Risks of using membrane filtration for trace metal analysis and assessing the dissolved metal fraction of aqueous media--a study on zinc, copper and nickel

Membrane filtration is commonly performed for solid-liquid separation of aqueous solutions prior to trace metal analysis and when assessing “dissolved” metal fractions. Potential artifacts induced by filtration such as contamination and/or adsorption of metals within the membrane have been investigated for different membrane materials, metals, applied pressures and pre-cleaning steps. Measurements have been conducted on aqueous solutions including well-defined metal standards, ultrapure water, and on runoff water from corroded samples.Filtration using both non-cleaned and pre-cleaned filters revealed contamination and adsorption effects, in particular pronounced for zinc, evident for copper but non-significant for nickel. The results clearly show these artifacts to be non-systematic both for non-cleaned and pre-cleaned membranes. The applied pressure was of minor importance.Measurements of the labile fraction by means of stripping voltammetry clearly elucidate that membrane filtration followed by total metal analysis cannot accurately assess the labile or the dissolved metal fraction.     

DNA damage in caged Gammarus fossarum amphipods: a tool for freshwater genotoxicity assessment

The aim of this study was to propose a tool for freshwater environmental genotoxicity assessment using Gammarus fossarum, a high ecologically relevant species. In a first part, gammarids were caged upstream and downstream wastewater treatment plant effluent output. The sensitivity of genotoxic responses of haemocytes, oocytes and spermatozoa was compared using the Comet assay. Spermatozoa appeared to be the most sensitive, suitable and relevant cell type for genotoxicity risk assessment. In a second part, a watershed-scale study was conducted over 2 years to evaluate the applicability of our caging procedure. The genotoxic impact of a contamination was followed, taking into account seasonal variability. DNA damage in spermatozoa exhibited low basal level and low variability in control upstream sites, providing a reliable discrimination of polluted sites. Finally, DNA damage in caged G. fossarum has been proved to be a sensitive and reproducible tool for freshwater genotoxicity assessment.     

Concentration of trace elements in feathers of three Antarctic penguins: Geographical and interspecific differences

Antarctica is often considered as one of the last pristine regions, but it could be affected by pollution at global and local scale. Concentrations of Al, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Cd and Pb were determinated by ICP-MS in feathers (n = 207 individuals) of gentoo, chinstrap and Adélie penguin collected in 8 locations throughout the Antarctic Peninsula (2006-2007). The highest levels of several elements were found in samples from King George Island (8.08, 20.29 and 1.76 μg g⁻¹ dw for Cr, Cu and Pb, respectively) and Deception Island (203.13, 3.26 and 164.26 μg g⁻¹ dw for Al, Mn and Fe, respectively), where probably human activities and large-scale transport of pollutants contribute to increase metal levels. Concentrations of Cr, Mn, Cu, Se or Pb, which are similar to others found in different regions of the world, show that some areas in Antarctica are not utterly pristine.     

The effects of dietary nickel on the detoxification enzymes, innate immunity and resistance to the fungus Beauveria bassiana in the larvae of the greater wax moth Galleria mellonella

In this study, we tested the effects of dietary nickel on the activity of glutathione S-transferase (GST), esterases, phenoloxidase, and encapsulation in the haemolymph of larvae of the greater wax moth Galleria mellonella. We also explored the effects of dietary nickel on larval resistance to infection by the fungus Beauveria bassiana. Larvae fed a low dose of nickel (10 μg g⁻¹) had significantly higher GST, phenoloxidase activity and encapsulation responses than controls fed on a nickel-free diet. We also found that larvae fed a sublethal dose of nickel (50 μg g⁻¹) had increased GST, esterase activity and encapsulation rates but decreased phenoloxidase activity. Although, a sublethal dose of dietary nickel enhanced innate immunity, we found that this reduced resistance against the real pathogen. Our results suggest that enhanced immunity and detoxification enzyme activity of insects may not be beneficial to resistance to fungal infection. It appears that there is a trade off between different resistance mechanisms in insects under different metal treatments.     

Comparison of EDTA-enhanced phytoextraction and phytostabilisation strategies with Lolium perenne on a heavy metal contaminated soil

Phytoremediation is a promising and cost-effective strategy to manage heavy metal polluted sites. In this experiment, we compared simultaneously phytoextraction and phytostabilisation techniques on a Cd and Zn contaminated soil, through monitoring of plant accumulation and leaching. Lolium perenne plants were cultivated for 2 months under controlled environmental conditions in a 27.6 dm³-pot experiment allowing the collect of leachates. The heavy metal phytoextraction was promoted by adding Na-EDTA (0.5 g kg⁻¹ of soil) in watering solution. Phytostabilisation was assessed by mixing soil with steel shots (1%) before L. perenne sowing. Presence of plants exacerbated heavy metal leaching, by improving soil hydraulic conductivity. Use of EDTA for phytoextraction led to higher concentration of heavy metal in shoots. However, this higher heavy metal extraction was insufficient to satisfactory reduce the heavy metal content in soil, and led to important heavy metal leaching induced by EDTA. On the other hand, addition of steel shots efficiently decreased both Cd and Zn mobility, according to 0.01 M CaCl₂ extraction, and leaching. However, improvement of growth conditions by steel shots led to higher heavy metal mass in shoot tissues. Therefore, soil heavy metal mobility and plant metal uptake are not systematically positively correlated.     

Salinity increases mobility of heavy metals in soils

The effect of salinity induced by CaCl₂, MgCl₂, NaCl and Na₂SO₄ on the mobility of Cu, Cd, Pb and Zn was studied. An increase of ionic strength by any salts promoted a higher release of Cd than the others metals. When CaCl₂ and NaCl were applied, Cd and Pb showed the highest degree of mobilization. When MgCl₂ was applied, Cd and Cu were mobilized the most. Finally, an increase of Na₂SO₄ also promoted the strongest mobilization of Cd and Cu.As the total heavy metal content was higher, the percentage of Pb and Cu released upon salinization decreased, indicating that these metals are strongly bound to soil constituents. An increase of carbonates in the soil promoted a higher release of Pb for all used salts and for Zn when MgCl₂ and NaCl were used. This indicates that Pb and Zn are adsorbed on the surface of carbonate crystals. An increase of fine particles promoted a decrease of percentage of released Cd for all salts, indicating that Cd is strongly retained in the fine fractions.The main mechanism regulating Pb and Cd mobility was competition with Ca²⁺ for sorption sites followed for metal chloro-complexation, association between the Cd/Pb-sulfates and competition with Mg²⁺. The main mechanism regulating Cu mobility was the formation of Cu-sulfate, followed by competition with cations (Mg > Ca) and chloride. For Zn, competition with Ca²⁺ for sorption sites was the most important process for its mobility; followed by Zn-sulfate association and, finally, chloride and competition with Mg with the same effect.     

Body metal concentrations and glycogen reserves in earthworms (Dendrobaena octaedra) from contaminated and uncontaminated forest soil

Stress originating from toxicants such as heavy metals can induce compensatory changes in the energy metabolism of organisms due to increased energy expenses associated with detoxification and excretion processes. These energy expenses may be reflected in the available energy reserves such as glycogen. In a field study the earthworm, Dendrobaena octaedra, was collected from polluted areas, and from unpolluted reference areas. If present in the environment, cadmium, lead and copper accumulated to high concentrations in D. octaedra. In contrast, other toxic metals such as aluminium, nickel and zinc appeared to be regulated and kept at low internal concentrations compared to soil concentrations. Lead, cadmium and copper accumulation did not correlate with glycogen reserves of individual worms. In contrast, aluminium, nickel and zinc were negatively correlated with glycogen reserves. These results suggest that coping with different metals in earthworms is associated with differential energy demands depending on the associated detoxification strategy.     

Plant communities in relation to flooding and soil contamination in a lowland Rhine River floodplain

Using canonical correspondence analysis (CCA), relationships were investigated between plant species composition and flooding characteristics, heavy metal contamination and soil properties in a lowland floodplain of the Rhine River. Floodplain elevation and yearly average flooding duration turned out to be more important for explaining variation in plant species composition than soil heavy metal contamination. Nevertheless, plant species richness and diversity showed a significant decrease with the level of contamination. As single heavy metal concentrations seemed mostly too low for causing phytotoxic effects in plants, this trend is possibly explained by additive effects of multiple contaminants or by the concomitant influences of contamination and non-chemical stressors like flooding. These results suggest that impacts of soil contamination on plants in floodplains could be larger than expected from mere soil concentrations. In general, these findings emphasize the relevance of analyzing effects of toxic substances in concert with the effects of other relevant stressors.     

Atmospheric particle characterization, distribution, and deposition in Xi'an, Shaanxi Province, Central China

Physical characterization and chemical analysis of settled dusts collected in Xi’an from November 2007 to December 2008 show that (1) dust deposition rates ranged from 14.6 to 350.4 g m⁻² yr⁻¹. The average deposition rate (76.7 g m⁻² yr⁻¹) ranks the 11th out of 56 dust deposition rates observed throughout the world. The coal-burning power was the major particle source; (2) on average (except site 4), ∼10% of the settled dusts having size <2.6, ∼30% having size <10.5, and >70% having size <30 μm; (3) the concentrations for 20 out of 27 elements analyzed were upto 18 times higher than their soil background values in China. With such high deposition rates of dusts that contain elevated levels of toxic elements, actions should be taken to reduce emission and studies are needed to assess the potential impacts of settled particles on surface ecosystem, water resource, and human health in the area.     

大宝山矿区水体和沉积物中重金属的污染评价

分别于丰水期和枯水期对广东省大宝山矿区铁龙拦泥坝至凉桥河段水体中溶解态的重金属进行了调查,应用EPA推荐的健康风险评价模型发现,水体中非致癌物通过饮水途径所导致平均个人年风险排列顺序是Cu〉Pb〉Zn,最大值的平均个人年风险在丰水期和枯水期的平均值分别是2.14×10-7 a-1和4.13×10-7 a-1,小于国际防辐射委员会（ICRP）推荐的最大可接受平均个人年风险5.0×10-5a-1。致癌物Cd的平均个人年风险在丰水期和枯水期的平均值分别是3.52×10-4 a-1和4.53×10-4 a-1,大于ICRP推荐的最大可接受值,同时也大于非致癌物3～4个数量级。另外,通过对枯水期沉积物的重金属总量分析,发现凉桥槽对坑支流受水体pH的影响,导致其沉积物重金属的浓度最高。根据Long和Macdonald利用生物效应数据库法建立的沉积物质量基准,发现除冷水泾外,其他采样点的平均效应中值指数（mERMQ）值都大于1.5,可见沉积物中的重金属会对当地底栖生物产生毒害作用。