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The increased use of silver nanoparticles (AgNP) in industrial and consumer products worldwide has resulted in their release to aquatic environments. Previous studies have mainly focused on the effects of AgNP on pelagic species, whereas few studies have assessed the risks to benthic invertebrates despite the fact that the sediments act as a large potential sink for NPs. In this study, the toxicity of sediment-associated AgNP was evaluated using the standard sediment toxicity test for chemicals provided by the Organization of Economic Cooperation and Development. The freshwater benthic oligochaete worm Lumbriculus variegatus was exposed to sediment-associated AgNP in artificial and natural sediments at concentrations ranging from 91 to 1098 mg Ag/kg sediment dry weight. Silver nitrate (AgNO3) was used as a reference compound for Ag toxicity. The measured end points of toxicity were mortality, reproduction, and total biomass. In addition, the impact of sediment-associated AgNP on the feeding rate of L. variegatus was studied in a similar test set-up as mentioned previously. The addition of AgNP into the sediment significantly affected the feeding rate and reproduction of the test species only at the highest concentration (1098 mg/kg) of Ag in the natural sediment with the lowest pH. In comparison, the addition of AgNO3 resulted in reproductive toxicity in every tested sediment, and Ag was more toxic when spiked as AgNO3 than AgNP. In general, sediments were observed to have a high capacity to eliminate the AgNP-derived toxicity. However, the capacity of sediments to eliminate the toxicity of Ag follows a different pattern when spiked as AgNP than AgNO3. The results of this study emphasize the importance of sediment-toxicity testing and the role of sediment properties when evaluating the environmental effects and behavior of AgNP in sediments.

We evaluated the utility of chironomid and lamprey larval responses in ecotoxicity assessment of polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/F)-, polychlorinated biphenyls (PCB)- and mercury (Hg)-contaminated river sediments. Sediment samples were collected from the River Kymijoki with a known industrial pollution gradient. Sediment for the controls and lamprey larvae were obtained from an uncontaminated river nearby. Contamination levels were verified with sediment and tissue PCDD/F, PCB and Hg analyses. Behaviour of sediment-exposed chironomid and lamprey larvae were measured with Multispecies Freshwater Biomonitor© utilizing quadrupole impedance conversion technique. In addition, mortality, growth and head capsule deformity incidence of chironomids were used as ecotoxicity indicators. WHOPCDD/F+PCB-TEQ in the R. Kymijoki sediments ranged from the highest upstream 22.36 ng g(-1) dw to the lowest 1.50 ng g(-1) near the river mouth. The sum of PCDD/Fs and PCBs correlated strongly with Hg sediment concentrations, which ranged from <0.01 to 1.15 μg g(-1). Lamprey tissue concentrations of PCDD/Fs were two orders and PCBs one order of magnitude higher in the R. Kymijoki compared to the reference. Chironomid growth decreased in contaminated sediments and was negatively related to sediment ∑PCDD/Fs, WHOPCDD/F+PCB-TEQ and Hg. There were no significant differences in larval mortality or chironomid mentum deformity incidence between the sediment exposures. The distinct behavioural patterns of both species indicate overall applicability of behavioural MFB measurements of these species in sediment toxicity bioassays. Chironomids spent less and lampreys more time in locomotion in the most contaminated sediment compared to the reference, albeit statistically significant differences were not detected. Lamprey larvae had also a greater activity range in some of the contaminated sediments than in the reference. High pollutant levels in lamprey indicate risks for biomagnification in the food webs, with potential health risks to humans consuming fish.

There were two main objectives in this study. The first was to compare the accuracy of different prediction methods for the chemical concentrations of polyaromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in the organism, based on the measured chemical concentrations existing in sediment dry matter or pore water. The predicted tissue concentrations were compared to the measured ones after 28-day laboratory test using oligochaeta worms (Lumbriculus variegatus). The second objective was to compare the bioaccumulation of PAHs and PCBs in the laboratory test with the in situ bioaccumulation of these compounds. Using the traditional organic carbon-water partitioning model, tissue concentrations were greatly overestimated, based on the concentrations in the sediment dry matter. Use of an additional correction factor for black carbon with a two-carbon model, significantly improved the bioaccumulation predictions, thus confirming that black carbon was important in binding the chemicals and reducing their accumulation. The predicted PAH tissue concentrations were, however, high compared to the observed values. The chemical concentrations were most accurately predicted from their freely dissolved pore water concentrations, determined using equilibrium passive sampling. The patterns of PCB and PAH accumulation in sediments for laboratory-exposed L. variegatus were similar to those in field-collected Lumbriculidae worms. Field-collected benthic invertebrates and L. variegatus accumulated less PAHs than PCBs with similar lipophilicity. The biota to sediment accumulation factors of PAHs tended to decrease with increasing sediment organic carbon normalized concentrations. The presented data yields bioconcentration factors (BCF) describing the chemical water-lipid partition, which were found to be higher than the octanol-water partition coefficients, but on a similar level with BCFs drawn from relevant literature. In conclusion, using the two-carbon model method, or the measured freely dissolved pore water concentrations method is recommended for predicting the bioaccumulation of PAHs and PCBs., (Copyright © 2016. Published by Elsevier B.V.)

The nonbiting midge Chironomus riparius was used to study the remediation potential and secondary effects of activated carbon (AC, ø 63-200 μm) in PCB contaminated sediments. AC amendments efficiently reduced PCB bioavailability determined by Chironomus riparius bioaccumulation tests and passive samplers. PCBs were shown to transfer from larvae to adults. Lower PCB concentrations were observed in adult midges emerging from AC amended compared to unamended sediments. Increased reproduction, survival, larval growth and gut wall microvilli length were observed with low AC dose (0.5% sediment dw) compared to unamended sediment, indicating an improved success of larvae in the sediment with low organic carbon content. On the other hand, higher AC doses (2.5% sediment dw) caused adverse effects on emergence and larval development. In addition, morphological changes in the gut wall microvilli layer were observed. This study showed that the secondary effects of AC amendments are dependent on the dose and the sediment characteristics. Metamorphic species, such as C. riparius, may act as a vector for organic pollutants from aquatic to terrestrial ecosystems and according to this study the AC amendments may reduce this transport.

The sorption efficiency and possible secondary effects of activated carbon (AC) (ø 63-200 μm) was studied with Lumbriculus variegatus in three PCB contaminated sediments applying long AC-sediment contact time (3 years). AC amendment efficiently reduced PCB bioavailability as determined with both, L. variegatus bioaccumulation test and passive samplers. However, dose related secondary effects of AC on egestion rate and biomass were observed (applied doses 0.25% and 2.5% sediment dry weight). The sorption capacity and secondary effects remained similar when the experiments were repeated after three years of AC-sediment contact time. Further, transmission electron microscopy (TEM) samples revealed morphological changes in the L. variegatus gut wall microvilli layer. Sediment properties affected both sorption efficiency and secondary effects, but 2.5% AC addition had significant effects regardless of the sediment. In, conclusion, AC is an efficient and stable sorbent to decrease the bioavailability of PCBs. However, sediment dwelling organisms, such as Oligochaete worms in this study, may be sensitive to the carbon amendments. The secondary effects and possible morphological changes in benthic organisms should not be overlooked as in many cases they form the basis of the aquatic food webs., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The possible toxicity of nanoparticles (NPs) to aquatic organisms needs to be investigated for chronic effects at low concentrations. Chronic effects of carbon NPs, fullerenesC60, on the midges of Chironomus riparius at different life stages on larvae and adult midges were investigated. Sediment associated fullerenesC60 were studied by 10-day growth and 42-day emergence tests with artificial sediment at nominal concentration ranges 0.0004-80 mg/kg dry weight. The body length decreased in the lower tested concentrations (0.0025-20 mg/kg), but the effect vanished with higher concentrations. Delayed emergence rate observed at 0.5 mg/kg. The observed effects correlated with analyzed sediment particle sizes indicating that small agglomerates of fullerene have more significant effects on C. riparius than larger agglomerates observed with higher C60 doses. The results reveal that fullerene may pose risks to benthic organisms, emerging as changes in the ecotoxic parameters studied here which inflects by the survival of the population., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The influence of temperature on the bioaccumulation, toxicokinetics, biotransformation and depuration of pyrene was studied in the arctic marine amphipod Gammarus setosus. A two-compartment model was used to fit experimental values of total body burden, total metabolites and parent pyrene concentrations and to calculate toxicokinetic variables derived for two experimental treatments (2 and 8 °C). No statistically significant differences were observed with temperature for these toxicokinetic variables or bioconcentration factors. Contrarily, the Q10 values suggested that the toxicokinetic variables ke and km were temperature-dependent. This may be explained by the high standard deviation of the Q10 values. Q10 is the variation in the rate of a metabolic reaction with a 10 °C increase in temperature. Depuration rate constants were calculated from linear best fit equations applied to measured pyrene concentrations over time during the depuration phase of the experiment. During depuration, the parent pyrene was eliminated in two stages with faster elimination observed at 8 °C compared to 2 °C. This finding was also indicated by the Q10. No changes in total body burdens of metabolite concentrations were observed during the monitoring of depuration over a period of 96 h. The biotransformation pathway of pyrene in G. setosus was also investigated in this study with two main phase II biotransformation products discovered by liquid chromatography. These products are conditionally identified as the sulphate and glucose conjugates of 1-hydroxy-pyrene. Overall, the study contributes new knowledge to the understanding of the fate of PAHs in arctic biota. In particular, the study provides valuable insight into the bioaccumulation and biotransformation of an important PAH and its metabolites in a species that serves as both a predator and prey in the arctic ecosystem., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Multixenobiotic resistance is a phenomenon in which ATP-binding cassette (ABC) family proteins transfer harmful compounds out of cells. Daphnia magna and Lumbriculus variegatus are model species in aquatic ecotoxicology, but the presence and activity of ABC proteins have not been well described in these species. The aim of this work was to study the presence, activity, and inhibition of ABC transport proteins in D. magna and L. variegatus. The presence of abcb1 and abcc transcripts in 8-9-day-old D. magna was investigated by qRT-PCR. The activity of MXR in D. magna and L. variegatus was explored by influx of the fluorescent ABC protein substrates rhodamine B and calcein-AM, with and without the model inhibitors verapamil (unspecific ABC inhibitor), reversin 205 (ABCB1 inhibitor) and MK571 (ABCC inhibitor). Juvenile D. magna possessed all examined abcb and abcc transcripts, but only reversin 205 inhibited MXR activity. The MXR activity in L. variegatus was inhibited by MK571, and to a lesser extent by verapamil, whereas reversin 205 seemed to stimulate the transport activity. Whereas calcein-AM worked better as an MXR substrate in D. magna, rhodamine B was a better substrate for L. variegatus MXR activity measurements. This is the first report on MXR activity in the order Lumbriculida, subclass Oligochaeta, and class Clitellata., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Depending on environmental conditions, fullerenes (nC60) have the potential to settle to the bottom sediments. In this study the distribution of nC60 was investigated in the labile zone between sediment and water. Three freshwater-sediment systems representing oligohumic, mesohumic, and polyhumic lakes with varying sediment composition and structure were used to investigate the target of fullerenes. The largest portion of water suspended fullerenes was found in the sediment, but a part re-suspended relatively quickly to water-stabile particles associated with natural particles. Rapid initial re-suspending was followed by a slower one offering a continuous pathway to the water phase. Re-suspending was highest from the sediment with a high amount of amorphous matter, small particles and a highly aliphatic character, amounting to 9±1% of the initial amount of fullerenes, whereas it was 4±1% in aromatic sediments with larger particles and less amorphous matter. These results indicate that bottom sediments can retain fullerenes but a portion may remain mobile depending on sediment character. Re-suspended fullerenes may again be available to aquatic species-this knowledge should thus be taken into account in the environmental risk assessment of fullerenes., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Understanding the fate of persistent organic chemicals in the environment is fundamental information for the successful protection of ecosystems and humans. A common dilemma in risk assessment is that monitoring data reveals contaminant concentrations in wildlife, while the source concentrations, route of uptake and acceptable source concentrations remain unsolved. To overcome this problem, different models have been developed in order to obtain more precise risk estimates for the food webs. However, there is still an urgent need for studies combining modelled and measured data in order to verify the functionality of the models. Studies utilising field-collected data covering entire food webs are particularly scarce. This study aims to contribute to tackling this problem by determining the validity of two bioaccumulation models, BIOv1.22 and AQUAWEBv1.2, for application to a multispecies aquatic food web. A small boreal lake, Lake Kernaalanjärvi, in Finland was investigated for its food web structure and concentrations of PCBs in all trophic levels. Trophic magnification factors (TMFs) were used to measure the bioaccumulation potential of PCBs, and the site-specific environmental parameters were used to compare predicted and observed concentrations. Site-specific concentrations in sediment pore water did not affect the modelling endpoints, but accurate site-specific measurements of freely dissolved concentrations in water turned out to be crucial for obtaining realistic model-predicted concentrations in biota. Numerous parameters and snapshot values affected the model performances, bringing uncertainty into the process and results, but overall, the models worked well for a small boreal lake ecosystem. We suggest that these models can be optimised for different ecosystems and can be useful tools for estimating the bioaccumulation and environmental fate of PCBs., (© 2013 Elsevier B.V. All rights reserved.)

The regulation of endogenous metabolites is still not fully understood in aquatic invertebrates exposed concurrently to toxicants and hypoxia. Despite the prevalence of hypoxia in the aquatic environment, toxicity estimations seldom account for multiple stressors thereby differing from natural conditions. In this study, we examined the influence of hypoxia (<30% O2) on contaminant uptake and the composition of intracellular metabolites in Lumbriculus variegatus exposed to benzo(a)pyrene (B(a)P, 3μgL(-1)), chlorpyrifos (CPF, 100μgL(-1)) or pentachlorophenol (PCP, 100μgL(-1)). Tissue extracts of worms were analyzed for 123 metabolites by gas chromatography-mass spectrometry and metabolite levels were then related to treatments and exposure time. Hypoxia markedly increased the accumulation of B(a)P and CPF, which underlines the significance of oxygen in chemical uptake. The oxygen effect on PCP uptake was less pronounced. Succinate and glycerol-3-phosphate increased significantly (p<0.0001) following hypoxic treatment, whereas sugars, cysteine, and cholesterol were effectively repressed. The buildup of succinate coupled with the corresponding decline in intracellular 2-oxo- and 2-hydroxy glutaric acid is indicative of an active hypoxia inducible factor mechanism. Glutamate, and TCA cycle intermediates (fumarate, and malate) were disturbed and evident in their marked suppression in worms exposed concurrently to hypoxia and PCP. Clearly, hypoxia was the dominant stressor for individuals exposed to B(a)P or CPF, but to a lesser extent upon PCP treatment. And since oxygen deprivation promotes the accumulation of different toxicants, there may be consequences on species composition of metabolites in natural conditions., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Increasing usage of fullerenes (C60 ) increases their opportunities to be released into the environment. For risk assessment, it is important to understand the environmental fate and ecotoxicological effects of C60 . In the present study, fullerene settling was measured during a 1-yr period with 4 different lake waters and an artificial freshwater, and Daphnia magna immobilization and fullerene accumulation was also measured in each of the lake waters. Depending on the characteristics of the lake waters, fullerenes either exhibited extended water stability or settled rapidly; in all waters, there was a fraction that remained stable after 1 yr. Water stability was affected by the quality and molecular size distribution of dissolved natural organic matter (DNOM). Increasing DNOM molecular sizes with high aromatic content enhanced water stability. Immobilization of D. magna was generally quite low (under 20%) and highly variable after 24 h and 48 h at initial fullerene concentrations up to 10 mg/L. Substantial settling occurred during the time period for acute toxicity assays (i.e., 48 h), which should be anticipated when conducting toxicity assays. There were no significant differences in the quantity of accumulated fullerenes among the different lake waters at fullerene concentrations of 0.5 mg/L, but there were differences at 2 mg/L., (Copyright © 2013 SETAC.)

Assessment of the underlying molecular events leading to xenobiotic toxicity is challenging especially when techniques are applied in isolation. We examined transcriptional and metabolic changes in Lumbriculus variegatus exposed to benzo(a)pyrene (B(a)P), cadmium (Cd) or pentachlorophenol (PCP) by DNA microarrays (7422 ESTs) and gas chromatography-mass spectrometry (GC-MS), respectively. In addition, the DNA damage response of worms exposed to B(a)P was assessed by a capillary electrophoresis laser induced fluorescence (CE-LIF) immunoassay. We found elevated expression of oxidative stress responsive genes, which correlated positively with the changes in antioxidant vitamin precursors including alpha-tocopherol and cholecalciferol. Other genes with strong differential expressions were mostly involved in actin related processes and proteolysis, despite an apparent delayed Cd response. Phosphates, sugars and fatty acids were effectively reduced and suggested that chemical treatments may have interfered with energy metabolism. The increased amount of B(a)P diol-epoxide (BPDE)-DNA adducts in exposed worms appeared to correlate with the variability in uridine, inosine and xanthine, which are key components of nucleoside metabolism. This suggests that DNA damage was imminent or peaked within 6h. The results conformed to transcriptional changes in B(a)P exposed worms and compliment other approaches to elucidate underlying molecular changes., (Copyright © 2012 Elsevier Inc. All rights reserved.)

The trophic transfer of pyrene metabolites was studied using Gammarus setosus as a predator and the invertebrates Lumbriculus variegatus and Chironomus riparius as prey. The results obtained by liquid scintillation counting confirmed that the pyrene metabolites produced by the aquatic invertebrates L. variegatus and C. riparius were transferred to G. setosus through the diet. More detailed analyses by liquid chromatography discovered that two of the metabolites produced by C. riparius appeared in the chromatograms of G. setosus tissue extracts, proving their trophic transfer. These metabolites were not present in chromatograms of G. setosus exclusively exposed to pyrene. The present study supports the trophic transfer of PAH metabolites between benthic macroinvertebrates and common species of an arctic amphipod. As some PAH metabolites are more toxic than the parent compounds, the present study raises concerns about the consequences of their trophic transfer and the fate and effects of PAHs in natural environments., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Activated carbon (AC) amendment is a recently developed sediment remediation method. The strong hydrophobic organic contaminant sorption efficiency of AC has been shown in several studies, but effects on benthic organisms require more investigation. The AC induced effects on egestion rate, growth and reproduction of Lumbriculus variegatus were studied by applying bituminous coal based AC in three different particle size fractions, namely <63 μm (90%, AC(p)), 63-200 μm (AC(m)) and 1000 μm (AC(g)), to natural uncontaminated (HS) and artificial sediment (AS). Egestion rate, growth and reproduction decreased with increasing AC concentration and finer AC particle fractions, effects being stronger on HS than on AS sediment. Lipid content in AS was reduced already at the lowest AC doses applied (AC(p) and AC(m) 0.05%, AC(g) 0.25%). In addition, hormesis-like response was observed in growth (AS) and reproduction (AS, HS) indicating that AC may disturb organisms even at very low doses. Potential ecological effects need to be further evaluated in an amendment- and site-specific manner.

The aim of this study was to combine different lines of evidence on the impact of chemical pollution on benthic invertebrate communities in three European river basins (Elbe, Scheldt, and Llobregat). The study integrates chemical analyses, a battery of different sediment toxicity tests, and field data from soft-sediment meio- and macrobenthic fauna within a sediment-quality triad in which chironomids, oligochaetes, and nematodes are identified on the species level. The use of TU (toxic units) and msPAF (multi-substance potentially affected fraction) in an approach assessing the chemical impact as well as the integration of sediment toxicity tests with bacteria (Vibrio fischeri), benthic invertebrates (Caenorhabditis elegans, Potamopyrgus antipodarum, Lumbriculus variegatus, Chironomus riparius), and fish embryos (Danio rerio), together with univariate and non-parametric multivariate statistical analyses of the biological data revealed significant differences between unpolluted and polluted sites in all three river basins. To combine the different results obtained in the sediment-quality triad, a scoring system was successfully developed based on a simple algorithm. This system provides an easily understandable scheme for non-experts among decision makers and water managers., (Copyright © 2012 Elsevier B.V. All rights reserved.)

An environmentally realistic method to test fullerene (C(60) ) toxicity to the benthic organism Chironomus riparius was created by allowing suspended fullerenes to settle down, making a layer on top of the sediment. To test the hypothesis that higher food concentrations will reduce toxic responses, two food concentrations were tested (0.5 and 0.8% Urtica sp.) in sediment containing fullerene masses of 0.36 to 0.55 mg/cm(2) using a 10-d chronic test. In the 0.5% food level treatments, there were significant differences in all growth-related endpoints compared with controls. Fewer effects were observed for the higher food treatment. Fullerene agglomerates were observed by electron microscopy in the gut, but no absorption into the gut epithelial cells was detected. In the organisms exposed to fullerenes, microvilli were damaged and were significantly shorter. The potential toxicity of fullerene to C. riparius appears to be caused by morphological changes, inhibiting larval growth., (Copyright © 2012 SETAC.)

The trophic transfer of pyrene metabolites was evaluated by a 2-month exposure of the freshwater annelid Lumbriculus variegatus (Oligochaeta) to pyrene, followed by feeding to juvenile brown trout (Salmo trutta). The results obtained by scintillation counting (SC) proved that the pyrene metabolites produced by L. variegatus were transferred to juvenile S. trutta through diet. More detailed analyses by LC-FLD (liquid chromatography with fluorescence detection) showed that an unknown pyrene metabolite originating from L. variegatus was present in fish liver. This metabolite, although yet not properly identified, may be the glucose conjugate of 1-hydroxy-pyrene. This metabolite was not present in chromatograms of fish that were fed pyrene-spiked food pellets. In addition, the strongly bound tissue residue of L. variegatus, which was nonextractable neither by organic solvents nor by the proteolytic enzyme Proteinase K, was most likely not available for the fish through diet. Altogether, the present study shows that the metabolites of pyrene produced at low levels of the food chain may be potentially available for upper levels through diet, raising a concern about their potential toxicity to predators and supporting their inclusion in the risk assessment of PAHs., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

New analytical methods are available for detecting novel xenobiotic compounds in freshwater systems. Pharmaceuticals are suspected of having effects on freshwater biota at very low concentrations, although the nature of these effects remains unclear. Previous data from the Llobregat River revealed a positive statistical relationship between the biomass of benthic macroinvertebrates and the presence of certain non-steroidal anti-inflammatory drugs (NSAIDs) and beta-blockers. Here, experiments were conducted with the midge Chironomus riparius and the freshwater snail Physella (Costatella) acuta in sediments and water, respectively. The sediments and water were treated with the pharmaceuticals propranolol and indomethacin, with the aims of assaying the effects of these compounds on the organisms and testing the statistical relationships observed in field. The variables measured were survival; C. riparius biomass; and the carbon/nitrogen ratio, lipid content and fertility of freshwater snails. Indomethacin in treated sediments induced an increase in C. riparius biomass, whereas propranolol inhibited growth, albeit at marginal statistical significance. By contrast, indomethacin in water had no effect on any of the parameters measured in P. acuta., (Copyright © 2011 Elsevier Inc. All rights reserved.)

The functionality of dissolved organic matter (DOM) was studied by assessing the availability of polycyclic aromatic hydrocarbons (PAHs) spiked in pore water samples separated from sediments by water extraction and centrifugation with or without subsequent filtration. The purpose was to compare the effects of traditionally defined DOM (0.45-μm cut off) and larger colloidal material present in the separated pore water samples on the partitioning and bioavailability of PAHs. The tested PAHs included phenanthrene (Phe), fluoranthene (Flu), pyrene (Pyr) and benzo[a]pyrene (BaP). Bioavailability of the selected PAHs was tested with two ecologically different organisms: pelagic filter feeder Daphnia magna and sediment-dwelling deposit feeder Lumbriculus variegatus. Sorption to DOM (i.e. in filtered samples) was clearly higher for BaP than for the other PAH. This was also reflected in significantly reduced bioavailability for both model organisms in the filtered samples compared to DOM-free conditions. For the other PAHs the sorption was significant only in the unfiltered samples indicating the importance of larger colloidal material. Thus, the bioavailability of PAHs was also more effectively reduced by the colloidal material. This holds true for both the model organisms, indicating that the ecological differences i.e. filter feeder vs. deposit feeder do not affect in this respect. It appears that considering only traditionally defined DOM, material that may be present in environmental samples and is important for the speciation and bioavailability of contaminants is ignored., (Copyright © 2011 Elsevier Inc. All rights reserved.)

This study evaluated the toxicological sensitivity of non-feeding larval stages of a key Antarctic species (Antarctic krill, Euphausia superba) to p,p'-dichlorodiphenyl dichloroethylene (p,p'-DDE) exposure. The aqueous uptake clearance rate of 84 mL g(-1) preserved weight (p.w.) h(-1) determined for p,p'-DDE in Antarctic krill larvae is comparable to previous findings for small cold water crustaceans and five times slower than the rates reported for an amphipod inhabiting warmer waters. Natural variations in larval physiology appear to influence contaminant uptake and larval krill behavioural responses, strongly highlighting the importance of time of measurement for ecotoxicological testing. Sublethal narcosis (immobility) was observed in larval Antarctic krill from p,p'-DDE body residues of 0.2 mmol/kg p.w., which is in agreement with findings for adult krill and temperate aquatic species. The finding of comparable body residue-based toxicity of p,p'-DDE between polar and temperate species supports the tissue residue approach for environmental risk assessment of polar ecosystems., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Effects of fullerene-spiked sediment on a benthic organism, Lumbriculus variegatus (Oligochaeta), were investigated. Survival, growth, reproduction, and feeding rates were measured to assess possible adverse effects of fullerene agglomerates produced by water stirring and then spiked to a natural sediment. L. variegatus were exposed to 10 and 50 mg fullerenes/kg sediment dry mass for 28 d. These concentrations did not impact worm survival or reproduction compared to the control. Feeding activities were slightly decreased for both concentrations indicating fullerenes' disruptive effect on feeding. Depuration efficiency decreased in the high concentration only. Electron and light microscopy and extraction of the worm fecal pellets revealed fullerene agglomerates in the gut tract but not absorption into gut epithelial cells. Micrographs also indicated that 16% of the epidermal cuticle fibers of the worms were not present in the 50 mg/kg exposures, which may make worms susceptible to other contaminants., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Persistent organic pollutants (POPs) are persistent, toxic and bioaccumulative anthropogenic organic chemicals, capable of undergoing long range environmental transport to remote areas including the Antarctic. p,p'-dichlorodiphenyl dichloroethylene (p,p'-DDE) has been identified as a dominant POP accumulating in Antarctic krill (Euphausia superba), which is a key Southern Ocean species. This study examined the developmental toxicity of p,p'-DDE via aqueous exposure to Antarctic krill larvae. p,p'-DDE exposure was found to stimulate developmental timing in the first three larval stages of Antarctic krill, while extended monitoring of larvae after a five day exposure period had ended, revealed delayed inhibitory responses during development to the fourth larval stage. Stimulatory responses were observed from the lowest p,p'-DDE body residue tested of 10.1±3.0 μmol/kg (3.2±0.95 mg/kg) preserved wet weight, which is comparable to findings for temperate species and an order of magnitude lower than the exposure level found to cause sublethal behavioural effects in Antarctic krill. The delayed responses included increased mortality, which had doubled in the highest p,p'-DDE treatment (95±8.9% mortality at 20 μg/L p,p'-DDE) compared to the solvent control (44±11% mortality) 2 weeks after end of exposure. Development of surviving metanauplius larvae to calyptopis 1 larvae was delayed by 2 days in p,p'-DDE exposed larvae compared with untreated larvae. Finally, the developmental success of surviving p,p'-DDE exposed larvae was reduced by 50 to 75% compared to the solvent control (100% developmental success). The lowest observed effect concentration for all delayed effects was 1 μg/L, the lowest exposure concentration tested. These findings demonstrate the importance of delayed and indirect effects of toxicant exposure. Further, the findings of this study are important for environmental risk assessment of POPs in the Southern Ocean ecosystem and strongly highlight the significance of developmental endpoints for ecotoxicological testing., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Fate of organic contaminants under UV irradiation as environmental variable was studied. Aqueous solutions of pentachlorophenol and phenanthrene were subjected to simulated solar radiation and monitored during ≤ 93 h. Immobilization tests were conducted using Daphnia magna neonates in pre-irradiated water for the assessment of photoproduct-mediated toxicity. We observed a time-dependent decrease in exposure concentrations following irradiation, which correlated positively with reduced immobilization of the animals. A complete disappearance of the lowest and highest concentrations of pentachlorophenol was noted after 25 h and 75 h, respectively. Survivorship of the animals increased until 100% and correlated positively with irradiation time. However, phenanthrene was rather persistent under irradiation, with less than 25% decline in exposure concentrations after 93 h. Neonates were not immobilized at maximum aqueous solubility of phenanthrene. Rate constants (k) for the photodegradation of pentachlorophenol at 0.41, 0.59, 1.1, and 2.1 mg l(-1) were in the range of 7.2 × 10(-2) and 4.9 × 10(-2)h(-1), showing a slight decrease with increasing initial pentachlorophenol concentration. Nonetheless, pentachlorophenol degradation in the studied concentration range could still be described by the pseudo-first-order kinetics. K values for phenanthrene at 0.12 and 0.22 mg l(-1) were 2.9 × 10(-3)h(-1) and 4.2 × 10(-3)h(-1), respectively., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Using the freshwater annelid Lumbriculus variegatus (Oligochaeta), the presence of cytochrome P450 (CYP) isozymes was investigated by analyzing metabolites of the polycyclic aromatic hydrocarbon (PAH) pyrene in treatments with and without the CYP inhibitor piperonyl butoxide (PBO). The results show a low biotransformation capability of L. variegatus (7% of total pyrene body burden as metabolites at 168 h). Addition of PBO resulted in a significant reduction of metabolites, suggesting the presence of a CYP in L. variegatus. Besides 1-hydroxypyrene, three peaks representing unknown metabolites were detected in LC-FLD (liquid chromatography with fluorescence detection) chromatograms of L. variegatus. Deconjugations showed that sulfonation and glucosidation are involved in the formation of these unknowns. Further studies with the time of flight mass analyzer provided the identification of the glucose-sulfate conjugate of 1-hydroxypyrene. The same metabolites were detected in the solvent-nonextractable fraction by incubation of the tissue residues with proteinase K, suggesting that part of these metabolites are bound to proteins. Overall, the slow biotransformation of pyrene by L. variegatus (involving CYP) supports the use of this species in standard bioaccumulation tests; however, the tissue-bound metabolite fraction described in the current study deserves further investigation for its toxicity and availability to upper trophic levels through diet., (Copyright © 2011 SETAC.)

The toxicity of four polluted sediments and their corresponding reference sediments from three European river basins were investigated using a battery of six sediment contact tests representing three different trophic levels. The tests included were chronic tests with the oligochaete Lumbriculus variegatus, the nematode Caenorhabditis elegans and the mudsnail Potamopyrgus antipodarum, a sub-chronic test with the midge Chironomus riparius, an early life stage test with the zebra fish Danio rerio, and an acute test with the luminescent bacterium Vibrio fischeri. The endpoints, namely survival, growth, reproduction, embryo development and light inhibition, differed between tests. The measured effects were compared to sediment contamination translated into toxic units (TU) on the basis of acute toxicity to Daphnia magna and Pimephales promelas, and multi-substance Potentially Affected Fractions of species (msPAF) as an estimate for expected community effects. The test battery could clearly detect toxicity of the polluted sediments with test-specific responses to the different sediments. The msPAF and TU-based toxicity estimations confirmed the results of the biotests by predicting a higher toxic risk for the polluted sediments compared to the corresponding reference sediments, but partly having a different emphasis from the biotests. The results demonstrate differences in the sensitivities of species and emphasize the need for data on multiple species, when estimating the effects of sediment pollution on the benthic community., (Copyright © 2010 Elsevier Inc. All rights reserved.)

In the current study, the toxicokinetics of pyrene in Daphnia magna was determined in detail, and the role of dissolved organic matter (DOM) in these processes was investigated. Uptake, biotransformation, parent compound and metabolite elimination rates (k(u), k(m), k(ep), k(em)), depuration rates, bioconcentration factors (BCFs), and biological half-lives were studied in one natural humic water, in two waters made from DOM isolates, and in DOM-free artificial fresh water. The daphnids were exposed to pyrene for 24 h and depurated for another 24 h. To analyze the data, the two-compartment model was used to obtain toxicokinetic parameters, and the depuration data were analyzed by linear regression. Extensive biotransformation of pyrene resulted in high metabolite concentration in the organisms (83% of total radioactivity) after 24 h exposure. Depuration of the parent compound seemed to be biphasic: at first, depuration was rapid, but after 4 to 10 h in uncontaminated water, the disappearance rate came close to zero. After a 24-h depuration time, 7.8% of the pyrene accumulated remained in the organism. Overall, the elimination of parent compound was faster than the elimination of metabolites, which might imply inefficient excretion of water-soluble biotransformation products from daphnids. The effect of DOM on accumulation of pyrene was seen in a decreased uptake rate, indicating lower bioavailability of the compound in waters that contain high-aromaticity DOM. In the same waters, DOM significantly accelerated pyrene biotransformation and overall elimination. Altogether, DOM appears to be able to affect toxicokinetics through mechanisms that are connected to interaction with the contaminant but also directly through interaction with biotransformation systems., (Copyright © 2010 SETAC.)

This study assessed the partitioning of 2,2',4,4'-tetrabromo diphenyl ether (BDE-47), 2,2',4,4',5-pentabromo diphenyl ether (BDE-99) and benzo[a]pyrene (BaP) among water, dissolved organic carbon (DOC: 4.93-8.72 mg/L), and particulate organic carbon (POC: 191-462 µg/L) along the salinity gradient (0-5.5‰) of the Baltic Sea off the coast of Finland. Equilibrium dialysis and two solid-phase extraction techniques using polyoxymethylene polymer (POM) were used to determine partitioning coefficients. Experiments using artificial coastal water (ACW) with Nordic fulvic (FAs) and humic acids (HAs) were used to assess the effect of salinity (0 and 5.5‰) on the DOC-water partitioning of the model compounds. All three compounds bound more (2.2-3.8-fold) to the HAs than to the FAs. Increasing salinity from 0 to 5.5‰ decreased sorption to dissolved humic substances in the ACW and Baltic Sea water samples. Along the salinity gradient, the sorption of compounds to organic material decreased when the salinity increased. Particulate organic matter sorbed model compounds per unit of carbon more than dissolved organic matter. Along the studied salinity gradient, the freely dissolved portion increased from 10 to 29% to 52 to 80% in the coastal water samples, mainly because of the increasing salinity and changes in DOC and quality of POC., (© 2010 SETAC.)

Many insectivores have been shown to be sensitive to heavy metals and therefore suitable for biomonitoring purposes. In Finland, the hibernation period of the European hedgehog (Erinaceus europaeus) is long, and during hibernation the stress caused by environmental toxins may be crucial. Concentrations of cadmium (Cd), copper (Cu), iron (Fe), magnesium (Mg), manganese (Mn), molybdenum (Mo), nickel (Ni), lead (Pb), arsenic (As), and selenium (Se) were measured in a population of hedgehogs in the town of Joensuu in eastern Finland during the summers of 2004 and 2005. The analyzed tissues were kidney, liver, hair, and spine. The sampled hedgehogs (n = 65) were mainly road-killed animals. As expected, the concentrations of heavy metals were low because the hedgehogs were living in a comparatively unpolluted area. Significant increases with age were found in Cd concentrations (kidney, liver, and spine) and some essential elements (Se in spine, kidney, and liver; Mo in kidney and liver; Cu in spine; Fe in liver; and Mn in spine). Age accumulation and correlations between Se and Cd and between Mo and Cd may indicate the protective roles of Se and Mo against Cd toxicity in hedgehogs, in which Cd is already at comparatively low concentrations. Sex had no significant effect on concentrations of the elements studied. In conclusion, age is an important parameter to be taken into account when studying heavy-metal concentrations in hedgehogs and other insectivores.

Black carbon (BC) and chemical properties may play a significant role in defining the bioavailability of hydrophobic organic compounds (HOCs) in sediment. In the current study, bioavailability of four HOCs with differing planarity was determined in sediments amended with two types of BC (soot and charcoal) at different concentrations by matrix solid-phase microextraction (matrix-SPME) and bioaccumulation testing using the freshwater oligochaete Lumbriculus variegatus. Furthermore, the applicability of the matrix-SPME method to bioavailability estimation in BC-amended sediment was tested. The charcoal treatment significantly reduced the bioaccumulation of the planar compounds (3,3',4,4'-tetrachlorobiphenyl and benzo[a]pyrene) in L. variegatus, and the matrix-SPME method showed a similar trend as contaminant bioaccumulation in L. variegatus. Conversely, manipulation of sediment with soot had no effect or slightly increased bioavailability of the planar compounds in both bioaccumulation and matrix-SPME tests. Little if any affect was noted in bioavailability of the nonplanar compounds (2,2',4,4',5,5'-hexachlorobiphenyl and permethrin) with the soot and charcoal amendments. Results showed that the role of BC in defining bioavailability of HOCs depends not only on the type and concentrations of BC present, but also the planarity of the HOCs., (Copyright 2010 SETAC.)

This study presents the bioavailability of four spiked compounds to Lumbriculus variegatus, in sediment samples from three river basins in Europe: the Elbe, the Llobregat, and the Scheldt. Twenty sediment samples differing in physical and chemical properties were spiked with chlorpyrifos, pyrene, tetrachloribiphenyl, and tetrabromo diphenyl ether. The main focus of this study was to compare the suitability of two chemical approaches-the rapidly desorbing fraction method based on the Tenax extraction and the freely dissolved chemical concentration method based on polyoxymethylene passive sampling-for predicting the bioavailability of sediment-associated hydrophobic compounds. It appears that accessible concentration estimated by Tenax extraction does not result in equal freely dissolved concentrations based on polyoxymethylene passive sampling results. The present data show that freely dissolved concentration in pore water mainly determines the uptake by organisms and, therefore, the polyoxymethylene passive sampling method was a successful approach to estimating the bioavailability of sediment-associated lipophilic contaminants (log octanol-water partitioning coefficient >6). The sediment characteristics or river basin differences had only a minor effect on the bioavailability estimates. Overall, passive samplers have not been tested to a sufficient extent in various chemicals or exposure matrixes. For this reason, bioassays are still needed in the risk assessment process in order to verify results based on passive sampling methods.

A simple method for analyzing masses of water suspended fullerenes (nC60) in Daphnia magna by extracting to toluene and measuring by ultraviolet-vis spectrophotometry was developed. This method was used to assess bioaccumulation and depuration rates by daphnia after nC60 exposure in artificial freshwater. Accumulation was rapid during the first few hours, and based on accumulation modeling, 90% of the steady-state concentration was reached in 21 h. After exposure for 24 h to a 2 mg/L fullerene solution, the daphnia accumulated 4.5+/-0.7 g/kg wet weight, or 0.45% of the organism wet mass. Daphnids exposed to 2 mg/L fullerenes for 24 h eliminated 46 and 74% of the accumulated fullerenes after depuration in clean water for 24 and 48 h, respectively. Transmission electron microscopy revealed that the majority of the fullerenes present in the gut of daphnids were large agglomerates. The significant fullerene uptake and relatively slow depuration suggest that D. magna may play a role as a carrier of fullerene from one trophic level to another. Additionally, D. magna may impact the fate of suspended fullerene particles in aquatic ecosystems by their ability to pack fullerene agglomerates into larger particles than were found in the exposure water, and then excrete agglomerates that are not stable in water, causing them to settle out of solution. This process decreases fullerene exposure to other aquatic organisms in the water column but may increase exposure to benthic organisms in the sediment., (Copyright (c) 2010 SETAC.)

The effects of temperature and sediment-chemical contact time on desorption and bioaccumulation of sediment-spiked (14)C-labelled 2,2',4,4'-tetrabromo diphenyl ether (BDE-47) and benzo(a)pyrene (BaP) were examined. Experiments were performed after 2 or 6 weeks and 23 or 24 months sediment-chemical contact time at 10 and 20 degrees C. Desorption was measured in a sediment-water suspension using Tenax extraction, and bioaccumulation was measured by exposing Lumbriculus variegatus (Oligochaeta) to BDE-47 and BaP-spiked sediments in a 10d kinetic study. Biota-sediment accumulation factors (BSAFs) ranged between 2.9 and 4.3 for BDE-47 and between 0.5 and 0.9 for BaP. Thus, temperature and aging had a minor effect on bioavailability estimates. On the other hand, the difference between the chemicals was clear and could not be interpreted solely by reference to the size of the desorbing fractions, although the rapidly desorbing fraction-revised estimate clearly reduced the difference. The remaining discrepancy may be related to methodological (Tenax extraction vs. worm exposure) and/or biological (digestive extraction) causes. However, the data support the role of diffusional forces in the bioavailability of sediment-associated organic contaminants. Therefore, desorption-revised bioavailability estimates would lead to more precise bioavailability estimates than the traditional sediment organic carbon-organisms' lipids-based equilibrium partitioning approach.

The relationship between desorption kinetics and bioavailability of sediment-associated 2,2',4,4,5' pentabromo diphenyl ether [(14)C] (BDE-99) and 2,3,7,8 tetrachlorodibenzo(p)dioxin [(3)H] (TCDD) was examined in the contaminated sediments. The desorption kinetics were measured in a sediment-water suspension using Tenax extraction, and bioaccumulation was examined by exposing Lumbriculus variegatus (Oligochaeta) to BDE-99 and TCDD spiked sediment in a 14-day kinetic study. Both chemicals had a high affinity to the finest particle size fraction (<20 microm) and the large, very slowly desorbing fraction (58-75%). The biota-sediment accumulation factors ranged between 1.9 and 4.4 for BDE-99 and between 1.4 and 2.8 for TCDD. The chemical outflux from the rapidly desorbing fraction and influx into organisms shows the connection between desorption and bioavailability. Despite this, normalization to the rapidly desorbing fraction was unable to reduce differences in bioavailability estimates between the chemicals. Thus, it is evident that chemical extraction in the mixed system (Tenax tubes) does not fully describe the bioavailable fraction that worms face in stagnant sediments in a similar way for all chemicals. However, when all desorbing domains were included in the calculation, the difference between the chemicals disappears. Desorbing fractions were also able to reduce variability in the biota-sediment accumulation factors between the tested sediments when organic carbon-based sediment chemical concentrations were modified by the desorbing fractions.

It is inevitable that carbon nanotubes (CNTs) will be released to and widely dispersed in environmental ecosystems, given their numerous expected applications. Determination of their potential for bioaccumulation by ecological receptors is thus critical. Previous, research involving several different terrestrial and benthic organisms has indicated that CNTs spiked to soils or sediments do not bioaccumulate. Conversely, we report here distinctly different uptake and depuration behaviors for an aquatic organism, Daphnia magna, in a water-only system. After 48 h of exposure of this organism to a 0.4 microg/mL solution of dispersed nanotubes, the CNTs comprised 6.3 +/- 1.5% of the residual organism dry mass. Moreover, these organisms were unable to excrete the nanotubes to either clean artificial freshwater or filtered Lake Kontiolampi water after 24 h depuration periods, even though the lake water had a substantial concentration of natural organic matter. Addition of algae to the water during the depuration period did result however in release of a significant fraction (approximately 50-85%) of the accumulated CNTs within the first few hours, but little thereafter. Light microscopy results suggest that the vast majority of the accumulated CNTs remained in the organisms' guts and were not absorbed into cellular tissues.

The aim of this work was to study the toxicity and biotransformation of polyaromatic hydrocarbon (PAH) pyrene in the oligochaete aquatic worm, Lumbriculus variegatus. PAHs are ubiquitous environmental pollutants that pose a hazard to aquatic organisms, and metabolizing capability is poorly known in the case of many invertebrate species. To study the toxicity and biotransformation of pyrene, the worm was exposed for 15 days to various concentrations of water-borne pyrene. The dorsal blood vessel pulse rate was used as a sublethal endpoint. Pyrene biotransformation by L. variegatus was studied and the critical body residues (CBR) were estimated for pyrene toxicity. The toxicokinetics of pyrene uptake was evaluated. A combination of radiolabeled (14C) and nonlabeled pyrene was used in the exposures, and liquid scintillation counting (LSC) and high-pressure liquid chromatography were employed in both water and tissue residue analyses. The results showed that L. variegatus was moderately able to metabolize pyrene to 1-hydroxypyrene (1-HP), thus demonstrating that the phase-I-like oxidizing enzyme system metabolizes pyrene in L. variegatus. The amount of the 1-HP was 1-2% of the amount of pyrene in the worm tissues. The exposure to pyrene reduced the blood vessel pulse rate significantly (p<0.05), showing that pyrene had a narcotic effect. The estimated CBRs remained constant during the exposure time, varying from 0.120 to 0.174 mmol pyrene/kg worm wet weight. The bioconcentration factors (BCF) decreased as exposure concentration increased. It was suggested that the increased toxicity of pyrene accounted for the decrease in BCFs by lowering the activity of the organism.

A small peatland catchment in eastern Finland was monitored for runoff and export of dissolved organic carbon. To exemplify the response of a peatland under years of different meteorological conditions, data from one very dry and one wet growing season are presented. Runoff was 194 and 387 mm, and DOC export was 4.2 and 11.3 gC m(-2) in the dry and wet year respectively. Analysis of the hydrographs showed that in both years most runoff and DOC export was generated during peak flow events, with low baseflow in the intermediate periods. Runoff response to rain events was strongest under a high water table in the spring and autumn, with a summer runoff minimum. The effect of drought on runoff occurred only after mid June when the effects of snowmelt had dissipated. Snowmelt therefore dominated DOC export in the dry year (61%) but contributed much less (29%) in the wet year. The relationship between runoff and the water table was highly similar in both years. Any variation that was observed herein was potentially related to a superficial subsidence of the peat surface under drier summer conditions and to raised spring water levels, causing restricted drainage due to flooding. The observed variation of DOC concentrations in both years generally had a limited impact on DOC export. During peak runoff events, concentrations dropped proportionally to the magnitude of the events. This decrease in available DOC is argued to be caused by a dominance of leaching over supply and production and by the specific hydraulic characteristics of the peatland surface. DOC concentrations were some 25% higher under drought conditions. These elevated concentrations were dispelled by spring snowmelt of the next year, demonstrating that a winter snowpack in boreal regions may be instrumental in limiting the longer term hydrological and biochemical effects of a drought.

The bioaccumulation of the pesticides chlorpyrifos and atrazine to the benthic oligochaeta Lumbriculus variegatus from four diverse artificially contaminated lake sediments (OC 0.13-21.5%) was studied in the laboratory. The steady state of bioaccumulation was not reached within 10d. Chlorpyrifos showed stronger bioaccumulation than the less lipophilic atrazine, the biota-sediment accumulation factors (BSAFs) being 6.2-99 for the former and 1.9-5.3 for the latter. While bioaccumulation factors (BAFs) dropped with increasing organic content of the sediments, the high level and considerable range of the obtained BSAFs indicate other sediment qualities, such as the age and characteristics of the organic material, having a strong effect on the bioavailability of these compounds. The slow and incomplete desorption of chlorpyrifos from the most inorganic sediment indicates also that this compound may be strongly bound to some type of inorganic material. Any specific influential sediment fraction or characteristic could not be identified.

Epidermal papillomatosis in fish has been proposed as an indicator of environmental stress but experimental evidence of connection between contaminants and papillomatosis in fish is scarce. We studied changes in the intensity of epidermal papillomatosis and the expression of heat shock protein 70 (HSP70) in roach, Rutilus rutilus, exposed to treated pulp mill and municipal effluents. In male roach, the increase in papillomatosis intensity was higher in fish exposed to 15% than in fish exposed to 1.5% concentration of municipal effluent. No differences were observed in papillomatosis development in females, or in HSP70 expression. In all the experiments conducted, the increasing effect of effluents seemed to be more pronounced in male fish suggesting that sex-related factors affected the intensity of papillomatosis after exposure to effluents. The present results indicate that environmentally relevant concentrations of municipal effluents may be contributing to the development of papillomatosis in fish.

Joint effects of temperature and oxygen concentrations for the results of sediment toxicity tests were studied at 10 and 20 degrees C with 40% and 80% dissolved oxygen (DO) saturation. Growth, feeding rate, and reproduction of Lumbriculus variegatus (Oligochaete) and growth, emergence, and survival of Chironomus riparius (Diptera) were tested in a polluted and in a reference sediment. Both the feeding of L. variegatus and the emergence of C. riparius were significantly retarded at low temperature. Additionally, differences in the sex ratio of the emerged adults of C. riparius were observed. The oxygen concentration alone did not have any significant effect on the endpoints, but significant combined effects of polluted sediment and low DO were observed on the biomass of L. variegatus. The standard sediment toxicity tests might offer only limited data for risk assessment of contaminated sediments at sites where the actual conditions largely differ from the laboratory conditions.

The transport and bioavailability of sediment-associated contaminants are often controlled by the contaminants' desorbing behaviour. This study examines the desorption kinetics of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), diphenyl ethers (PCDEs) and hydroxydiphenyl ethers (HO-PCDEs) from the highly contaminated River Kymijoki sediment in Finland. The desorption kinetics data were generated using Tenax((R)) extraction, and a first-order three-compartment kinetic model was fitted to the data. The desorption data was compared to the previously published accumulation data from this same location to investigate the relationship between the rapidly desorbing fraction (F(r)) and biota-sediment accumulation factors (BSAFs) as well as semipermeable membrane device sediment accumulation factors (SSAFs). The PCDDs, PCDFs, PCDEs and HO-PCDEs were tightly attached to sediment particles and formed a large very slowly desorbing fraction (F(vs)). Rapidly desorbing fractions (F(r)) varied between 0.8% and 8% of total amount in sediment. The size of the desorbing fraction was congener-specific and F(r) decreased with the increasing lipophilicity of congeners. The size of the F(r) was unable to explain the small variation in the BSAFs of Lumbriculus variegatus but may help to explain the observed variation in the SSAFs. To our best knowledge, this study is the first effort to investigate the desorption of PCDDs, PCDFs, PCDEs and HO-PCDEs in field-contaminated sediments. The major finding that the very slow desorption of these chemicals will continue years, provides essential information for the modern risk assessment process.

The desorption and bioavailability of 3,3',4,4'-tetrachlorobiphenyl (PCB 77) were studied in spiked natural sediments at six concentrations. The desorption kinetics were measured in a sediment-water suspension using Tenax resin extraction, and the bioavailability was measured by exposing Lumbriculus variegatus (Oligochaeta) to PCB 77-spiked sediment in a 14-d kinetic study. In addition, freely dissolved pore-water concentrations were measured using the polyoxymethylene solid-phase extraction method. The present study examined whether bioavailability can be defined more accurately by measuring the size of desorbing fractions and the pore-water concentrations than by using the standard equilibrium partitioning approach. The importance of ingested sediment in bioaccumulation also was investigated. Our data showed a clear, decreasing trend in the rapid-desorbing fractions and in the standard biota-sediment accumulation factors (BSAF) with increasing concentration in sediment. Desorbing fractions-refined BSAFs were more uniform across the concentration treatments, and the pore-water PCB 77 concentration predicted tissue concentrations close to observed values. In the risk assessment process, pore-water concentration or desorbing fractions would lead to more precise bioavailability estimates compared with those from the traditional equilibrium partitioning approach. The result also showed, however, that sediment-ingesting worms had access to an additional bioavailable chemical fraction that was especially evident when PCB 77 pore-water concentrations most likely approached the solubility limit. Thus, feeding may modify the bioavailable fraction that cannot be explained by simple equilibrium partitioning models.

Humic substances may influence the bioavailability of polycyclic aromatic hydrocarbons (PAHs) in aquatic environment. Relatively little is known how humic substances affect the biotransformation of PAHs in aquatic animals. Here we report how two different types of humic substances affected the accumulation of pyrene, a four-ringed PAH, to yolk-sac fry of landlocked salmon (Salmo salar m. sebago). The accumulation of pyrene to yolk-sac fry tissues was inversely related to humic substance concentration in a short term (72h) exposure. However, the biotransformation of pyrene was not affected by humic substances. Pyrene or humic substances did not induce CYP1A activity in yolk-sac fry tissues contrasting to beta-naphthoflavone, which was used as a positive control. Yolk-sac fry were capable to biotransform pyrene to phase I (1-hydroxypyrene) and phase II (pyrene-1-sulphate) products. Interestingly, glucuronide conjugate (i.e. pyrene-1-glucuronide) was not present in yolk-sac fry tissues. The concentration of parent pyrene and 1-hydroxypyrene remained the same throughout the experiment but the concentration of pyrene-1-sulphate more than doubled from 24 to 72h. This finding suggests that salmon yolk-sac fry are not capable to excrete phase II biotransformation products or the excretion is very slow. Further, this could indicate that early life stage toxicity of many CYP1A inducing compounds is related to accumulation of phase II conjugates in fry tissues.

Hypoxia, which occurs frequently in aquatic ecosystems and is mainly due to increasing eutrophication can cause severe environmental stress in fish. We investigated experimentally the hypothesis that hypoxia could be one of the environmental stress factors that can induce papillomatosis in fish. Male roach Rutilus rutilus exposed to periodic oxygen deficiency and accompanied temperature increases (OT group) showed the highest increase in the intensity of papillomatosis, as measured by the number of scales covered by papillomatosis tumors. The second highest increase in disease intensity was among male roach exposed to periodical temperature increases. The incidence of such tumors was lowest in the control group, which was exposed to neither hypoxia nor increased temperature. The mortality of fish during the 17 d experiment was highest and the condition factor was lowest in the OT group, indicating this group experienced a higher level of stress. The apparent interaction of hypoxia and temperature suggests that these environmental stressors are among the multifactorial elements leading to papillomatosis in roach. Furthermore, these results provide experimental evidence to indicate that hypoxia may contribute to tumor development in fish.

The xenobiotics accumulated in sediments represent a hazard to organisms. In order to study the toxic effects of xenobiotics in organisms, body residue has been proposed as a more relevant dose-metric than the environmental concentration of the chemical. In this study, the benthic oligochaetes Lumbriculus variegatus were exposed to sediment-spiked pentachlorophenol (PCP) in a chronic study at different exposure concentrations. The aim was to examine sublethal toxic effects in sediment-dwelling and sediment-ingesting organisms, and to link the effects with chemical body residues. Growth, reproduction, and egestion rate were used as sublethal endpoints. Bioaccumulation, sublethal toxic effects, and biotransformation of PCP were investigated by exposing organisms to both artificial and natural sediments with similar organic carbon content. Sediment characteristics were assumed to have an effect on toxicity since PCP retarded both growth and reproduction in L. variegatus in the artificial sediment. In natural sediment, growth, and reproduction was also reduced in control treatments, probably indicating poor nutritional quality. Most of the extracted chemicals in L. variegatus tissues were water-soluble metabolites, indicating that L. variegatus was capable of biotransforming PCP. The extractable parent PCP body residues (CBR(50)) for L. variegatus growth and reproduction were in agreement with the values estimated for respiratory uncouplers in the literature.

In some kinetic studies with aquatic invertebrates, the bioaccumulation of polyaromatic hydrocarbons (PAHs) has been observed to peak at the beginning of the test. This has been explained by the depletion of PAHs from pore water due to limited desorption during the bioaccumulation test or, alternatively, by the activation of biotransformation mechanisms in the organisms. In the present study, we exposed the aquatic oligochaetes, Lumbriculus variegatus, to creosote oil-contaminated sediments to examine the bioaccumulation of PAHs and to clarify the importance of contaminant depletion and biotransformation for it. The contaminant depletion was studied by replanting test organisms into fresh, nondepleted test sediments at 3-d intervals over 12 d and by comparing the resulting body burdens to those of the organisms that were not replanted. The biotransformation capability of L. variegatus was assessed by following the concentration of 1-hydroxypyrene (1-HP), a phase I metabolite of pyrene, in oligochaete tissue during a 15-d test. We observed that the bioaccumulation of most PAHs indeed peaked at the beginning of the test. The concentrations in the replanted organisms were only 1.5 to 2 times higher than in nonreplanted organisms during the first 9 d of the test and, by day 12, no differences were detected. 1-Hydroxypyrene was detected in oligochaete tissue throughout the exposures, and concentrations decreased over time. However, the proportion of 1-HP to pyrene increased linearly during the test. These results indicated that the depletion of contaminants has only a minor effect on their bioaccumulation in oligochaetes and that the cause for the observed bioaccumulation curve shape is rapid elimination of the contaminants and, possibly to some degree, their metabolites.

The objective of this study is to discern the effects of increased waterborne lithium and potassium on rainbow trout gill histology, lipid composition, and enzyme activity. The study aims to elucidate the effects of these ions in the laboratory in concentrations similar to those prevailing in a forest lake Poppalijärvi in a contaminated mining area in NW Russia. Under the lithium and potassium exposure, the fish were further stressed by high pH (8.2 as in Lake Poppalijärvi) and lack of food. These multiple stress conditions altered the gill membrane fluidity by increasing sphingomyelin (5.5+/-0.6 compared to 2.9+/-0.3% in the control) and reducing cholesterol (4+/-1 compared to 17+/-3 mg g(-1) in the control). The total ATPase activity tended to be higher in the lithium-potassium-exposed group (46+/-6 compared to 34+/-2 micromol Pi h(-1) mg(-1)protein in the control). Lithium toxicity was lowered here by the protective role of higher potassium contents.

The bioaccumulation potential and environmental fate of polychlorinated hydroxydiphenyl ethers (HO-PCDEs; polychlorinated phenoxyphenols, PCPP), the major impurities of chlorophenol formulations and their methoxy analogues (MeO-PCDEs; polychlorinated methoxyanisoles, PCPAs) were investigated. Oligochaete worms (Lumbriculus variegatus) exposed to sediment spiked with a model substance of one HO-hexaCDE (4'-HO-PCDE 161) or its methoxy analogue (4'-MeO-PCDE 161) clearly accumulated the test compounds revealing the potential for environmental risk of HO-PCDEs and MeO-PCDEs. The HO-PCDE tested has earlier been reported as an abundant component in a Finnish chlorophenol formulation (Ky-5) and its methoxy analogue is recognized as an abundant MeO-PCDE in sawmill soil contaminated by the formulation. The occurrence of 4'-HO-PCDE 161 and its methoxy analogue among other HO-PCDEs and MeO-PCDEs in lake mussels (Anodonta piscinalis) incubated in a river contaminated via the manufacture of Ky-5 showed that these compounds are bioavailable and transported in the aquatic environment. Mussel comparison with sediment data pointed to a higher accumulation potential for MeO-PCDEs than for HO-PCDEs. The finding of HO-PCDEs in groundwater samples collected from a groundwater reservoir, which had been contaminated by chlorophenols, points to potential of HO-PCDEs for transport with water in soil.

Dissolved organic matter from natural sources (DNOM) is omnipresent in aquatic ecosystems. Besides affecting bioavailability of substances including xenobiotics, it directly influences physico-chemistry of the habitat and there is increasing evidence for it is interaction with organisms. We investigated direct and interacting effects of DNOM from three sources, Lake Valkea-Kotinen, Svartberget Brook, and Lake Fuchskuhle with the herbicide paraquat on the oligochaete worm Lumbriculus variegatus. Bioavailability of paraquat to L. variegates as well as activities of antioxidative enzymes catalase (CAT) and peroxidase (POD) and biotransformation enzyme soluble glutathione S-transferase (sGST) were assessed without and in the presence of DNOM. Furthermore, metabolic heat dissipation due to the exposure was quantified. Uptake of paraquat into the worms was concentration dependently reduced by DNOM, and with differences concerning the DNOM sources. sGST and CAT responded with increased activities to DNOM (5 and 25 mg C l-1) and paraquat (5.0, 50, and 500 microg l-1) separately. Paraquat at 5.0 microg l-1 and DNOM in combination caused increased activities of sGST, especially at 5 mgC l-1, but inhibition of CAT activities. The latter probably occurred due to saturation of the enzyme. Changes in enzyme activities were independent from the source of DNOM. Increasing DNOM concentrations raised metabolic heat dissipation in L. variegatus with maximum at 3h of exposure. In the combined treatments, metabolic heat dissipation changed more due to the source of DNOM than due to the bioavailability of paraquat.

In 1989, researchers discovered that amphibians, particularly frogs and toads from many parts of the world, appeared to be declining. In many ecosystems amphibians play a central role in ecosystem energy flow and nutrient cycling, and they act as keystone species. The recent increase in solar ultraviolet-B radiation (UVB, 280-320nm) has been thought to be one stressor responsible for the decline in amphibian populations. Along with other stressors, such as habitat destruction, anthropogenic influences and natural causes, UVB radiation could contribute to adverse effects among amphibians. Amphibians provide a good model for examining the effects of environmental stressors, because both lethal and sub-lethal responses are well documented in a range of studied xenobiotics in many species. In this experiment, the effects of UVB radiation on the accumulation and depuration kinetics of bisphenol A (BPA) were studied. Additionally, the accumulation was further modeled with correction for growth dilution. The results indicate that UVB radiation did not affect the toxicokinetics of BPA, and that the applied growth correction had only a negligible influence on the toxicokinetic estimations in this experiment. However, BCFs values calculated as k(u)/k(e) where closer to C(a)/C(w) calculated values when growth dilution was incorporated in the model. This method can be used in other experiments, where the growth dilution can affect toxicokinetic estimations.