Biodegradation of microplastic in freshwaters: A long-lasting process affected by the lake microbiome.

Plastics have been produced for over a century, but definitive evidence of complete plastic biodegradation in different habitats, particularly freshwater ecosystems, is still missing. Using 13 C-labelled polyethylene microplastics (PE-MP) and stable isotope analysis of produced gas and microbial membrane lipids, we determined the biodegradation rate and fate of carbon in PE-MP in different freshwater types. The biodegradation rate in the humic-lake waters was much higher (0.45% ± 0.21% per year) than in the clear-lake waters (0.07% ± 0.06% per year) or the artificial freshwater medium (0.02% ± 0.02% per year). Complete biodegradation of PE-MP was calculated to last 100-200 years in humic-lake waters, 300-4000 years in clear-lake waters, and 2000-20,000 years in the artificial freshwater medium. The concentration of 18:1ω7, characteristic phospholipid fatty acid in Alpha- and Gammaproteobacteria, was a predictor of faster biodegradation of PE. Uncultured Acetobacteraceae and Comamonadaceae among Alpha- and Gammaproteobacteria, respectively, were major bacteria related to the biodegradation of PE-MP. Overall, it appears that microorganisms in humic lakes with naturally occurring refractory polymers are more adept at decomposing PE than those in other waters.

Submicron Plastic Adsorption by Peat, Accumulation in Sphagnum Mosses and Influence on Bacterial Communities in Peatland Ecosystems.

The smallest fraction of plastic pollution, submicron plastics (SMPs <1 µm) are expected to be ubiquitous in the environment. No information is available about SMPs in peatlands, which have a key role in sequestering carbon in terrestrial ecosystems. It is unknown how these plastic particles might behave and interact with (micro)organisms in these ecosystems. Here, we show that the chemical composition of polystyrene (PS) and poly(vinyl chloride) (PVC)-SMPs influenced their adsorption to peat. Consequently, this influenced the accumualtion of SMPs by Sphagnum moss and the composition and diversity of the microbial communities in peatland. Natural organic matter (NOM), which adsorbs from the surrounding water to the surface of SMPs, decreased the adsorption of the particles to peat and their accumulation by Sphagnum moss. However, the presence of NOM on SMPs significantly altered the bacterial community structure compared to SMPs without NOM. Our findings show that peatland ecosystems can potentially adsorb plastic particles. This can not only impact mosses themselves but also change the local microbial communities.

Toxicity of Tire Rubber Microplastics to Freshwater Sediment Organisms.

High emission of tire rubber particles to the surrounding environment is an inevitable consequence of the current habits of transportation. Although most of the emissions stay within a close range of the sources, it has been proven that the smallest particles can be transported to remote locations through the atmosphere, including inland water bodies. It has been estimated that a relevant portion of the global emissions of tire rubber particles reach surface waters, but effects on aquatic life in the receiving water bodies are not completely understood. In the present study, we used the freshwater sediment dwellers Lumbriculus variegatus and Chironomus riparius to examine the toxicity of tire rubber particles at environmentally relevant concentrations, using different types of sediment and two particle sizes of tire rubber. Overall, the experiments were unable to discern any effects on the growth, survival or reproduction of the two animals tested. Significant differences were found among the animals dwelling on different sediments, but the effects were not attributable to the presence of tire rubber particles. This study provides important information regarding the lack of effect of tire rubber particles in laboratory experiments with model sediment dwellers and opens more questions about the potential effects of tire rubber particles in the real environment with longer durations and varying environmental factors. The influence of other factors such as the leaching of additives in the overall toxicity of tire rubber particles should be also considered.

Interacting effects of simulated eutrophication, temperature increase, and microplastic exposure on Daphnia.

The effects of multiple stressors are difficult to separate in field studies, and their interactions may be hard to predict if studied in isolation. We studied the effects of decreasing food quality (increase in cyanobacteria from 5 to 95% simulating eutrophication), temperature increase (by 3 °C), and microplastic exposure (1% of the diet) on survival, size, reproduction, and fatty acid composition of the model freshwater cladoceran Daphnia magna. We found that food quality was the major driver of Daphnia responses. When the amount of cyanobacteria increased from 5 to 95% of the diet, there was a drastic decrease in Daphnia survival (from 81 ± 15% to 24 ± 21%), juvenile size (from 1.8 ± 0.2 mm to 1.0 ± 0.1 mm), adult size (from 2.7 ± 0.1 mm to 1.1 ± 0.1 mm), and reproduction (from 13 ± 5 neonates per surviving adult to 0), but the decrease was not always linear. This was most likely due to lower availability of lipids, eicosapentaenoic acid (EPA), and sterols from the diet. Microplastic exposure did not affect Daphnia survival, size, or reproduction. Food quality had an interactive effect with temperature on fatty acid content of Daphnia. Total fatty acid content of Daphnia was almost 2-fold higher at 20 °C than at 23 °C when fed 50% cyanobacteria. This may have implications for higher trophic level consumers, such as fish, that depend on zooplankton for energy and essential lipids. Our findings suggest that as proportions of cyanobacteria increase, in tandem with water temperatures due to climate change, fish may encounter fewer and smaller Daphnia with lower lipid and EPA content.

The Influence of Solar Power Plants on Microclimatic Conditions and the Biotic Community in Chilean Desert Environments.

The renewable energy sector is growing at a rapid pace in northern Chile and the solar energy potential is one of the best worldwide. Therefore, many types of solar power plant facilities are being built to take advantage of this renewable energy resource. Solar energy is considered a clean source of energy, but there are potential environmental effects of solar technology, such as landscape fragmentation, extinction of local biota, microclimate changes, among others. To be able to minimize environmental impacts of solar power plants, it is important to know what kind of environmental conditions solar power plants create. This study provides information about abiotic and biotic conditions in the vicinity of photovoltaic solar power plants. Herein, the influence of these power plants as drivers of new microclimate conditions and arthropods diversity composition in the Atacama Desert was evaluated. Microclimatic conditions between panel mounts was found to be more extreme than in the surrounding desert yet beneath the panels temperature is lower and relative humidity higher than outside the panel area. Arthropod species composition was altered in fixed-mount panel installations. In contrast, solar tracking technology showed less influence on microclimate and species composition between Sun and Shade in the power plant. Shady conditions provided a refuge for arthropod species in both installation types. For example, Dipterans were more abundant in the shade whereas Solifugaes were seldom present in the shade. The presented findings have relevance for the sustainable planning and construction of solar power plants.

Effects of Activated Carbon on PCB Bioaccumulation and Biological Responses of Chironomus riparius in Full Life Cycle Test.

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.

Exposure protocol for ecotoxicity testing of microplastics and nanoplastics.

Despite the increasing concern about the harmful effects of micro- and nanoplastics (MNPs), there are no harmonized guidelines or protocols yet available for MNP ecotoxicity testing. Current ecotoxicity studies often use commercial spherical particles as models for MNPs, but in nature, MNPs occur in variable shapes, sizes and chemical compositions. Moreover, protocols developed for chemicals that dissolve or form stable dispersions are currently used for assessing the ecotoxicity of MNPs. Plastic particles, however, do not dissolve and also show dynamic behavior in the exposure medium, depending on, for example, MNP physicochemical properties and the medium's conditions such as pH and ionic strength. Here we describe an exposure protocol that considers the particle-specific properties of MNPs and their dynamic behavior in exposure systems. Procedure 1 describes the top-down production of more realistic MNPs as representative of MNPs in nature and particle characterization (e.g., using thermal extraction desorption-gas chromatography/mass spectrometry). Then, we describe exposure system development for short- and long-term toxicity tests for soil (Procedure 2) and aquatic (Procedure 3) organisms. Procedures 2 and 3 explain how to modify existing ecotoxicity guidelines for chemicals to target testing MNPs in selected exposure systems. We show some examples that were used to develop the protocol to test, for example, MNP toxicity in marine rotifers, freshwater mussels, daphnids and earthworms. The present protocol takes between 24 h and 2 months, depending on the test of interest and can be applied by students, academics, environmental risk assessors and industries.

Responses of Lumbriculus variegatus to activated carbon amendments in uncontaminated sediments.

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.

On the borderline of dissolved and particulate organic matter: partitioning and bioavailability of polycyclic aromatic hydrocarbons.

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.

Optical Monitoring of Microplastics Filtrated from Wastewater Sludge and Suspended in Ethanol.

The abundance of microplastics (MPs) in the atmosphere, on land, and especially in water bodies is well acknowledged. In this study, we establish an optical method based on three different techniques, namely, specular reflection to probe the medium, transmission spectroscopy measurements for the detection and identification, and a speckle pattern for monitoring the sedimentation of MPs filtrated from wastewater sludge and suspended in ethanol. We used first Raman measurements to estimate the presence and types of different MPs in wastewater sludge samples. We also used microscopy to identify the shapes of the main MPs. This allowed us to create a teaching set of samples to be characterized with our optical method. With the developed method, we clearly show that MPs from common plastics, such as polypropylene (PP), polyethylene terephthalate (PET), polystyrene (PS), and polyethylene (PE), are present in wastewater sludge and can be identified. Additionally, the results also indicate that the density of the plastics, which influences the sedimentation, is an essential parameter to consider in optical detection of microplastics in complex natural environments. All of the methods are in good agreement, thus validating the optics-based solution.

Analysis of fullerene-C60 and kinetic measurements for its accumulation and depuration in Daphnia magna.

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.

Predicting the bioavailability of sediment-associated spiked compounds by using the polyoxymethylene passive sampling and tenax extraction methods in sediments from three river basins in Europe.

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.

Sex, age, and tissue specific accumulation of eight metals, arsenic, and selenium in the European hedgehog (Erinaceus europaeus).

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.

Temperature determines the rate at which retene affects trout embryos, not the concentration that is toxic.

The toxicity of waterborne retene (7-isopropyl-1-methyl phenanthrene) to post-hatch embryos of rainbow trout (Oncorhynchus mykiss) was assessed at 5 and 11 °C. Survival times of retene-exposed embryos were 70 % longer at 5 °C than at 11 °C, but survival times and LC50 s did not vary when time was expressed as degree-days (thermal units), i.e., at a common stage of development. The size of survivors decreased with increasing retene concentrations, but not with temperature. Retene did not bioconcentrate to any extent (bioconcentration factors < 2) at either temperature, indicating effective biotransformation by embryos. However, concentrations of retene metabolites were slightly higher at 5 °C, suggesting slower excretion rates than at 11 °C. The relative expression of cytochrome P450 proteins (CYP1A) did not vary with temperature but increased with retene concentration, as indicated by cyp1a mRNA concentrations. The induction of CYP1A protein by retene exposure was evident in the vasculature of eye, brain, heart, kidney, liver, gill, mouth, intestine, muscle, and yolk-sac. However, immunohistochemical staining was greater at 5 than at 11 °C for all tissues except liver and muscle. Overall, temperature effects on retene toxicity disappeared when the duration of embryo development and retene exposure were expressed as thermal units (degree-days). Temperature controlled the rate of embryo development and the rate of toxicity (time to a toxic endpoint), but not the concentrations that were toxic.

The influence of summer seasonal extremes on dissolved organic carbon export from a boreal peatland catchment: evidence from one dry and one wet growing season.

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.

Desorption and bioavailability of spiked pentabromo diphenyl ether and tetrachlorodibenzo(p)dioxin in contaminated sediments.

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.

How to preserve and handle fish liver samples to conserve RNA integrity.

As transcriptomic studies are becoming more and more common, it is important to ensure that the RNA used in the analyses is of good quality. The RNA integrity may be compromised by storage temperature or freeze-thaw cycles, but these have not been well studied in poikilothermic fishes. This work studied the effects of tissue storage time and temperature, and freeze-thaw cycles of tissue and extracted RNA on RNA integrity in brown trout (Salmo trutta L.) liver. The storage time and temperature had an effect on RNA integrity, but RNA suitable for quantitative reverse transcription PCR (RT-qPCR) (RIN > 7) was still obtained from samples preserved at - 20 °C for 6 months. Freeze-thaw cycles of tissue or RNA did not compromise the integrity of RNA. RNA degradation had an effect on RT-qPCR results, and the effect depended on gene. The RT-qPCR analysis of historical samples from a bleached kraft pulp mill effluent exposure in 1984 revealed no significant cyp1a induction. Recommendations are given for the preservation and handling procedures of samples designated for transcriptomic analyses.

Desorption of sediment-associated polychlorinated dibenzo-p-dioxins, dibenzofurans, diphenyl ethers and hydroxydiphenyl ethers from contaminated sediment.

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.

Hypoxia increases intensity of epidermal papillomatosis in roach Rutilus rutilus.

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.

Influence of sediment ingestion and exposure concentration on the bioavailable fraction of sediment-associated tetrachlorobiphenyl in oligochaetes.

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.