Accumulation, transformation, and release of inorganic arsenic by the freshwater cyanobacterium Microcystis aeruginosa

Arsenic (As) as a major hazardous metalloid was affected by phytoplankton in many aquatic environments. The toxic dominant algae Microcystis aeruginosa was exposed to different concentrations of inorganic arsenic (arsenate or arsenite) for 15 days in BG11 culture media. Arsenic accumulation, toxicity, and speciation in M. aeruginos as well as the changes of As species in media were examined. M. aeruginosa has a general well tolerance to arsenate and a definite sensitivity to arsenite. Additionally, arsenate actively elevated As methylation by the algae but arsenite definitely inhibited it. Interestingly, the uptake of arsenite was more pronounced than that of arsenate, and it was correlated to the toxicity. Arsenate was the predominant species in both cells and their growth media after 15 days of exposure to arsenate or arsenite. However, the amount of the methylated As species in cells was limited and insignificantly affected by the external As concentrations. Upon uptake of the inorganic arsenic, significant quantities of arsenate as well as small amounts of arsenite, DMA, and MMA were produced by the algae and, in turn, released back into the growth media. Bio-oxidation was the first and primary process and methylation was the minor process for arsenite exposures, while bioreduction and the subsequent methylation were the primary metabolisms for arsenate exposures. Arsenic bioaccumulation and transformation by M. aeruginosa in aquatic environment should be paid more attention during a period of eutrophication.     

Effects of sodium arsenate exposure on liver fatty acid profiles and oxidative stress in rats

The present study aimed to evaluate the effect of arsenic on liver fatty acids (FA) composition, hepatotoxicity and oxidative status markers in rats. Male rats were randomly devised to six groups (n?=?10 per group) and exposed to sodium arsenate at a dose of 1 and 10 mg/l for 45 and 90 days. Arsenate exposure is associated with significant changes in the FA composition in liver. A significant increase of saturated fatty acids (SFA) in all treated groups (p?<?0.01) and trans unsaturated fatty acids (trans UFA) in rats exposed both for short term for 10 mg/l (p?<?0.05) and long term for 1 and 10 mg/l (p?<?0.001) was observed. However, the cis UFA were significantly decreased in these groups (p?<?0.05). A markedly increase of indicator in cell membrane viscosity expressed as SFA/UFA was reported in the treated groups (p?<?0.001). A significant increase in the level of malondialdehyde by 38.3 % after 90 days of exposure at 10 mg/l was observed. Compared to control rats, significant liver damage was observed at 10 mg/l of arsenate by increasing plasma marker enzymes after 90 days. It is through the histological investigations in hepatic tissues of exposed rats that these damage effects of arsenate were confirmed. The antioxidant perturbations were observed to be more important at groups treated by the high dose (p?<?0.05). An increase in the level of protein carbonyls was observed in all treated groups (p?<?0.05). The present study provides evidence for a direct effect of arsenite on FA composition disturbance causing an increase of SFA and TFAs isomers, liver dysfunction and oxidative stress. Therefore, arsenate can lead to hepatic damage and propensity towards liver cancer.     

Effect of sulfide on the cytotoxicity of arsenite and arsenate in human hepatocytes (HepG2) and human urothelial cells (UROtsa)

Arsenic, a common poison, is known to react with sulfide in vivo, forming thioarsenates. The acute toxicity of the inorganic thioarsenates is currently unknown. Our experiments showed that a fourfold sulfide excess reduced acute arsenite cytotoxicity in human hepatocytes (HepG2) and urothelial cells (UROtsa) significantly, but had little effect on arsenate toxicity. Speciation analysis showed immediate formation of thioarsenates (up to 73 % of total arsenic) in case of arsenite, but no speciation changes for arsenate. Testing acute toxicity of mono- and trithioarsenate individually, both thioarsenates were found to be more toxic than their structural analogue arsenate, but less toxic than arsenite. Toxicity increased with the number of thio groups. The amount of cellular arsenic uptake after 24 h corresponded to the order of toxicity of the four compounds tested. The dominant to almost exclusive intracellular arsenic species was arsenite. The results imply that thiolation is a detoxification process for arsenite in sulfidic milieus. The mechanism could either be that thioarsenates regulate the amount of free arsenite available for cellular uptake without entering the cells themselves, or, based on their chemical similarity to arsenate, they could be taken up by similar transporters and reduced rapidly intracellularly to arsenite.     

Lead accumulation and elimination in tissues of Prussian carp, Carassius gibelio (Bloch, 1782), after long-term dietary exposure, and depuration periods

We studied the bioaccumulation of lead in selected tissues of Prussian carp Carassius gibelio (Bloch, 1782) during 12 and 24 months exposure to different doses of this metal in feed and the elimination of lead from tissues during the following 12-month depuration period. Lead concentration was determined using atomic absorption spectrometry method. The highest lead concentrations were observed at 2.0?±?0.54 to 7.4?±?1.1 mg?kg^?1 in the kidney, 3.0?±?0.13 to 5.2?±?0.17 mg?kg^?1 in the bone, and 4.5 (±0.4)?mg?kg^?1 in the hepatopancreas of fish from groups exposed to lead dietary concentration from 8 to 49 mg?kg^?1 for 24 months. The rate of accumulation were generally the highest at the beginning of exposure as evidenced by the highest monthly increments of bioaccumulation observed after 3 months of contamination for muscles, hepatopancreatic gland, intestine, and gills. Also analysis of the monthly increments of lead bioaccumulation in bone tissue and the highly significant coefficients of correlation indicate that the dynamics of accumulation are clearly dependent on dose of exposure. Depuration of accumulated lead from the organs depended mainly on tissue and duration of elimination period. Very rapid depuration was observed in soft tissues such as the intestine or muscles. Very low elimination was observed for scales and bones where until the end of the experiment highly significant lead concentration differences were observed in all groups in relation to the control group. Chronic dietary exposure in the range of 8–49 mg Pb?kg^?1 resulted in no significant effects on the growth and survival of Prussian carp females.     

Removal of arsenic species from water by batch and column operations on bagasse fly ash

Bagasse fly ash (BFA, a sugar industrial waste) was used as low-cost adsorbent for the uptake of arsenate and arsenite species from water. The optimum conditions for the removal of both species of arsenic were as follows: pH 7.0, concentration 50.0 μg/L, contact time 50.0 min, adsorbent dose 3.0 g/L, and temperature 20.0 °C, with 95.0 and 89.5 % removal of arsenate and arsenite, respectively. The Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich adsorption isotherms were used to analyze the results. The results of these models indicated single-layer uniform adsorption on heterogeneous surface. Thermodynamic parameters, i.e., ΔG°, ΔH°, and ΔS°, were also calculated. At 20.0 to 30.0 °C, the values of ΔG° lie in the range of ?4,722.75 to ?4,878.82 and ?4,308.80 to ?4,451.73 while the values of ΔH° and ΔS° were ?149.90 and ?121.07, and 15.61 and 14.29 for arsenate and arsenite, respectively, indicating that adsorption is spontaneous and exothermic. Pseudo-first-order kinetics was followed. In column experiments, the adsorption decreased as the flow rate increased with the maximum removal of 98.9 and 95.6 % for arsenate and arsenite, respectively. The bed depth service time and Yoon and Nelson models were used to analyze the experimental data. The adsorption capacity (N _o) of BFA on column was 3.65 and 2.98 mg/cm³ for arsenate and arsenite, respectively. The developed system for the removal of arsenate and arsenite species is economic, rapid, and capable of working under natural conditions. It may be used for the removal of arsenic species from any contaminated water resources.     

Sodium arsenate induce changes in fatty acids profiles and oxidative damage in kidney of rats

Six groups of rats (n?=?10 per group) were exposed to 1 and 10 mg/l of sodium arsenate for 45 and 90 days. Kidneys from treated groups exposed to arsenic showed higher levels of trans isomers of oleic and linoleic acids as trans C181n-9, trans C18:1n-11, and trans C18:2n-6 isomers. However, a significant decrease in eicosenoic (C20:1n-9) and arachidonic (C20:4n-6) acids were observed in treated rats. Moreover, the “Δ5 desaturase index” and the saturated/polyunsaturated fatty acids ratio were increased. There was a significant increase in the level of malondialdehyde at 10 mg/l of treatment and in the amount of conjugated dienes after 90 days (p?p?p?p?n-6 polyunsaturated fatty acids and leads to an increase in the trans FAs isomers. Therefore, FA-induced arsenate kidney damage could contribute to trigger kidney cancer.     

Behavioural and biochemical responses of two marine invertebrates Scrobicularia plana and Hediste diversicolor to copper oxide nanoparticles

Engineered nano-sized Cu oxide particles are extensively used in diverse applications. Because aquatic environments are the ultimate “sink” for all contaminants, it is expected that nanoparticles (NP) will follow the same fate. In this study, two marine invertebrates Scrobicularia plana and Hediste diversicolor were chosen as ecotoxicological models. The aim was to evaluate behavioural (burrowing kinetics, feeding rate) and biochemical (biomarkers) responses of S. plana and H. diversicolor exposed in the laboratory to Cu (10 μg L⁻¹) added in natural seawater either in the form of engineered nanoparticles (NPs) of CuO or as dissolved Cu in 2% HNO₃. Exposure was characterized by considering (i) the physico-chemical fate of NP (ii) the fraction of labile Cu in experimental media and (iii) Cu bioaccumulation. Results showed high aggregation of CuO NPs in seawater and no additional bioavailable Cu concentrations. Behavioural impairments were observed in S. plana exposed to CuO NPs or soluble Cu whereas in H. diversicolor, only the exposure to soluble Cu led to a burrowing decrease. No obvious neurotoxicity effects were revealed since in both species, no changes in cholinesterasic activity occurred in response to both forms of Cu exposure. Biomarkers of oxidative-stress catalase and glutathione-S-transferase were enhanced in both species whereas superoxide dismutase was increased only in S. plana exposed to CuO NPs. Metallothionein-like protein was increased in bivalves exposed to both forms of Cu. Since, no detectable release of soluble Cu from CuO NPs occurred during the time of experiment, ecotoxicity effects seem to be related to CuO NPs themselves.     

Thermodynamic and kinetic studies of As(V) removal from water by zirconium oxide-coated marine sand

Arsenic contamination of groundwater is a major threat to human beings globally. Among various methods available for arsenic removal, adsorption is fast, inexpensive, selective, accurate, reproducible and eco-friendly in nature. The present paper describes removal of arsenate from water on zirconium oxide-coated sand (novel adsorbent). In the present work, zirconium oxide-coated sand was prepared and characterised by infrared and X-ray diffraction techniques. Batch experiments were performed to optimise different adsorption parameters such as initial arsenate concentration (100–1,000 μg/L), dose (1–8 g/L), pH of the solution (2–14), contact time (15–150 min.), and temperature (20, 30, 35 and 40 °C). The experimental data were analysed by Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models. Furthermore, thermodynamic and kinetic parameters were evaluated to know the mode of adsorption between ZrOCMS and As(V). The maximum removal of arsenic, 97 %, was achieved at initial arsenic concentration of 200 μg/L, after 75 min at dosage of 5.0 g/L, pH?7.0 and 27?±?2 °C. For 600 μg/L concentration, the maximum Langmuir monolayer adsorption capacity was found to be 270 μg/g at 35 °C. Kinetic modelling data indicated that adsorption process followed pseudo-second-order kinetics. The mechanism is controlled by liquid film diffusion model. Thermodynamic parameter, ΔH°, was ?57.782, while the values of ΔG° were ?9.460, ?12.183, ?13.343 and ?13.905 kJ/mol at 20, 30, 35 and 40 °C, respectively, suggesting exothermic and spontaneous nature of the process. The change in entropy, ΔS°?=??0.23 kJ/mol indicated that the entropy decreased due to adsorption of arsenate ion onto the solid adsorbent. The results indicated that the reported zirconium oxide-coated marine sand (ZrOCMS) was good adsorbent with 97 % removal capacity at 200 μg/L concentration. It is interesting to note that the permissible limit of arsenic as per World Health Organization is 10 μg/L, and in real situation, this low concentration can be achieved through this adsorbent. Besides, the adsorption capacity showed that this adsorbent may be used for the removal of arsenic from any natural water resource.     

The influence of salinity on metal uptake and effects in the midge Chironomus maddeni

The influence of different porewater salinities (up to 12 g/L) on the toxicity and bioaccumulation of copper, zinc and lead from metal-spiked sediments was assessed using the midge, Chironomus maddeni. Survival of the larvae was significantly reduced at a porewater salinity of 12 g/L, but no effects were observed at 4 or 8 g/L. Both growth and survival of C. maddeni were reduced after exposure to salt/metal spiked sediments as compared to those exposed to sediments spiked with metals or salt alone. Increased salinity resulted in increased bioaccumulation of copper and zinc, but decreased bioaccumulation of lead. The observed patterns of bioaccumulation were not entirely explained by the modelled free ion activities of the metals, indicating that factors such as osmotic stress, consumption of metal-contaminated sediments or metal interactions may have been important as well. These results highlight the need to consider the influence of existing or potential salinization when undertaking hazard assessments of freshwater systems impacted by contaminants such as trace metals.     

Bioaccumulation and the soil factors affecting the uptake of arsenic in earthworm, Eisenia fetida

To better understand arsenic (As) bioaccumulation, a soil invertebrate species was exposed to 17 field soils contaminated with arsenic due to mining activity. Earthworms (Eisenia fetida) were kept in the soils for 70 days under laboratory conditions, as body burden increased and failed to reach equilibrium in all soils. After 70 days of exposure, XANES spectra determined that As was biotransformed to a highly reduced form. Uptake kinetics for As was calculated using one compartment model. Stepwise multiple regression suggested that sorbed As in soils are bioaccessible, and uptake is governed by soil properties (iron oxide, sulfate, and dissolved organic carbon) that control As mobility in soils. As in soil solution are highly related to uptake rate except four soils which had relatively high chloride or phosphate. The results imply that uptake of As is through As interaction with soil characteristics as well as direct from the soil solution. Internal validation showed that empirically derived regression equations can be used for predicting As uptake as a function of soil properties within the range of soil properties in the data set.     

Rapid biotransformation of arsenic by a model protozoan Tetrahymena pyriformis GL-C. [corrected

Arsenic biomethylation and biovolatilization are thought to be two important metabolic pathways in aquatic and soil environments. Tetrahymena thermophila is a genus of free-living ciliated protozoan that is widely distributed in freshwater environments around the world. In this study, we studied arsenic accumulation, speciation, efflux, methylation and volatilization in this unicellular eukaryote exposed to various concentrations of arsenate. Our results show that T. thermophila accumulated 187 mg.kg⁻¹ dry weight of arsenic when exposed to 40 μM for 48 h, with MMAs(V) (monomethylarsenate) and DMAs(V) (dimethylarsenate) as the dominant species, accounting for 66% of the total arsenic. Meanwhile, arsenate, arsenite, MMAs(V) and DMAs(V) were detected in the culture medium; the last three were released by the cells. The production of volatile arsenic increased with increasing external As(V) concentrations and exposure time. To our knowledge, this is the first study on arsenic metabolism, particularly biomethylation and biovolatilization, in protozoa.     

Comparative study of different exposure routes on the biotransformation and genotoxicity of PAHs in the flatfish species, Scophthalmus maximus

In this study, laboratory experiments were carried out in order to come to a better understanding of the fate of polycyclic aromatic hydrocarbons (PAHs) in the marine environment and especially on their bioaccumulation, biotransformation and genotoxic effects in fish. Juveniles of turbot (Scophthalmus maximus) were exposed to PAHs through different routes via (1) a mixture of dissolved PAHs, (2) a PAH-polluted sediment and (3) an oil fuel elutriate. Fish were exposed 4 days followed by a 6-day depuration period. In each experiment, PAH concentrations in the seawater of the tanks were analysed regularly by gas chromatography coupled with mass spectrometry. Muscle and liver samples were also analysed for parent PAH levels and PAH bioconcentration factors were calculated. Biotransformation was evaluated by measuring the levels of PAH metabolites in fish bile. Genotoxicity was assessed by the alkaline comet assay. Regardless of exposure route, the parent PAH concentrations in the liver and muscle showed a peak level 1 day after the beginning of the exposure, followed by a decrease up to the background level towards the end of the experiment, except for the exposure to dissolved PAHs for which levels were relatively low throughout the study. As a consequence, no bioaccumulation was observed in fish tissues at the end of the experiment. In contrast, regardless of exposure routes, a rapid production of biliary metabolites was observed throughout the whole exposure experiment. This was especially true for 1-hydroxypyrene, the major metabolite of pyrene. After 6 days of recovery in clean water, a significant decrease in the total metabolite concentrations occurred in bile. Fish exposed through either route displayed a significant increase in DNA strand breaks after 4 days of exposure, and significant correlations were observed between the level of biliary PAH metabolites and the level of DNA lesions in fish erythrocytes. Overall results indicate that exposure to either a mixture of dissolved PAHs, a PAH-contaminated sediment or a dispersed oil fuel elutriate leads to biotransformation and increase in DNA damage in fish. The quantification of PAH metabolites in bile and DNA damage in erythrocytes appear to be suitable for environmental monitoring of marine pollution either in the case of accidental oil spills or sediment contamination.     

The removal of arsenate from water using iron-modified diatomite (D-Fe): isotherm and column experiments

Iron hydroxide supported onto porous diatomite (D-Fe) is a low-cost material with potential to remove arsenic from contaminated water due to its affinity for the arsenate ion. This affinity was tested under varying conditions of pH, contact time, iron content in D-Fe and the presence of competitive ions, silicate and phosphate. Batch and column experiments were conducted to derive adsorption isotherms and breakthrough behaviours (50 μg L^?1) for an initial concentration of 1,000 μg L^?1. Maximum capacity at pH 4 and 17 % iron was 18.12–40.82 mg of arsenic/g of D-Fe and at pH 4 and 10 % iron was 18.48–29.07 mg of arsenic/g of D-Fe. Adsorption decreased in the presence of phosphate and silicate ions. The difference in column adsorption behaviour between 10 % and 17 % iron was very pronounced, outweighing the impact of all other measured parameters. There was insufficient evidence of a correlation between iron content and arsenic content in isotherm experiments, suggesting that ion exchange is a negligible process occurring in arsenate adsorption using D-Fe nor is there co-precipitation of arsenate by rising iron content of the solute above saturation.     

Assessment of plant-driven uptake and translocation of clofibric acid by Scirpus validus

Pharmaceutical compounds are now considered as emerging contaminants of environmental concern. The overall objective of this study was to evaluate the uptake and translocation of clofibric acid (CA) by the macrophyte Scirpus validus growing hydroponically. A set of the three replicates was established for each exposure time and for each CA concentration. Plants were grown in 4 L vessels (four plants per vessel corresponding to the three exposure period studies, i.e., 7, 14, 18, and 21 days) which contained an aerated modified Hoagland nutrient solution that was spiked with CA at concentrations of 0.5, 1.0, and 2.0 mg?L^?1. At each exposure period, CA concentration was measured in the nutrient solutions. A sea sand disruption method was employed for the extraction of CA from plant tissues. The determination of the pharmaceutical concentration was carried out using solid phase extraction (SPE) followed by chromatographic analysis. The quantification of CA concentrations in both nutrient solutions (after SPE) and plant tissues (after extraction) was conducted by chromatographic analysis. CA concentrations of 5.4–26.8 μg?g^?1 (fresh weight) were detected in the roots and 7.2–34.6 μg?g^?1 (fresh weight) in the shoots after 21 days. Mass balance calculations showed that S. validus uptake alone accounted for a significant contribution (6–13 % for the roots and 22–49 % for the shoots) of the total loss of CA. The bioaccumulation factors (BAFs) based on fresh weight for the roots ranged from 6.6 to 23.2, while values for the shoots ranged from 9.5 to 32.1. All the BAFs for the shoots were greater than those in the roots, implying that CA has greater tendency to be translocated to the shoots, rather than the roots of S. validus. All the shoot-to-root concentration ratios were more than 1, denoting that the shoots of S. validus do preferentially accumulate CA. We demonstrated that CA can be actively taken up, subsequently translocated and accumulated by aboveground tissues of S. validus. Since S. validus could account for the removal of 28–62 % of the total mass loss of CA from the system, such phytoremediation technology has great potential for the removal of pharmaceuticals such as CA from inflowing waters.     

Can Hediste diversicolor (Nereidae, Polychaete) be considered a good candidate in evaluating PAH contamination? A multimarker approach

The aim of this study was to develop a preliminary characterization of the biological responses of Hediste diversicolor to polycyclic aromatic hydrocarbons (PAHs) under controlled laboratory conditions. In order to test the effects of PAH exposure, a battery of biomarkers was applied to the polychaetes by exposing them to sublethal concentrations of benzo[a]pyrene (0.1 and 0.5 mg L⁻¹) for 10 d under laboratory conditions. The battery of biomarkers tested included oxidative stress biomarkers (glutathione content, enzymatic activities of catalase, glutathione S-transferases, glutathione reductase, glutathione peroxidases), total oxyradical scavenging capacity (TOSC) toward peroxyl and hydroxyl radicals and activity of acyl CoA oxidase (AOX) as a marker of peroxisome proliferation measured in the entire body; lipofuscin and neutral lipid accumulations and levels of Ca²⁺-ATPase activity analyzed in the intestinal epithelium; lysosomal membrane stability and genotoxic effects measured as DNA strand breaks and frequency of micronuclei in coelomocytes. Chemical analyses were also carried out to verify the polychaete’s benzo[a]pyrene (B[a]P) bioaccumulation levels after the exposure period. The results obtained indicate that B[a]P caused significant changes in most of the parameters measured in H. diversicolor. Biological responses to the organic compound were particularly significant for the biomarkers measured in the intestinal epithelium and in coelomocytes, emphasizing that these tissues were more affected during our experimental conditions. Considering the key trophic role of this benthic species in estuarine and coastal ecosystems, this study confirmed that H. diversicolor is an appropriate bioindicator of organic contamination.     

Speciation of five arsenic species (arsenite, arsenate, MMAAV, DMAAV and AsBet) in different kind of water by HPLC-ICP-MS

A method using Ion Chromatography hyphenated to an Inductively Coupled Plasma-Mass Spectrometer has been developed to accurately determine arsenite (As(III)), arsenate (As(V)), mono-methylarsonic acid (MMAA(V)), dimethylarsinic acid (DMAA(V)) and arsenobetaine (AsBet) in different water matrices. The developed method showed a high sensitivity with detection limits for each arsenic species close to 0.4pg injected. Arsenite and arsenate were the major species found in surface and well waters, but AsBet and DMAA(V) were found in some surface waters, which has never been reported before, while in some natural mineral waters located in volcanic region, the arsenic content exceeded the maximal admissible arsenic content by European legislation standards and the predominant form was As(V).     

Dietary arsenic consumption and urine arsenic in an endemic population: response to improvement of drinking water quality in a 2-year consecutive study

We assessed the association between arsenic intake through water and diet, and arsenic levels in first morning-void urine under variable conditions of water contamination. This was done in a 2-year consecutive study in an endemic population. Exposure of arsenic through water and diet was assessed for participants using arsenic-contaminated water (≥50 μg L^?1) in a first year (group I) and for participants using water lower in arsenic (<50 μg L^?1) in the next year (group II). Participants with and without arsenical skin lesions were considered in the statistical analysis. Median dose of arsenic intake through drinking water in groups I and II males was 7.44 and 0.85 μg kg body wt.^?1 day^?1 (p <0.0001). In females, it was 5.3 and 0.63 μg kg body wt.^?1 day^?1 (p <0.0001) for groups I and II, respectively. Arsenic dose through diet was 3.3 and 2.6 μg kg body wt.^?1 day^?1 (p?=?0.088) in males and 2.6 and 1.9 μg kg body wt.^?1 day^?1 (p?=?0.0081) in females. Median arsenic levels in urine of groups I and II males were 124 and 61 μg L^?1 (p?=?0.052) and in females 130 and 52 μg L^?1 (p?=?0.0001), respectively. When arsenic levels in the water were reduced to below 50 μg L^?1 (Indian permissible limit), total arsenic intake and arsenic intake through the water significantly decreased, but arsenic uptake through the diet was found to be not significantly affected. Moreover, it was found that drinking water mainly contributed to variations in urine arsenic concentrations. However, differences between male and female participants also indicate that not only arsenic uptake, but also many physiological factors affect arsenic behavior in the body and its excretion. As total median arsenic exposure still often exceeded 3.0 μg kg body wt.^?1 day^?1 (the permissible lower limit established by the Joint Expert Committee on Food Additives) after installation of the drinking water filters, it can be concluded that supplying the filtered water only may not be sufficient to minimize arsenic availability for an already endemic population.     

Environmental fate and bioavailability of wood preservatives in freshwater sediments near an old sawmill site.

Impacts of an old contaminated sawmill site located in Eastern Finland were studied, with emphasis on transportation and bioaccumulation of wood preservatives in the surrounding water system. To assess the transportation of chlorophenols and chromated copper arsenate (CCA) from the sawmill to the nearby lake, the concentrations of these compounds in selected sediment samples were analyzed. To assess the contribution of a pulp mill further upstream, the concentration of extractable organic halogens (EOX) was analyzed. Bioaccumulation of wood preservatives from sediments was examined using Lumbriculus variegatus as test organism. In sediments collected from the sawmill area, concentrations of chlorophenols, arsenic, chromium and copper were high. In the surrounding area the concentrations of these compounds were slightly elevated at some sampling points but were mostly within the natural range of variation. Thus, it can be concluded that transportation of wood preservatives from the sawmill area to its surroundings is fairly low. However, 60 microg/l of arsenic and 50 microg/l of copper were found in water taken from a brook that runs through a landfill area of the sawmill to the nearby river, and the concentration of arsenic in the surface sediment at one sampling point in the lake was slightly elevated. The total amount of organohalogens in sediment was higher in the river and the lake than in the sawmill area. Of all the wood preservatives studied, only arsenic was found to bioaccumulate in present conditions, reaching a tissue concentration of 362 microg/g dw in organisms exposed for 28 days to sediment from the brook. High concentration of arsenic in oligochaeta tissue was related to high concentration of arsenic in the pore water.     

Physiological and molecular responses of the earthworm <Emphasis Type="Italic">Eisenia fetida</Emphasis> to polychlorinated biphenyl contamination in soil

Polychlorinated biphenyls (PCBs) are a class of man-made organic compounds ubiquitously present in the biosphere. In this study, we evaluated the toxic effects of different concentrations of PCBs in two natural soils (i.e. red soil and fluvo-aquic soil) on the earthworm Eisenia fetida. The parameters investigated included anti-oxidative response, genotoxic potential, weight variation and biochemical responses of the earthworm exposed to two different types of soils spiked with PCBs after 7 or 14 days of exposure. Earthworms had significantly lower weights in both soils after PCB exposure. PCBs significantly increased catalase (CAT), superoxide dismutase (SOD), and guaiacol peroxidase (POD) activity in earthworms exposed to either soil type for 7 or 14 days and decreased the malondialdehyde (MDA) content in earthworms exposed to red soil for 14 days. Of the enzymes examined, SOD activity was the most sensitive to PCB stress. In addition, PCB exposure triggered dose-dependent coelomocyte DNA damage, even at the lowest concentration tested. This response was relatively stable between different soils. Three-way analysis of variance (ANOVA) showed that the weight variation, anti-oxidant enzyme activities, and MDA contents were significantly correlated with exposure concentration or exposure duration (P < 0.01). Furthermore, weight variation, CAT activity, and SOD activity were significantly affected by soil type (P < 0.01). Therefore, the soil type and exposure time influence the toxic effects of PCBs, and these factors should be considered when selecting responsive biomarkers.     

The formation of trimethylarsine oxide from arsenobetaine by biodegradation with marine microorganisms

Bottom sediments collected from coastal waters were aerobically incubated in inorganic medium containing arsenobetaine as a carbon source. An arsenic compound converted from arsenobetaine during incubation was purified from the medium by ion exchange chromatography. The purified compound was identified to be trimethylarsine oxide by TLC, HPLC, FAB-MS and NMR.