Mobility of heavy metals from tailings to stream waters in a mining activity contaminated site

In this paper the results of a recent characterization of Rio Piscinas (SW of Sardinia, Italy) hydrological basin are reported. In such area (about 50 km2), previous mining activities caused a serious heavy metal contamination of surface waters, groundwater, soils and biota. Acid mine drainage phenomena were observed in the area. The main sources of contamination are the tailings stored in mine tunnels and abandoned along fluvial banks. A methodological approach was adopted in order to identify relations between tailings and water contamination. Representative samples of tailings and stream sediments samples were collected. XRD analyses were performed for mineralogical characterization, while acid digestion was carried out for determining metal contents. Batch sequential leaching tests were performed in order to assess metal mobility. Also groundwater and stream water were sampled in specific locations and suitably characterized. All information collected allowed the understanding of the effect of tailings on water contamination, thus contributing to the qualitative prediction of pollution evolution on the basis of metal mobility. Finally, a potential remediation strategy of stream water is proposed.     

Direct and indirect effects of metal contamination on soil biota in a Zn-Pb post-mining and smelting area (S Poland)

Effects of metal contamination on soil biota activity were investigated at 43 sites in 5 different habitats (defined by substratum and vegetation type) in a post-mining area. Sites were characterised in terms of soil pH and texture, nutrient status, total and exchangeable metal concentrations, as well as plant species richness and cover, abundances of enchytraeids, nematodes and tardigrades, and microbial respiration and biomass. The concentrations of total trace metals were highest in soils developed on mining waste (metal-rich dolomite), but these habitats were more attractive than sandy sites for plants and soil biota because of their higher content of organic matter, clay and nutrients. Soil mesofauna and microbes were strongly dependent on natural habitat properties. Pollution (exchangeable Zn and Cd) negatively affected only enchytraeid density; due to a positive relationship between enchytraeids and microbes it indirectly reduced microbial activity.     

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.     

Is PCBs concentration variability between and within freshwater fish species explained by their contamination pathways?

Many chemical, physiological, and trophic factors are known to affect bioaccumulation of polychlorinated biphenyls (PCBs) in biota. Understanding the primary factors affecting fish contamination is critical for predicting and assessing risks to upper-trophic level consumers, including humans. Here we identify PCB contamination pathways that could explain within- and between-species variability in fish concentration levels. Three freshwater river fish species (barbel, chub and bream) were sampled at three sites along the Rhone River (France) where fish consumption is partially prohibited because of PCB levels exceeding the European health-based benchmark. The trophic position was assessed using an innovative approach based on stable isotope analyses and Bayesian inference, which takes into account both isotope data variability and parameter uncertainty. The effect of foraging habitat on fish contamination was addressed using stable isotope mixing models. The fish trophic position and PCB concentrations were found to be unrelated while the exploitation of sediment detrital carbon as a food source appeared to be a critical factor affecting fish contamination. Fish length, PCB concentration of the sediment, and individual fish foraging habitat (exploitation of detrital versus planktonic carbon sources) explained 80% of within- and between-species variability observed in PCB concentrations. These results, obtained for species that have overlapping TPs and exploit different carbon sources, reveal that the important factor in fish PCB contamination is not only what fish consume, but also and essentially the feeding location.     

Metal partitioning and uptake in central Ontario forests

Evaluation of the potential environmental risk posed by metals depends to a great extent on modeling the fate and mobility of metals with soil-solution partitioning coefficients (Kd). However, the effect of biological cycling on metal partitioning is rarely considered in standard risk assessments. We determined soil-solution partitioning coefficients for 5 metals (Cd, Zn, Pb, Co and Ni) at 46 forested sites that border the Precambrian Shield in central Ontario, where soil pHaq varied from 3.9 to 8.1. Foliage from the dominant tree species and forest floor samples were also collected from each site to compare their metal levels with Kd predictions. Analogous to other studies, log Kd values for all metals were predicted by empirical linear regression with soil pH (r2=0.66-0.72), demonstrating that metal partitioning between soil and soil solution can be reliably predicted for relatively unpolluted forest mineral soils by soil pH. In contrast, whereas the so-called bioavailable water-soluble metal fraction could be predicted from soil pH, metal concentrations in foliage and the forest floor at each site were not consistently related to pH. Risk assessment of metals should take into account the role of biota in metal cycling and partitioning in forests, particularly if metal bio-accumulation and chronic toxicity in the food chain, rather than metal mobility in soils, are of primary concern.     

Impact of metals on histopathology and expression of HSP 70 in different tissues of Milk fish (Chanos chanos) of Kaattuppalli Island, South East Coast, India

Histological and Immunohistochemical studies were carried out to document the possible impact of heavy metal contamination in different tissues of Chanos chanos. Heavy metals such as Cu, Pb, Zn, Cd, Mn and Fe were predominant in water, sediment and biota of Kaattuppalli Island and varied significantly between two different sites. Histological changes such as swelling of muscle fiber and break down of muscle bundles were noted in the muscle. Similarly gill filament cell proliferation, increase in intercellular spaces and primary and secondary lamellar epithelium were evident in gills. The hepatocytes showed damage of central vein and rupture of irregular hepatic plate with more number of vacuoles in the fish collected from polluted site compared to that from the less polluted site. The impact of pollution was also assessed in different tissues by immunohistochemistry using primary antibody (mouse monoclonal HSP70 antibody 1:2000) and secondary antibody (HRP conjugated antibody) for expression of stress protein. Immunostaining analysis showed expression of HSP70 with high intensity in the tissues of fish collected from polluted site compared to less polluted sites. Further, HSP70 positive cells were analyzed from six locations per fish tissue section. One-way analysis of variance (ANOVA) followed by least significant difference (LSD) was used to check if the expression was significant. Results indicate that the values are statistically significant at the two different sampling sites (P<0.05).     

Biomonitoring for metal contamination near two Superfund sites in Woburn, Massachusetts, using phytochelatins

Characterizing the spatial extent of groundwater metal contamination traditionally requires installing sampling wells, an expensive and time-consuming process in urban areas. Moreover, extrapolating biotic effects from metal concentrations alone is problematic, making ecological risk assessment difficult. Our study is the first to examine the use of phytochelatin measurements in tree leaves for delimiting biological metal stress in shallow, metal-contaminated groundwater systems. Three tree species (Rhamnus frangula, Acer platanoides, and Betula populifolia) growing above the shallow groundwater aquifer of the Aberjona River watershed in Woburn, Massachusetts, display a pattern of phytochelatin production consistent with known sources of metal contamination and groundwater flow direction near the Industri-Plex Superfund site. Results also suggest the existence of a second area of contaminated groundwater and elevated metal stress near the Wells G&H Superfund site downstream, in agreement with a recent EPA ecological risk assessment. Possible contamination pathways at this site are discussed.     

Metal accumulation in arthropods near a lead/zinc smelter in Arnoldstein, Austria. I

This study reports on accumulation of lead, cadmium, copper and zinc in soil, plants and arthropod species in the vicinity of a closed-down lead/zinc smelter with a long history of pollution in Arnoldstein, Austria. Significant site-dependent metal accumulations were measured in most species, increasing in line with site contamination. Within a site, clear species-specific differences were found, even between closely related species. Within some species, developmental-, sex- and/or seasonal-specificities occurred, reflecting individual metal budgeting capabilities. Evidence for copper regulatory mechanisms appeared to be established in most cases, whereas lead, the main pollutant of the region, became heavily accumulated in some organisms. Higher levels of lead than previously reported in field surveys were detected in Carabidae and Caelifera at the most polluted site. It is recommended to take ecological and physiological parameters of species into consideration in interpreting field data on arthropod metal accumulation.     

Fate and effects of anthropogenic chemicals in mangrove ecosystems: a review

The scientific literature for fate and effects of non-nutrient contaminant concentrations is skewed for reports describing sediment contamination and bioaccumulation for trace metals. Concentrations for at least 22 trace metals have been reported in mangrove sediments. Some concentrations exceed sediment quality guidelines suggesting adverse effects. Bioaccumulation results are available for at least 11 trace metals, 12 mangrove tissues, 33 mangrove species and 53 species of mangrove-habitat biota. Results are specific to species, tissues, life stage, and season and accumulated concentrations and bioconcentration factors are usually low. Toxicity tests have been conducted with 12 mangrove species and 8 species of mangrove-related fauna. As many as 39 effect parameters, most sublethal, have been monitored during the usual 3 to 6 month test durations. Generalizations and extrapolations for toxicity between species and chemicals are restricted by data scarcity and lack of experimental consistency. This hinders chemical risk assessments and validation of effects-based criteria.     

Biota–sediment accumulation factor (BSAF), bioaccumulation factor (BAF), and contaminant levels in prey fish to indicate the extent of PAHs and OCPs contamination in eggs of waterbirds

Samples of pond sediment, fish, and shrimp were collected from the Ramsar site at Mai Po marshes, Hong Kong (south China), and samples of pond sediment, fish, and shrimp, as well as eggs of water birds (Chinese Pond Herons (Ardeola bacchus) and Little Egrets (Egretta garzetta)), were collected from two smaller wetland sites at Jiangsu Province (mid-China), between 2004 and 2007. Accumulation levels of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) in the biota were used to calculate biota–sediment accumulation factor (BSAF) and bioaccumulation factor (BAF). For fish and shrimp, BSAFs of OCPs (3.8–56) were greater than those of PAHs (0.12–6.3). BSAFs and BAFs of 11–79 and 4–34, respectively, were registered for OCPs in eggs of the birds and were greater than those for PAHs (0.11–1.5 and 0.02–1.3, respectively). Assuming that fish were the main prey of the birds, greater bioaccumulation of OCPs was detected for both bird species (BAFs?=?4.5–34), while accumulation of PAHs was only detected in Little Egret (BAF?=?1.3). A significant linear relationship (p?<?0.01) was observed between concentrations of OCPs in bird eggs and in the prey fish. The present study provides a new possibility of using OCP levels detected in prey fish to predict the extent of OCPs contamination in eggs of waterbirds including the endangered species, as a noninvasive method.     

Impact of the earthworm Lumbricus terrestris (L.) on As, Cu, Pb and Zn mobility and speciation in contaminated soils

To assess the risks that contaminated soils pose to the environment properly a greater understanding of how soil biota influence the mobility of metal(loid)s in soils is required. Lumbricus terrestris L. were incubated in three soils contaminated with As, Cu, Pb and Zn. The concentration and speciation of metal(loid)s in pore waters and the mobility and partitioning in casts were compared with earthworm-free soil. Generally the concentrations of water extractable metal(loid)s in earthworm casts were greater than in earthworm-free soil. The impact of the earthworms on concentration and speciation in pore waters was soil and metal specific and could be explained either by earthworm induced changes in soil pH or soluble organic carbon. The mobilisation of metal(loid)s in the environment by earthworm activity may allow for leaching or uptake into biota.     

Trophic transfer of persistent organochlorine contaminants (OCs) within an Arctic marine food web from the southern Beaufort-Chukchi Seas

Stable isotope values (13C, 15N) and concentrations of persistent organochlorine contaminants (OCs) were determined to evaluate the near-shore marine trophic status of biota and biomagnification of OCs from the southern Beaufort-Chukchi Seas (1999-2000) near Barrow, AK. The biota examined included zooplankton (Calanus spp.), fish species such as arctic cod (Boreogadus saida), arctic char (Salvelinus alpinus), pink salmon (Oncorhynchus gorbuscha), and fourhorn sculpin (Myoxocephalus quadricornis), along with marine mammals, including bowhead whales (Balaena mysticetus), beluga whales (Delphinapterus leucas), ringed seals (Phoca hispida) and bearded seals (Erignathus barbatus). The isotopically derived trophic position of biota from the Beaufort-Chukchi Seas marine food web, avian fauna excluded, is similar to other coastal food webs in the Arctic. Concentrations of OCs in marine mammals were significantly greater than in fish and corresponded with determined trophic level. In general, OCs with the greatest food web magnification factors (FWMFs) were those either formed due to biotransformation (e.g. p,p'-DDE, oxychlordane) or considered recalcitrant (e.g. -HCH, 2,4,5-Cl substituted PCBs) in most biota, whereas concentrations of OCs that are considered to be readily eliminated (e.g. -HCH) did not correlate with trophic level. Differences in physical-chemical properties of OCs, feeding strategy and possible biotransformation were reflected in the variable biomagnification between fish and marine mammals. The FWMFs in the Beaufort-Chukchi Seas region were consistent with reported values in the Canadian Arctic and temperate food webs, but were statistically different than FWMFs from the Barents and White Seas, indicating that the spatial variability of OC contamination in top-level marine Arctic predators is attributed to differences in regional sources of contamination rather than trophic position.     

Levels and body distribution of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in freshwater fishes from the Yangtze River, China

Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) were determined in muscle, liver and eggs of freshwater fishes from the lower reach of the Yangtze River, China. The present study is the first to report HBCD concentrations in the environment of China. The concentrations of PBDEs and HBCDs in muscle of freshwater fishes from the Yangtze River ranged from 18 to 1100ng/g and 12 to 330ng/g lipid weight (wt.), respectively. When compared with other regions of the world, the contamination of PBDEs in biota could be regarded as moderate, whereas contamination of HBCDs in biota was relatively high. The PBDE congener profiles in fishes of the present study were markedly different from those observed in freshwater and marine fishes from other regions of the world. In the present study, BDE-15, BDE-28 and BDE-47 were the predominant congeners in the fishes. This particular congener profile in fishes from the Yangtze River revealed that a specific commercial PBDE formulation (probably made in China) might have been used in the Yangtze River Delta region.     

Mercury,zinc, and copper accumulation in mangrove sediments surrounding a large landfill in southeast Brazil

The accumulation of Hg, Zn, and Cu was evaluated in mangrove sediments located between a large, 20-years-old landfill and waters of Guanabara Bay (southeast Brazil). The contamination history of the area provides substantial evidence that metal accumulation in the study site is influenced by past metal emissions from multiple sources (e.g. contaminated rivers and the landfill surrounding the site). At the southern part of the site, metal levels are up to 890 ng g(-1) Hg, 850 microg g(-1) Zn, and 58 microg g(-1) Cu. Enrichment factors and excess (background-deducted) concentration inventories show a high spatial variability of metal contamination and storage in the site, with differences often by a factor higher than two within a sampling station and higher than five between sampling stations. These contrasts are attributable to a coupling between spatial variability of anthropogenic metal input and metal behavior and retention within the sediments. Results indicate that during the last few decades mangrove sediments retained a substantial part of metal emissions to the site, probably reducing the metal transport to Guanabara Bay waters, and suggest the suitability of mangrove ecosystems as physical and biogeochemical barriers to metal contaminant transport.     

The effects of multiple metal contamination on ectomycorrhizal Scots pine (Pinus sylvestris) seedlings

Experiments were conducted to investigate the effects of single and multiple metal contamination (Cd, Pb, Zn, Sb, Cu) on Scots pine seedlings colonised by ectomycorrhizal (ECM) fungi from natural soil inoculum. Seedlings were grown in either contaminated field soil from the site of a chemical accident, soils amended with five metals contaminating the site, or in soil from an uncontaminated control site. Although contaminated and metal-amended soil significantly inhibited root and shoot growth of the Scots pine seedlings, total root tip density was not affected. Of the five metals tested in amended soils, Cd was the most toxic to ECM Scots pine. Field-contaminated soil had a toxic effect on ECM fungi associated with Scots pine seedlings and caused shifts in ECM species composition on ECM seedlings. When compared to soils amended with only one metal, soils amended with a combination of all five metals tested had lower relative toxicity and less accumulation of Pb, Zn and Sb into seedlings. This would indicate that the toxicity of multiple metal contamination cannot be predicted from the individual toxicity of the metals investigated.     

Threat of heavy metal pollution in halophytic and mangrove plants of Tamil Nadu, India

Mangrove and halophytic plants occur along the coastal areas of Tamil Nadu, south India and these plants have been used in traditional medicine for centuries. Heavy metals are known to pose a potential threat to terrestrial and aquatic biota. However, little is known on the toxic levels of heavy metals found in mangrove and halophytic plants that are used in traditional medicine in India. To understand heavy metal toxicity, we investigated the bioconcentration factors (BCF) of heavy metals in leaves collected from eight mangroves and five halophytes in the protected Pichavaram mangrove forest reserve in Tamil Nadu State, south India. Data presented in this paper describe the impact of essential (Cu, Fe, Mg, Mn and Zn) and non-essential/environmentally toxic trace metals (Hg, Pb and Sn) in mangrove and halophytic medicinal plants. The concentrations of Pb among 13 plant species were higher than the normal range of contamination reported for plants. The average concentration of Hg in the halophytic plants (0.43+/-0.37mug/g) was seven times higher than mangrove plants (0.06+/-0.03mug/g) and it indicated pollutants from industrial sources affecting halophytes more than mangroves.     

Organochlorine pollution in tropical rivers (Guadeloupe): role of ecological factors in food web bioaccumulation

Concentrations of organochlorine pesticides and stable isotope ratios of nitrogen and carbon were measured in a tropical freshwater ecosystem to evaluate the contamination level of biota and examine the bioaccumulation patterns of pollutants through the food web. Chemical analyses showed a general and heavy contamination of the entire food web. They revealed the strong accumulation of pollutants by juveniles of diadromous fishes and shrimps, as they re-enter the river. The role of ecological factors in the bioaccumulation of pesticides was evaluated. Whereas the most persistent pollutants (chlordecone and monohydro-chlordecone) were related to the organisms diet and habitat, bioaccumulation of β-HCH was only influenced by animal lipid content. The biomagnification potential of chlordecone through the food chain has been demonstrated. It highlighted the importance of trophic transfer in this compound bioaccumulation process. In contrast, bioconcentration by passive diffusion from water seemed to be the main exposure route of biota to β-HCH.     

Effect of organic carbon and metal accumulation on the bacterial communities in sulphidogenic sediments

A unique geochemical setting in Lake Cadagno, Switzerland, has led to the accumulation of insoluble metal sulphides in the sedimentary record as the result of past airborne pollution. This offers an exceptional opportunity to study the effect of these metals on the bacterial communities in sediments, and in particular to investigate further the link between metal contamination and an increase in the populations of endospore-forming bacteria observed previously in other metal-contaminated sediments. A decrease in organic carbon and total bacterial counts was correlated with an increase in the numbers of endospores in the oldest sediment samples, showing the first environmental evidence of a decrease in nutrient availability as a trigger of sporulation. Proteobacteria and Firmicutes were the two dominant bacterial phyla throughout the sediment, the former in an area with high sulphidogenic activity, and the latter in the oldest samples. Even though the dominant Firmicutes taxa were stable along the sediment core and did not vary with changes in metal contamination, the prevalence of some molecular species like Clostridium sp. was positively correlated with metal sulphide concentration. However, this cannot be generalized to all endospore-forming species. Overall, the community composition supports the hypothesis of sporulation as the main mechanism explaining the dominance of endospore formers in the deepest part of the sediment core, while metal contamination in the form of insoluble metal sulphide deposits appears not to be linked with sporulation as a mechanism of metal tolerance in this sulphidogenic ecosystem.     

Distribution of Pb, Cd and Ba in soils and plants of two contaminated sites

Evaluation of metal accumulation in soils and plants is of environmental importance due to their health effects on humans and other biota. Soil material and plant tissue were collected along transects in two heavily contaminated facilities, a Superfund site and a lead-acid battery dump, and analyzed for metal content. Soil lead (Pb), cadmium (Cd) and barium (Ba) concentrations for the Superfund site averaged 55,480, 8.5 and 132.3 mg/kg, respectively. Soil Pb occurred primarily in the carbonate, sulfide/residual and organic chemical fractions (41.6, 28.6 and 16.7%, respectively). Soil Pb, Cd and Ba concentrations for the dump site averaged 29,400, 3.9 and 1130 mg/kg, respectively. Soil Pb occurred mostly in the organic and carbonate fractions as 48.5 and 42.5%, respectively. Pb uptake in the two sites ranged from non-detectable (Agrostemma githago, Plantago rugelii, Alliaria officinalis shoots), to 1800 mg/kg (Agrostemma githago root). Cd uptake was maximal in Taraxacum officinale at 15.4 mg/kg (Superfund site). In the majority > or =65%) of the plants studied, root Pb and Cd content was higher than that for the shoots. Tissue Pb correlated slightly with exchangeable and soluble soil Pb; however, tissue Cd was poorly correlated with soil Cd species. None of the sampled plants accumulated measurable amounts of Ba. Those plants that removed most Pb and Cd were predominantly herbaceous species, some of which produce sufficient biomass to be practical for phytoremediation technologies. Growth chamber studies demonstrated the ability of T. officinale and Ambrosia artemisiifolia to successfully remove soil Pb and Cd during repeated croppings. Tissue Pb was correlated with exchangeable soil Pb at r(2)=0.68 in Ambrosia artemisiifolia.     

To what extent are hepatic concentrations of heavy metals in Anguilla anguilla at a site in a contaminated estuary related to body size and age and reflected in the metallothionein concentrations?

We explored how hepatic [metal]s in Anguilla anguilla at a contaminated estuarine site are influenced by body size, age and season, and the extent that [Cu], [Cd] and [Zn]s are reflected in [metallothionein (MT)]s. Although each [metal] and [MT] increased significantly with length, weight and age, those biotic variables explained <10% of the variation in each [metal] and only 11-16% for [MT]. Seasonal changes in [Cu] and [Cd] were paralleled by [MT]. The variation in [MT] explained by Cu (42%) was greater than by Zn (16%) and Cd (13%), and seasonally lay between 43 and 69% for those metals collectively. Thus, hepatic [MT] in eels is closely correlated with hepatic [heavy metal]s. However, the great variability among [MT]s for eels of similar sizes and ages, which reflects marked variability in hepatic [heavy metal]s, means that this variable reflects imprecisely the contamination level at a particular site.