found that As, Se, Mg, Hg, Ca, Zn, and Fe levels were relatively higher than Pb, Cd, Ni, Co, Cr, and Mn in all fish species. In addition, in all fish species it seems that Pb, Cd, Ni, Co, Cr, and Mn levels were relatively higher than Cs and Cu. Cs and Cu levels were negligible in all fish species analyzed. Trace element levels found in these fish species were not high enough to render them dangerous for human consumption.     

Metal/metalloid contamination and isotopic composition of lead in edible mushrooms and forest soils originating from a smelting area

High metal contents in edible mushrooms growing in severely contaminated industrial areas pose an important toxicological risk. In the presented study, trace element (Pb, Cd, Zn, Cu, Ag, As, Se) contents were determined in caps and stipes of three different edible mushroom species (Boletus edulis Bull. Fr., Xerocomus badius Fr. Gilb., Xerocomus chrysenteron Bull. Quél.). Additionally, information about the chemical fractionation of metals in separate soil horizons and Pb isotopic data from soils and fruiting bodies allowed a more detailed insight on the uptake mechanisms of metals by the studied mushroom species. Total metal and metalloid concentrations in the organic soil horizons reached 36234 mg Pb kg(-1); 11.9 mg Cd kg(-1); 519 mg Zn kg(-1); 488 mg Cu kg(-1); 25.1 mg Ag kg(-1); 120 mg As kg(-1) and 5.88 Se mg kg(-1). In order to evaluate the accumulation capacity of the studied species, bioconcentration factors (BCF) were calculated for separate trace elements. For selected metals (Pb, Cd, Zn, Cu), a modified BCF calculation (using EDTA-extractable concentrations of metals in soil) was proposed. High contents of Pb (up to 165 mg kg(-1)) and Cd (up to 55 mg kg(-1)) exceeded all the regulatory limits in all the studied species. This was also the case for Se (up to 57 mg kg(-1)) in B. edulis. Intensive consumption of this species grown in such polluted areas can therefore pose toxicological risks for human health. A novel finding was that X. badius can act as an Ag accumulating species when grown at polluted sites due to the high concentrations of Ag (up to 190 mg kg(-1)) in caps. Pb isotopic data showed that Pb originating from the recent air pollution control residues is present mainly in the exchangeable/acid-extractable fraction of the organic horizons and is taken up by fruiting bodies; especially in the case of B. edulis, where fast Pb accumulation occurs. Due to the high species-dependent variations of metal contents, the studied mushrooms are not suitable as bioindicators of environmental pollution.     

Metal contamination of farming soils affected by industry

The contents of nine elements (As, Cd, Cr, Cu, Hg, Ni, Pb, Sb and Zn) have been assayed in the farming soils of Suszec commune (southern Poland). This area is affected by the main industrial centre of Poland (the Upper Silesian Industrial Region), the Czech Republic (Trzyniec smelter) and local contamination sources (coal mine). The contamination of the soils was assessed on the basis of geoaccumulation index, enrichment factor, contamination factor and degree of contamination. The tests revealed elevated contents of cadmium, lead, arsenic, antimony and mercury. The contents of the other elements were similar to the levels in the Earth's crust or pointed to metal depletion in the soil (EF<1).     

Speciation of elements in sediment samples collected at lakes Volvi and Koronia, N. Greece

A five-step sequential extraction procedure was applied for the determination of the distribution of seven elements (Cd, Pb, Cr, Cu, Mn, Zn, Fe) in sediment samples collected at two lakes, Volvi and Koronia, located in N. Greece. Samples were taken in two seasons, and the average concentration of the elements was calculated. The accuracy evaluated by comparing total trace metal concentrations with the sum of the five individual fractions proved to be satisfactory. Based on the results determined at one sampling point in Koronia and two sampling points along the lake Volvi, it seems that the two lakes have not yet been polluted. There were no significant changes in the individual seasonal concentrations of elements in this monitoring period. Cd, Pb, Cu and Cr are associated with the oxidizable, carbonates and residual fractions. Zn and Fe are associated with residual and reducible fractions. The metals that we most easily extracted in the samples analysed in both lakes are Pb, Cr, Cd, Cu and also Mn in the case of Koronia lake.     

经济发达县域耕地土壤重金属污染评价及其影响因素分析——以江苏省昆山市为例

通过对昆山市14个区镇91个土壤样品中As、Cd、Cr、Cu、Pb、Ni、Hg、Zn 8种重金属测定分析,对该市耕地土壤重金属污染进行评价并进行重金属污染的影响因素分析.结果表明,昆山市耕地土壤存在不同程度的轻微污染,重金属Cd、Cr、Cu、Pb、Hg、Zn均超过国家土壤背景值,旱地、水田中均以Hg污染范围较广、变异系数较大.综合污染指数表现为水田(1.15)＞旱地(1.00).区镇耕地重金属污染评价表明千灯、陆扬、石浦、锦溪、石牌处于警戒值之内,蓬朗、周庄、张浦、正仪、周市、巴城、淀山湖、花桥、陆家轻度污染;昆山市耕地土壤中重金属元素均未超过土壤环境基本容量,能够保证作物品质和农业持续发展.同时,研究表明区域重金属轻微污染具有复合污染的特性,Cd、Pb相关性最高(P=0.621 0), Pb与Hg、Cu、Zn、Cu与Cr也有相关性(0.438 7、0.426 0、0.350 9、0.394 0),区域重金属的轻微污染受人为因素影响显著,研究指出应加强对区域优先控制污染物Hg、次优先控制污染物Pb、Cd、Zn、Cu、Cr的控制与治理.     

Selenium and 17 other largely essential and toxic metals in muscle and organ meats of Red Deer (Cervus elaphus)--consequences to human health

Concentrations, composition and interrelationships of selenium and metallic elements (Ag, Ba, Cd, Co, Cr, Cs, Cu, Ga, Mn, Mo, Pb, Rb, Sb, Sr, Tl, V and Zn) have been examined in muscle and organ meats of Red Deer hunted in Poland. The analytical data obtained were also discussed in terms of Se supplementation and deficit to Deer as well as the benefits and risk to humans associated with the essential and toxic metals intake resulting from consumption of Deer meat and products. These elements were determined in 20 adult animals of both sexes that were obtained in the 2000/2001 hunting season from Warmia and Mazury in the north-eastern part of Poland. The whole kidneys contained Ba, Cd, Cr, Ga, Pb, Se, Sr and Tl at statistically greater concentrations than liver or muscle tissue from the same animal. Liver showed statistically greater concentrations of Ag, Co, Cu, Mn and Mo than kidneys or muscle tissue, and muscle tissue was richer in Zn, when compared to the kidneys or liver. Cs and Rb were similarly distributed between all three tissue types, while V was less abundant in liver than kidneys or muscle tissue. There were significant associations between some metallic elements retained in Red Deer demonstrated by Principal Component Analysis (PCA) of the data set. In organ and muscle meats (kidneys, liver and muscle tissue considered together) the first principal component (PC1) was strongly influenced by positively correlated variables describing Se, Ba and Cd and negatively correlated variables describing Ag, Co, Cs, Mn, Pb, Tl and V; PC2, respectively, by Cu, Mn and Mo (+) and Zn (-); PC3 by Ga (+) and PC4 by Sb (+). Selenium occurred in muscle tissue, liver and kidneys at median concentrations of 0.13, 0.19 and 4.0mg/g dry weight, respectively. These values can be defined as marginally deficient (< 0.6mg Se/kg liver dw) or satisfactory (≤ 3.0mg Se/kg kidneys dw) for the amount required to maintain the Deer's body condition and health, depending on the criterion for supplementation used. In terms of human nutritional needs, a relatively high selenium content of kidneys can be beneficial. The muscle meat, liver and kidneys of Red Deer can be considered as a very good source of essential Co, Cr, Cu, Mo, Mn, Se and Zn in the human diet. Lead is generally considered as toxic, and the concentrations found in Red Deer (via the food chain intake) were well below the European Union tolerance limit. Pb from the lead bullets can always create food hygienic problem, if not well recognized during sanitary inspection, and this was noted for one muscle meat sample in this study (5% surveyed). There is no tolerance limit of Cd in game animal meats. The median values of Cd noted in fresh muscle tissue, liver and whole kidneys were 0.07, 0.18, and 3.3mg/kg wet weight, respectively. Cd exists as a chemical element present at trace levels in plants and mushrooms in Deer's food chain in background (uncontaminated) areas. When these are consumed by the Deer, the amount of Cd sequestered with metallothioneins and retained in the organ and muscle meat in this study is low enough to be considered safe for human consumption.     

Soil-plant-animal transfer models to improve soil protection guidelines: a case study from Portugal

Food chain models are essential tools to assess risks of soil contamination in view of product quality including fodder crops and animal products. Here we link soil to plant transfer (SPT) models for potentially toxic elements (PTEs) including As, Ba, Cd, Co, Cu, Hg, Ni, Pb, Sb, U and Zn with models describing accumulation in animal organs. Current EU standards for food products and acceptable daily intake levels (ADI) for humans were used as critical limits. The combined model is used to assess the impact of soil contamination on animal health, product quality and human health using data from 100 arable fields. Results indicate that 42 existing arable fields near industrial and mining sites are unsuitable for animal grazing in view of food safety due to elevated intake of Cd, Cu, Hg and Pb by cows and sheep. At 10 sites daily intake levels of As by cows exceeded threshold concentrations regarding the quality of animal products.The food chain model also was used inversely to derive soil threshold concentrations in view of EU fodder standards. Calculated threshold levels in soil for As, Cd, Cu, Pb, Hg and Zn appear to be in line with those proposed or used in other EU countries. As such the approach applied here can form a conceptual basis for a more harmonized risk assessment strategy regarding the protection of animal and human health.     

Distribution of heavy metals in sediments of Mwanza Gulf of Lake Victoria,Tanzania

Sediment samples were analyzed for Cd, Cr, Cu, Pb, Hg and Zn by AAS. The highest concentrations (ppm) for Cu (26.1+/-4.8), Hg (0.2+/-0.05), Pb (30.7+/-5.6) and Zn (45.4+/-13.1) were found at approximately 25 m from the shoreline. Generally, heavy metals concentration in the sediment decreased with increasing distance from the shoreline except for Cd and Cr whose highest concentrations were found at approximately 2000 m from the shoreline.The data also indicated that sediment samples which were collected at the shores within the urban area of Mwanza showed elevated levels of Pb (54.6+/-11.1 ppm) and Zn (83.7+/-21.5 ppm). However, the highest concentrations of Cd (7.0+/-2.1 ppm), Cr (12. 9+/-1.0 ppm) and Hg (2.8+/-0.8 ppm) were recorded at sampling stations which were adjacent to river mouths.     

经济发达县域耕地土壤重金属污染评价及其影响因素分析

通过对昆山市14个区镇91个土壤样品中As、Cd、Cr、Cu、Pb、Ni、Hg、Zn 8种重金属测定分析，对该市耕地土壤重金属污染进行评价并进行重金属污染的影响因素分析。结果表明，昆山市耕地土壤存在不同程度的轻微污染，重金属Cd、Cr、Cu、Pb、Hg、Zn均超过国家土壤背景值，旱地、水田中均以Hg污染范围较广、变异系数较大。综合污染指数表现为水田（115）>旱地（100）。区镇耕地重金属污染评价表明千灯、陆扬、石浦、锦溪、石牌处于警戒值之内，蓬朗、周庄、张浦、正仪、周市、巴城、淀山湖、花桥、陆家轻度污染；昆山市耕地土壤中重金属元素均未超过土壤环境基本容量，能够保证作物品质和农业持续发展。同时，研究表明区域重金属轻微污染具有复合污染的特性，Cd、Pb相关性最高(〖WTBX〗P〖WTBZ〗=0621 0)， Pb与Hg、Cu、Zn、Cu与Cr也有相关性（0438 7、0426 0、0350 9、0394 0），区域重金属的轻微污染受人为因素影响显著，研究指出应加强对区域优先控制污染物Hg、次优先控制污染物Pb、Cd、Zn、Cu、Cr的控制与治理。     

Trace element and radionuclide mass balances at a coal-fired electric generating station

Coal, bottom ash, and fly ash from Milliken Station, a coal-fired 270 MW power plant, were analyzed for 20 elements (Ag, Al, As, Be, Cd, Co, Cr, Cu, Ga, Hg, Mn, Ni, Pb, Sb, Se, Sn, Te, Tl, V, and Zn) and the major natural radionuclides (²³⁸U series, ²³²Th series, and ⁴⁰K). Mass balance calculations showed that most of the Hg, and some of the Sb and Se, were unaccounted for by ash collection, suggesting their possible discharge into the atmosphere. Silver, As, Hg, Pb, Cd, and Zn were more concentrated in the fly ash than in the bottom ash while all of the other elements were equally distributed, by concentration, between the ash fractions. The radionuclides showed a 46% higher concentration in fly ash than in bottom ash, and ²¹⁰Pb was enriched in the fly ash relative to the other radionuclides by a factor of 2.4. Mass balance calculations indicated a balance within statistical error for the radionuclides, except for ²¹⁰Pb.     

滴水湖沉积物中重金属污染特征与评价

分析滴水湖及其周边沉积物中Hg、As、Cu、Cd、Pb、Zn和Cr等7种重金属含量特征,并用地累积指数法、潜在生态风险指数法和主成分分析法对沉积物中的重金属污染状况进行了评价和分析。结果表明,滴水湖沉积物中As和Pb低于上海市潮滩背景值,Hg、Cd、Zn和Cr均高于潮滩背景值,50%样点的Cu高于潮滩背景值;地累积指数法评价结果表明滴水湖沉积物中Cr的平均污染水平为偏中污染,Hg、Cd和Zn为轻度污染,As、Cu和Pb为清洁水平;潜在生态风险指数法评价结果表明滴水湖沉积物重金属为中等生态风险,Hg和Cd是潜在生态风险的主要贡献元素;主成分分析结果表明,滴水湖沉积物中Hg、Cu、Cd、Pb、Zn和Cr主要来自于人为源,As主要来自底质滩涂     

Effects of Se and Zn supplementation on the antagonism against Pb and Cd in vegetables

The antagonistic effects of supplementation of Zn and Se to the soil on vegetables were studied in this work. In the pot experiment, Se (Se4+) and Zn (Zn2+) were applied, respectively, to the soil, in which the Chinese cabbage (Brassica rapa) and the lettuce (Lactuca sativa L.) were planted. As a result, Se and Zn were enriched evidently in the two vegetables. The contents of Pb and Cd in the two vegetables were decreased markedly while contents of some healthy mineral elements, like Mn and Mg, were increased to some extent when Se and Zn were applied. The antagonism of Se and Zn against Pb and Cd in plants was suggested. The farmland experiment on the lettuce was conducted to explore further the effect of supplementation of Zn and Se under the actual field conditions. Result came out to be that the enrichment of Zn and Se restrained the accumulation of Pb and Cd in the lettuce remarkably, as well as enhanced the absorption of some other nutritional elements, like Fe, Mn, Cu, Ca and Mg. Therefore, application of Se and Zn was proved to be an effective and feasible method to improve trace elements nutrition in the vegetables.     

Organochlorine compounds and heavy metals in the soft tissue of the mussel Mytilus galloprovincialis collected from Lake Faro (Sicily, Italy)

Three hundred samples of Mytilus galloprovincialis were collected from five stations (north, south, east, west and centre) of Lake Faro to evaluate the concentrations of organochlorine compounds and heavy metals. Quantitative determinations of organochlorine pesticides and PCBs were made by GC-ECD and confirmed with GC-MS. Concentrations of "essential" (Cu, Se and Zn) and "toxic" (As, Cd, Hg and Pb) metals were determined by an atomic absorption spectrophotometer. The results obtained show the low residue levels of p,p'-DDE in six samples of M. galloprovincialis from southern (7.00-11.00 ng/g w.w. and 148.3-275 ng/g l.w.) and western (7.60-15.37 ng/g w.w. and 126.7-256.2 ng/g l.w.) areas of Lake Faro. No appreciable residues of PCBs were found in any of the samples examined. Zn concentrations (range 11.0-18.5 microg/g w.w.) were higher than Cu (range 188.3-396.0 ng/g w.w.) and Se (range 93.5-288.9 ng/g w.w.) in all areas of origin. Cd (range 41.9-63.8 ng/g w.w.), Pb (range 64.8-93.0 ng/g w.w.) and Hg levels (range 5.7-13.1 ng/g w.w.) showed lower concentrations than permitted MRLs. The As levels were below detection limits for the all mussel samples. In conclusion, the absence of PCBs, the low levels of p,p'-DDE, the concentrations of Cd, Hg and Pb below permitted MRLs in M. galloprovincialis, used as a "biological indicator", show that Lake Faro is not at contamination risk from these contaminants and moreover is free from health problems for the consumer of mussel products.     

Speciation of heavy metals in marine sediments from the East China Sea by ICP-MS with sequential extraction

Twelve elements (V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Sn, Cd and Pb) in 24 sediment samples at eight sites (S1-S8) from the East China Sea were analyzed with the BCR sequential extraction (SE) protocol to obtain the metal distribution patterns in this region. The results showed that the heavy metal pollutions in S4 and S8 were more severe than in other sampling sites, especially Cd and Pb pollution. In the top sediments at S4 and S8, both the total contents and the most dangerous non-residual fractions of Cd and Pb were extremely high. More than 90% of the total concentrations of V, Cr, Mo and Sn existed in the residual fraction. Fe, Co, Ni, Cu and Zn mainly (more than 60%) occurred in the residual fraction. While Mn, Pb and Cd dominantly presented in the non-residual fractions in the top sediments. The metal distribution patterns with depth and the correlations between total organic carbon (TOC) and the total Fe-Mn content were also investigated. The results showed that, for most of the elements except Fe, the concentration of elements in fraction A in the top sediments was higher than that in other depth. The similar rule was also found in fraction B but not in fraction C. Besides, the distributions of V, Cd in fraction B and Pb, Cd, Cu in fraction C might be affected by TOC.     

Elemental analysis of total suspended particulate matter in the ambient air of Baghdad

Samples of atmospheric particulate matter obtained from representative areas of the city of Baghdad were collected on glass fiber filters using a high-volume sampler. Atomic absorption techniques were used to analyze the total suspended particulates (TSP) for the following trace metals; Fe, Cu, Zn, Pb, Mn, Cr, Cd, Co, and Hg. Sulfates were measured by turbidemetric method. Ion-selective electrodes was used for chloride analysis. It is concluded that the major components of TSP in the ambient air of Baghdad consist of mineral dust. Pb and Cd gave high enrichment factor values, which implies enrichment of these two metals from anthropogenic sources. High enrichment factors were also obtained for Zn and Cu. It is also concluded that in this arid area, the black smoke reflectance method is not suitable for measuring total suspended matter gravimetrically.     

Earthquake-related chemical and radioactivity changes of thermal water in Kuzuluk-Adapazan,Turkey

The movements of the North Anatolian Fault Zone (NAFZ) caused two devastating earthquakes within an 87-day interval, epicentered on G?lcük-Izmit (17 August, 1999) and Düzce-Bolu (12 November, 1999). The Kuzuluk geothermal area (KGA) is located in the middle of the epicenters and the distance between the geothermal area and the fault zone is less than 5 km. Hot water samples were collected from two thermal boreholes that supply hot water to the Kuzuluk thermal complex. The water samples taken prior to and after earthquakes were analysed by Neutron Activation and Atomic Absorption Spectroscopy. Particularly, increase in total a and total beta activities, in the content of Pb, Cr, Ni, Cu and decrease in the content of Fe, Zn, Cd, Mn, and Co are significant. The highest values are 75, 35, 12 and 65 ppb for Pb, Cr, Ni and Cu, respectively. The lowest values are 45, 55, 15, 135 and 6 ppb for Fe, Zn, Cd, Mn and Co, respectively.     

Time history of trace elements in sediments from Standley Lake,Colorado

Eighteen trace elements were analyzed in sections from a 50 cm long sediment core from Standley Lake, Colorado. The core was dated by the use of bomb-produced ¹³⁷Cs. Ten of the elements measured (Ag, Cd, Cu, Ga, Hg, Pb, Se, Sn, Tl, and Zn) appear to be enriched in this sediment; seven (Al, As, Be, Co, Cr, Ni, and V) are probably of local geological origin; and Te was not detected. Several of the constituents increase with depth in the sediment, and the concentrations of some compare to levels in lake sediments near highly industrialized centers. Based upon comparisons with other work, fluxes, enrichment factors, benzo(a)pyrene concentrations, and other evidence we conclude that the primary source of the “excess” elemental concentrations is local stream pollution.     

Innovative ‘Artificial Mussels’ technology for assessing spatial and temporal distribution of metals in Goulburn–Murray catchments waterways,Victoria, Australia: Effects of climate variability (dry vs. wet years)

The “Artificial mussel” (AM), a novel passive sampling technology, was used for the first time in Australia in freshwater to monitor and assess the risk of trace metals (Cd, Cu, Hg, Pb, and Zn). AMs were deployed at 10 sites within the Goulburn–Murray Water catchments, Victoria, Australia during a dry year (2009–2010) and a wet year (2010–2011). Our results showed that the AMs accumulated all the five metals. Cd, Pb, Hg were detected during the wet year but below detection limits during the dry year. At some sites close to orchards, vine yards and farming areas, elevated levels of Cu were clearly evident during the dry year, while elevated levels of Zn were found during the wet year; the Cu indicates localized inputs from the agricultural application of copper fungicide. The impacts from old mines were significantly less compared ‘hot spots’. Our study demonstrated that climate variability (dry, wet years) can influence the metal inputs to waterways via different transport pathways. Using the AMs, we were able to identify various ‘hot spots’ of heavy metals, which may pose a potential risk to aquatic ecosystems (sub-lethal effects to fish) and public (via food chain metal bioaccumulation and biomagnification) in the Goulburn–Murray Water catchments. The State Protection Policy exempted artificial channels and drains from protection of beneficial use (including protection of aquatic ecosystems) and majority of sites (‘hot spots’) were located within artificial irrigation channels.