Bioaccumulation of mining derived metals in blood, liver, muscle and otoliths of two Arctic predatory fish species (Gadus ogac and Myoxocephalus scorpius).

Mining activities can cause adverse and long-lasting environmental impacts and detailed monitoring is therefore essential to assess the pollution status of mining impacted areas. Here we evaluated the efficacy of two predatory fish species (Gadus ogac i.e. Greenland cod and Myoxocephalus scorpius i.e. shorthorn sculpin) as biomonitors of mining derived metals (Pb, Zn, Cd and Hg) by measuring concentrations in blood, liver, muscle and otoliths along a distance gradient near the former Black Angel Pb-Zn mine (West Greenland). We detected metals in all tissues (except Cd and Hg in otoliths) and sculpin generally displayed higher concentrations than cod. For both species, concentrations were generally highest closest to the dominant pollution source(s) and gradually decreased away from the mine. The clearest gradient was observed for Pb in blood and liver (both species), and for Pb in otoliths (sculpin only). Similar to dissolved concentrations in seawater (but in contrast to bottom sediment), no significant decrease was found for Zn, Cd and Hg in any of the tissues. This demonstrates that by including tissues of blood (representing recent accumulation) and otolith (representing more long-term exposure signals) in the sampling collection, the temporal information on contaminant exposure and accumulation can be extended. We therefore conclude that both fish species are suitable as biomonitors near Arctic mine sites and, moreover, that blood and otoliths can serve as important supplementary monitoring tissues (in addition to liver and muscle traditionally sampled) as they provide extended temporal information on recent to long-term contaminant exposure.

Genetic damage induced by electronic waste leachates and contaminated underground water in two prokaryotic systems.

The inappropriate and unsafe management practices related to disposal and recycling of electronic wastes in Nigeria has led to environmental and underground water contamination. Reports on the level and type of contamination as well as the possible DNA damage effects of this contamination are insufficient. This study evaluated the DNA damaging potential of e-waste simulated and raw leachates, and its contaminated underground water using the SOS chromotest on Escherichia coli PQ37 and the Ames Salmonella fluctuation test on Salmonella typhimurium strains TA98 and TA100, without and with metabolic activation. Physico-chemical parameters of the samples were also analyzed. The result of the Ames test showed induction of base pair substitution and frameshift mutation by the test samples. However, the TA100 was the more responsive strain for the three samples in terms of mutagenic index in the absence and presence of metabolic activation. The SOS chromotest results were in agreement with those of the Ames Salmonella fluctuation test. Nevertheless, the E. coli PQ37 system was slightly more sensitive than the Salmonella assay for detecting genotoxins in the tested samples. Lead, cadmium, manganese, copper, nickel, chromium, arsenic, and zinc contents analyzed in the samples were believed to play a significant role in the observed DNA damage in the microbial assays. The results of this study showed that e-waste simulated and raw leachates, and its contaminated underground water are of potential mutagenic and genotoxic risks to the exposed human populace.

Cadmium impact, accumulation and detection in poplar callus cells.

Effect of cadmium cations and their interaction with silicon cations was determined in poplar calli and expressed as changes in callus growth, cell viability and cadmium cation accumulation. Cell viability throughout culture versus cadmium cation accumulation in cells is discussed. At the same time, the study sought appropriate methods for cadmium cation detection in callus cells and also in experiments with low plant material (e.g. protoplasts). Cadmium cations were determined by atomic absorption spectroscopy and using fluorescence microscopy with a specific cadmium cation fluorescent dye. The detection of cadmium cations in callus cells by the latter method appears suitable because the callus cells are surrounded by primary cell walls without auto-fluorescence and these values fit well with atomic absorption spectroscopy quantification. However, the visualisation method has some limits discussed below.

Improved physiologically based pharmacokinetic model for oral exposures to chromium in mice, rats, and humans to address temporal variation and sensitive populations.

A physiologically based pharmacokinetic (PBPK) model for hexavalent chromium [Cr(VI)] in mice, rats, and humans developed previously (Kirman et al., 2012, 2013), was updated to reflect an improved understanding of the toxicokinetics of the gastrointestinal tract following oral exposures. Improvements were made to: (1) the reduction model, which describes the pH-dependent reduction of Cr(VI) to Cr(III) in the gastrointestinal tract under both fasted and fed states; (2) drinking water pattern simulations, to better describe dosimetry in rodents under the conditions of the NTP cancer bioassay; and (3) parameterize the model to characterize potentially sensitive human populations. Important species differences, sources of non-linear toxicokinetics, and human variation are identified and discussed within the context of human health risk assessment.

Effects of sediment contamination on physiological and biochemical responses of the polychaete Diopatra neapolitana, an exploited natural resource.

The present study reports metal and arsenic contamination in sediments, as well as element accumulation and partitioning in the polychaete Diopatra neapolitana in the Ria de Aveiro lagoon (Portugal). The polychaetes biochemical performance and tissue regenerative capacity were also evaluated. The concentration of elements in sediments showed an increase of contamination among areas (areas A-G), but higher bioaccumulation was observed in organisms from a less contaminated area (area C, BAF>1). This study evidenced that individuals with higher elements bioaccumulation presented higher LPO and lower GSH/GSSG and also exhibited lower capacity for body regeneration. Polychaetes biotransformation capacity as well as antioxidant defense mechanisms were not sufficiently efficient to withstand the excess of ROS leading to increased LPO when organisms presented higher bioaccumulation levels. Additionally, an increase of methalotionines was also observed in individuals with higher bioaccumulation of metals and As, suggesting an induction of detoxification processes.

Methylmercury Induced Neurotoxicity and the Influence of Selenium in the Brains of Adult Zebrafish (Danio rerio).

The neurotoxicity of methylmercury (MeHg) is well characterised, and the ameliorating effects of selenium have been described. However, little is known about the molecular mechanisms behind this contaminant-nutrient interaction. We investigated the influence of selenium (as selenomethionine, SeMet) and MeHg on mercury accumulation and protein expression in the brain of adult zebrafish (Danio rerio). Fish were fed diets containing elevated levels of MeHg and/or SeMet in a 2 × 2 full factorial design for eight weeks. Mercury concentrations were highest in the brain tissue of MeHg-exposed fish compared to the controls, whereas lower levels of mercury were found in the brain of zebrafish fed both MeHg and SeMet compared with the fish fed MeHg alone. The expression levels of proteins associated with gap junction signalling, oxidative phosphorylation, and mitochondrial dysfunction were significantly (p < 0.05) altered in the brain of zebrafish after exposure to MeHg and SeMet alone or in combination. Analysis of upstream regulators indicated that these changes were linked to the mammalian target of rapamycin (mTOR) pathways, which were activated by MeHg and inhibited by SeMet, possibly through a reactive oxygen species mediated differential activation of RICTOR, the rapamycin-insensitive binding partner of mTOR.

Dissipation and runoff transport of metazachlor herbicide in rapeseed cultivated and uncultivated plots in field conditions.

The environmental fate of metazachlor herbicide was investigated under field conditions in rapeseed cultivated and uncultivated plots, over a period of 225 days. The cultivation was carried out in silty clay soil plots with two surface slopes, 1 and 5 %. The herbicide was detectable in soil up to 170 days after application (DAA), while the dissipation rate was best described by first-order kinetics and its half-life ranged between 10.92 and 12.68 days. The herbicide was detected in the soil layer of 10-20 cm from 5 to 48 DAA, and its vertical movement can be described by the continuous stirred tank reactor (CSTR) in series model. Relatively low amounts of metazachlor (less than 0.31 % of the initial applied active ingredient) were transferred by runoff water. More than 80 % of the total losses were transferred at the first runoff event (12 DAA), with herbicide concentrations in runoff water ranging between 70.14 and 79.67 µg L-1. Minor amounts of the herbicide (less than 0.07 % of the initial applied active ingredient) were transferred by the sediment, with a maximum concentration of 0.57 µg g-1 (12 DAA), in plots with 5 % inclination. Finally, in rapeseed plants, metazachlor was detected only in the first sampling (28 DAA) at concentrations slightly higher than the limit of quantification; when in seeds, no residues of the herbicide were detected.

Time dependent uptake, bioaccumulation and biotransformation of cell free crude extract microcystins from Lake Amatitlán, Guatemala by Ceratophyllum demersum, Egeria densa and Hydrilla verticillata.

Recent studies evidence that macrophytes can uptake and bioaccumulate microcystins (MC) from contaminated environments, suggesting their use in phytoremediation. In the present study Ceratophyllum demersum, Egeria densa and Hydrilla verticillata were exposed to cell free crude extracts (CE) containing three MC congeners MC-LR, MC-RR and MC-YR at a total MC concentration of 104.4 ± 7.6 µg/L from Lake Amatitlán, Guatemala. Time dependent total glutathione (tGSH), glutathione disulfide (GSSG), disappearance of MC from exposure medium and macrophyte uptake as well as calculated uptake and biotransformation rates and bioconcentration factors (BCF) were monitored after 1, 4, 8 hours (h) and 1, 3, 7 and 14 days (d). Results showed that tGSH concentrations in all exposed macrophytes were enhanced by CE. Disappearance of 62.1 ± 13, 40.8 ± 3.1 and 37.8 ± 3.5 µg/L total MCs from exposure mediums with E. densa, H. verticillata and C. demersum were observed after 1 h. Followed by the total elimination of MCs in exposure medium from H. verticillata after 14 d. Highest MC bioaccumulation capacity (BCF), was observed in E. densa followed by C. demersum and H. verticillata. The here presented results imply the strong MC phytoremediation potential of the evaluated macrophytes.

Mercury concentrations of a resident freshwater forage fish at Adak Island, Aleutian Archipelago, Alaska.

The Aleutian Archipelago is an isolated arc of over 300 volcanic islands stretching 1,600 km across the interface of the Bering Sea and North Pacific Ocean. Although remote, some Aleutian Islands were heavily impacted by military activities from World War II until recently and were exposed to anthropogenic contaminants, including mercury (Hg). Mercury is also delivered to these islands via global atmospheric transport, prevailing ocean currents, and biotransport by migratory species. Mercury contamination of freshwater ecosystems is poorly understood in this region. Total Hg (THg) concentrations were measured in threespine stickleback fish (Gasterosteus aculeatus) collected from eight lakes at Adak Island, an island in the center of the archipelago with a long military history. Mean THg concentrations for fish whole-body homogenates for all lakes ranged from 0.314 to 0.560 mg/kg dry weight. Stickleback collected from seabird-associated lakes had significantly higher concentrations of THg compared to non-seabird lakes, including all military lakes. The δ(13)C stable isotope ratios of stickleback collected from seabird lakes suggest an input of marine-derived nutrients and/or marine-derived Hg.

Distribution and spatial trends of PCBs in commercial scallops from Galician littoral (NW, Spain). Possible influence of biometric parameters.

UNLABELLED: Levels and profiles of 10 individual congeners of polychlorinated biphenyls (PCBs) were studied in 3 species of commercial scallops (Pecten maximus, Chlamys varia, and Chlamys opercularis) from several Rías in Galician littoral (NW, Spain). ΣPCBs levels ranged from 2.21 to 41.0 ng/g wet weight for P. maximus, from 13.9 to 24.9 ng/g wet weight for C. varia, and from 1.58 to 24.3 ng/g wet weight for C. opercularis. The possible influence between biometric parameters (lipid content, condition index, and shell size) and PCBs levels were studied using statistical analysis (ANOVA). No relationship between biometric parameters could be established in the studied samples. Multivariate analysis showed there were differences in bioaccumulation of some PCBs congeners. Principal component analysis classifies clearly the 3 studied Rías (Ría de Ferrol, Ría de Arousa, and Ría de Vigo) taking into account PCBs levels found in the shellfish. PRACTICAL APPLICATIONS: We investigated levels and profiles of 10 congeners of PCBs in 3 commercial scallop species from the Galician littoral zone. The influence of 3 biometric parameters on polychlorinated biphenyls (PCBs) levels was also studied in order to assess results from the monitoring programs of production areas. According to PCBs levels, geographical differences were observed in commercial scallops from the 3 studied estuarine bays (Ría de Ferrol, Ría de Arousa, and Ría de Vigo).

Bioaccumulation dynamics and exposure routes of Cd and Cu among species of aquatic mayflies.

Consumption of periphyton is a potentially important route of metal exposure to benthic invertebrate grazers. The present study examined the bioaccumulation kinetics of dissolved and dietary Cd and Cu in five species of mayflies (class Insecta). Artificial stream water and benthic diatoms were separately labeled with enriched stable metal isotopes to determine physiological rate constants used by a biokinetic bioaccumulation model. The model was employed to simulate the effects of metal partitioning between water and food, expressed as the bioconcentration factor (BCF), as well as ingestion rate (IR) and metal assimilation efficiency of food (AE), on the relative importance of water and food to metal bioaccumulation. For all test species, the contribution of dietary uptake of Cd and Cu increased with BCF. For a given BCF, the contribution of food to the body burden increased with k(uf) , the metal uptake rate constant from food that combined variation in IR and AE. To explore the relative importance of water and diet exposure routes under field conditions, we used estimated site-specific aqueous free-ion concentrations to model Cd and Cu accumulation from aqueous exposure, exclusively. The predicted concentrations accounted for less than 5% of the observed concentrations, implying that most bioaccumulated metal was acquired from food. At least for the taxa considered in this study, we conclude that consumption of metal-contaminated periphyton can result in elevated metal body burdens and potentially increase the risk of metal toxicity.

Selenium bioaccumulation and speciation in Chironomus dilutus exposed to water-borne selenate, selenite, or seleno-DL-methionine.

The objective of the present study was to describe the uptake and elimination kinetics of selenium (Se) administered in the forms of selenate, selenite, and selenomethionine (seleno-DL-methionine) in different life stages of the midge Chironomus dilutus, and to determine the relationship between Se bioavailability and Se speciation using X-ray absorption spectroscopy (XAS). Midge larvae exposed to 4.3 µg/L as dissolved selenate for 10 d of had negligible accumulation of Se (indistinguishable from control organisms). However, larvae rapidly accumulated Se over 10 d of exposure to 3.8 and 1.8 µg/L selenite and seleno-DL-methionine (Se-met), respectively. Most Se accumulated by larvae exposed to selenite or Se-met was retained after 10 d of elimination in clean water. When additional midge larvae were exposed to Se until emergence, Se accumulated during the larval stage was largely retained in the adults. Although a strong correlation was found between the adult whole-body Se concentration and the Se concentration in the exuvia after emergence, only a minor loss of Se occurred in the shed exuvia compared with larvae and adult whole-body concentrations. X-ray absorption spectroscopy analysis showed that organic selenides and diselenides, modeled as Se-met and selenocystine, respectively, were the dominant forms of Se in both the larval and adult insect stages. The proportion and concentration of organic selenides (selenomethionine) increased in larvae and adults exposed to Se-met and selenite compared with larvae exposed to selenate, whereas the concentration of diselenides (selenocystine) remained relatively constant for all treatments.

Chemical techniques for assessing bioavailability of sediment-associated contaminants: SPME versus Tenax extraction.

The traditional approach for predicting the risk of hydrophobic organic contaminants (HOCs) in sediment is to relate organic carbon normalized sediment concentrations to body residues or toxic effects to organisms. However, due to the multiple variables controlling bioavailability, this method has limitations. A matrix independent method of predicting bioavailability needs to be used in order to be universally applicable. Both chemical activity (freely dissolved chemical concentrations) measured by solid-phase microextraction (SPME) and bioaccessibility (rapidly desorbing fraction) estimated by Tenax extraction have been developed to predict bioavailability of sediment-associated HOCs. The objectives of this review are to summarize a number of studies using matrix-SPME or Tenax extraction to estimate bioavailability and/or toxicity of different classes of HOCs and evaluate the strengths and weakness of these two techniques. Although the two chemical techniques assess different components of the matrix, estimates obtained from both techniques have been correlated to organism body residues. The advantages of SPME fibers are their applicability for use in situ and their potential usage for a wide array of contaminants by selection of appropriate coatings. Single time-point Tenax extraction, however, is more time- and labor-effective. Tenax extraction also has lower detection limits, making it more applicable for highly toxic contaminants. This review also calls for additional research to evaluate the role of sequestrated contaminants and ingestion of sediment particles by organisms on HOC bioavailability. The use of performance reference compounds to reduce SPME sampling time and linking chemical based bioavailability estimates to toxicological endpoints are essential to expand the applications of these methods.

Utility of tissue residues for predicting effects of metals on aquatic organisms.

As part of a SETAC Pellston Workshop, we evaluated the potential use of metal tissue residues for predicting effects in aquatic organisms. This evaluation included consideration of different conceptual models and then development of several case studies on how tissue residues might be applied for metals, assessing the strengths and weaknesses of these different approaches. We further developed a new conceptual model in which metal tissue concentrations from metal-accumulating organisms (principally invertebrates) that are relatively insensitive to metal toxicity could be used as predictors of effects in metal-sensitive taxa that typically do not accumulate metals to a significant degree. Overall, we conclude that the use of tissue residue assessment for metals other than organometals has not led to the development of a generalized approach as in the case of organic substances. Species-specific and site-specific approaches have been developed for one or more metals (e.g., Ni). The use of gill tissue residues within the biotic ligand model is another successful application. Aquatic organisms contain a diverse array of homeostatic mechanisms that are both metal- and species-specific. As a result, use of whole-body measurements (and often specific organs) for metals does not lead to a defensible position regarding risk to the organism. Rather, we suggest that in the short term, with sufficient validation, species- and site-specific approaches for metals can be developed. In the longer term it may be possible to use metal-accumulating species to predict toxicity to metal-sensitive species with appropriate field validation.

Similarities and differences of metal distributions in the tissues of molluscs by using multivariate analyses.

Multivariate analysis including correlation, multiple stepwise linear regression, and cluster analyses were applied to investigate the heavy metal concentrations (Cd, Cu, Fe, Ni, Pb, and Zn) in the different parts of bivalves and gastropods. It was also aimed to distinguish statistically the differences between the marine bivalves and the gastropods with regards to the accumulation of heavy metals in the different tissues. The different parts of four species of bivalves and four species of gastropods were obtained and analyzed for heavy metals. The multivariate analyses were then applied on the data. From the multivariate analyses conducted, there were correlations found between the soft tissues of bivalves and gastropods, but none was found between the shells and the soft tissues of most of the molluscs (except for Cerithidea obtusa and Puglina cochlidium). The significant correlations (P < 0.05) found between the soft tissues were further complemented by the multiple stepwise linear regressions where heavy metals in the total soft tissues were influenced by the accumulation in the different types of soft tissues. The present study found that the distributions of heavy metals in the different parts of molluscs were related to their feeding habits and living habitats. The statistical approaches proposed in this study are recommended for use in biomonitoring studies, since multivariate analyses can reduce the cost and time involved in identifying an effective tissue to monitor the heavy metal(s) bioavailability and contamination in tropical coastal waters.

Removal and accumulation of mercury by aquatic macrophytes from an open cast coal mine effluent.

In this study, the mercury (Hg) removal capacities of two aquatic macrophytes, Pistia stratiotes and Azolla pinnata, were investigated against the coal mining effluent. These plants reduced mercury from the effluent via rhizofiltration and subsequent accumulation in plant. The removal rate of P. stratiotes and A. pinnata was 80% and 68%, respectively, after 21 days of exposure to the effluent containing 10 microg L(-1) of Hg. As mercury from the effluent was accumulated in the root and shoot tissues of both aquatic macrophytes, they were proven to be a root accumulator with a translocation factor of less than one during the entire study. The decreasing Hg content in effluent (from 10 to 2.0 microg L(-1)) was reflected by its accumulation in roots (0.57+/-0.02 mg g(-1) in P. stratiotes) and leaves of the experimental plants (0.42+/-0.01 mg g(-1), P. stratiotes). As a result, Hg concentrations in the coal mining effluent were tightly associated with those observed from macrophytes. Considering the high removal efficiencies of Hg by these aquatic macrophytes, these plants can be recommended for the actual treatment of Hg-containing waste waters.

Metallothionein role in the kinetic model of copper accumulation and elimination in the clam Ruditapes decussatus.

In order to clarify the role of metallothioneins (MT) in copper (Cu) toxicity, this work aimed to assess the involvement of this protein in the accumulation and elimination strategies of Cu in the clam Ruditapes decussatus exposed to two sublethal concentrations (25 and 50 microgCul(-1)). The behaviour of MT in three different tissues of clams during the accumulation and depuration processes was also followed by gel-filtration chromatography to assess if Cu was bound to MT or to other cytosolic components. The 96 h LC50 for water-borne copper was 715 microgL(-1) in R. decussatus. The Cu accumulation pattern was dependent on Cu exposure concentrations. In clams exposed to 25 microgl(-1), total Cu accumulation in the three tissues increased linearly during the exposure period, while in those exposed to 50 microgl(-1) it followed the first order kinetic model. The greatest amount of Cu accumulated in all tissues is associated to the low molecular weight cytosolic fraction (>50%). The chromatographic assay indicated that Cu in the cytosolic fraction is bound to MT and MT levels increase with the increase of Cu exposure confirming the binding affinity of Cu to MT in all tissues. However, a smaller percentage of Cu seems to be bond to other ligands, such as GSH. Copper was exponentially eliminated (only studied in clams exposed to 25 microgl(-1)) and the estimated half-life was tissue dependent (9, 5 and 14 days for the gills, digestive gland and remaining tissues, respectively). Copper bound to the thermostable compounds was eliminated more quickly (t(1/2)=4-7 days) in all tissues than those bound to the thermolabile compounds (t(1/2)=7-18 days). Interestingly, MT is rapidly degraded (t(1/2)=7 and 18 days), suggesting that this protein is actively involved in the elimination of this metal, through the Cu-MT complex since MT and Cu are turning over simultaneously. Therefore, when Cu exposure is low, the clam can cope efficiently with the excess of Cu levels by increasing MT induction as well as rapidly eliminating this metal via the MT-Cu complex. Copper toxicity in the clam R. decussatus is associated to the limited capacity of MT induction at higher and environmental unrealistic Cu exposures especially in the gills and remaining tissues.

Root uptake of lead by Norway spruce grown on 210Pb spiked soils.

The root uptake of lead (Pb) by trees and the transfer of Pb by leaf litter deposition to the forest floor were investigated through a pot experiment with Norway spruce. Natural Pb and radio isotopic lead (210Pb) were determined in needles and twigs and in the pot soil spiked with 210Pb. Calculations of the specific activity in plant material and in the supporting pot soil showed that less than 2% of the Pb content of needles and twigs originates from root uptake and approximately 98% are deposited from the atmosphere. Atmospheric Pb has declined by a factor of 7 from 1980 to 2007 but is still a major pathway of Pb to vegetation and topsoils. The conclusion from the experiment is that the internal circulation of Pb through root uptake, translocation and litterfall, gives an insignificant input of Pb to the forest floor compared to atmospheric deposition.

Overwinter alterations in energy stores and growth in juvenile fishes inhabiting areas receiving metal mining and municipal wastewater effluents.

The winter stress syndrome hypothesis proposes that the combination of winter conditions and contaminant exposure reduces overwinter survival in juvenile fishes, mainly due to increased depletion of stored energy (lipids). To test this hypothesis in the field, juvenile fathead minnows (Pimephales promelas), creek chub (Semotilus atromaculatus), and white sucker (Catostomus commersoni) were collected from three exposure sites along Junction Creek, Sudbury, Ontario, Canada, representing cumulative inputs from metal mining and municipal wastewater. Overwinter survival potential was determined through measurements of growth (length, weight, muscle RNA/DNA ratio, muscle proteins) and energy stores (whole body triglycerides) in fish collected just prior to and following the overwinter period. We hypothesized that fish collected from exposure sites would exhibit reduced growth and energy storage compared to reference fish in both fall and spring, and that fish from all sites would exhibit reduced energy storage in spring compared to the previous fall. Whole body Se concentrations were elevated (11-42 microg/g dry wt) in juvenile fathead minnows and white sucker collected at two exposure sites in comparison to fish collected from the reference site (3-6 microg/g dry wt). In contrast to our hypothesis, fathead minnows were larger with greater triglyceride stores at exposure sites compared to the reference site. White suckers were smaller at exposure sites but did not differ in triglycerides among sites. Overall, the results in these fish species exposed to metal mining and municipal wastewaters do not support the winter stress syndrome hypothesis. It is recommended that future studies focus on relating growth and energy storage with other environmental factors such as habitat and food availability in addition to anthropogenic contamination.