Persistent organic pollutants and related biological responses measured in coastal fish using chemical and biological screening methods.

The aim of this study was to investigate the spatial distribution, levels of dioxin-like compounds (DLC), and biological responses in two fish species. The viviparous eelpout (Zoarces viviparus) was collected from various locations in the Baltic Sea and in fjords of Kattegat and Skagerrak, while shorthorn sculpin (Myoxocephalus scorpius) was obtained at the polychlorinated biphenyl (PCB) polluted site in North West Greenland. Significant differences were detected both in contaminant levels and relative contributions from either polychlorinated dibenzodioxins (PCDD) or polychlorinated dibenzofurans (PCDF or furans) and mono-ortho- and non-ortho (coplanar) polychlorinated biphenyls (dl-PCB). Fish from the eastern Baltic Sea generally displayed higher contributions from PCDD/F compared to dl-PCB, whereas dl-PCB were generally predominated in fish from Danish, Swedish, and German sites. Levels of dl-PCB in muscle tissues were above OSPAR environmental assessment criteria (EAC) for PCB118, indicating a potential risk of adverse biological effects in the ecosystem, whereas levels of the total WHO-TEQs were below threshold for sea food suggesting limited risks for humans. No significant relationships between levels of DLC (expressed as WHO-TEQ), and biological responses such as the induction of CYP1A enzymatic activity and fry reproductive disorders were observed in eelpout. No marked relationship between WHO-TEQ and combined biological aryl hydrocarbon receptor-mediated transactivity (expressed as AhR-TEQ) was noted. However, there was a positive correlation between polycyclic aromatic hydrocarbon (PAH) metabolites and induction of CYP1A activity, suggesting that PAH exhibited greater potential than DLC to produce biological effects in eelpout from the Baltic Sea.

Aerosol-water distribution of PCDD/Fs and PCBs in the Baltic Sea region.

Atmospheric deposition is a major pathway of PCDD/Fs to the Baltic Sea. We studied the aerosol-water distribution for aerosols collected close to the Baltic Sea in order to investigate the availability of pollutants sorbed to aerosols deposited on water. Aerosols were analyzed for both total concentration (Soxhlet extraction) and the freely dissolved water concentration (extraction with 17-µm polyoxymethylene equilibrium passive samplers). Concentrations of PCDD/F and sum PCB-7 in aerosols were 65-1300 pg/g dw TEQ and 22-100 ng/g dw, respectively. Organic carbon (OC)-normalized aerosol-water distribution ratios (K(aer-water,OC)) were consistently lower (factor 2-60) than previously determined sediment organic carbon-water distribution ratios (K(sed,OC)). Hence PCDD/Fs and PCBs entering the Baltic Sea through aerosol deposition seem to be more available for desorption to the water phase than PCDD/Fs and PCBs sorbed to sediment. Further, we investigated whether aerosol-water distribution may be predicted from the air-aerosol partitioning constant multiplied by the Henry's Law constant. This proposed model for aerosol-water distribution underestimated measured values for PCBs by factors of 1-17 and for PCDD/Fs by more than a factor 10. These findings can be used to improve future fate modeling of PCBs and PCDD/Fs in marine environments and specifically the Baltic Sea.

Remediation of contaminated marine sediment using thin-layer capping with activated carbon--a field experiment in Trondheim harbor, Norway.

In situ amendment of contaminated sediments using activated carbon (AC) is a recent remediation technique, where the strong sorption of contaminants to added AC reduces their release from sediments and uptake into organisms. The current study describes a marine underwater field pilot study in Trondheim harbor, Norway, in which powdered AC alone or in combination with sand or clay was tested as a thin-layer capping material for polycyclic aromatic hydrocarbon (PAH)-contaminated sediment. Several novel elements were included, such as measuring PAH fluxes, no active mixing of AC into the sediment, and the testing of new manners of placing a thin AC cap on sediment, such as AC+clay and AC+sand combinations. Innovative chemical and biological monitoring methods were deployed to test capping effectiveness. In situ sediment-to-water PAH fluxes were measured using recently developed benthic flux chambers. Compared to the reference field, AC capping reduced fluxes by a factor of 2-10. Pore water PAH concentration profiles were measured in situ using a new passive sampler technique, and yielded a reduction factor of 2-3 compared to the reference field. The benthic macrofauna composition and biodiversity were affected by the AC amendments, AC + clay having a lower impact on the benthic taxa than AC-only or AC + sand. In addition, AC + clay gave the highest AC recoveries (60% vs 30% for AC-only and AC + sand) and strongest reductions in sediment-to-water PAH fluxes and porewater concentrations. Thus, application of an AC-clay mixture is recommended as the optimal choice of the currently tested thin-layer capping methods for PAHs, and more research on optimizing its implementation is needed.

Remobilization of polychlorinated biphenyl from Baltic Sea sediment: comparing the roles of bioturbation and physical resuspension.

The release of a [¹4C]-labeled tri-chloro-biphenyl compound ([¹4C]PCB 32) from sediment to water was quantified weekly in a 30 d microcosm experiment with re-circulating water. Two modes of bioturbation-driven PCB release: 1) bioturbation by the amphipod Monoporeia affinis (a particle bio-diffuser) and 2) bioturbation by the polychaete Marenzelleria sp. (a bio-irrigator) were compared to the PCB release caused by physical sediment resuspension generated by a motor-driven paddle, used twice a week. Bioturbation by the amphipod M. affinis caused a significantly higher remobilization of both particle-associated (PCBpart) and dissolved PCB (PCBdiss) than the other treatments. Bioturbation by Marenzelleria sp. and physical resuspension caused a similar release of PCBdiss despite a significantly higher amount of total suspended solids in the water column after physical resuspension. In all treatments, the release of PCBdiss was more than one order of magnitude higher than of PCBpart, indicating a significant potential exposure route to pelagic organisms, such as fish, of the most bioavailable PCB form. Calculated mass transfer coefficients (0.3-1.3 cm/d) correspond to previously reported values for tri-chlorinated PCBs. Results from this experiment indicate that biological reworking of sediments can be just as, or even more, important than physical resuspension for the remobilization of sediment-bound contaminants.

Effects of settling organic matter on the bioaccumulation of cadmium and BDE-99 by Baltic Sea benthic invertebrates.

Settling organic matter (OM) is the major food source for heterotrophic benthic fauna. The high sorption affinity of many contaminants for OM implies that OM can influence both the distribution and bioavailability of contaminants. Here, we experimentally examine the role of settling OM of various nutritional qualities on the bioaccumulation of cadmium and the flame retardant BDE-99 by three benthic invertebrates; Macoma balthica, Monoporeia affinis and Marenzelleria sp. Contaminants were associated with three types of OM; a microalgae (Tetraselmis spp.), lignin and sediment. Bioaccumulation of Cd was proportional to OM nutritional quality for all three species, and was species-specific in the order Marenzelleria>M. balthica>M. affinis. BDE-99 bioaccumulation was highest in the treatment with the most nutritious OM (Tetraselmis). Consequently, both benthic species composition and the nutritive value of organic matter settling to the seafloor can have a substantial effect on the bioaccumulation of both metals and organic contaminants.

Capping in situ with activated carbon in Trondheim harbor (Norway) reduces bioaccumulation of PCBs and PAHs in marine sediment fauna.

Three types of thin-layer caps with activated carbon (AC) were tested in situ in experimental plots (10 × 10 m) in Trondheim harbor, Norway, using AC + clay, AC-only or AC + sand. One year after capping, intact sediment cores were collected from the amended plots for ex situ surveys of the capping efficiency in reducing the PAH and PCB aqueous concentrations and bioaccumulation by the polychaete Hediste diversicolor and the clam Abra nitida. Reduced pore water concentrations were observed in all AC treatments. The capping efficiency was in general AC + clay > AC-only > AC + sand. AC + clay reduced bioaccumulation of PAH and PCB congeners between 40% and 87% in the worms and between 67% and 97% in the clams. Sediment capped with AC-only also led to reduced bioaccumulation of PCBs, while AC + sand showed no reduction in bioaccumulation. Thus the best thin-layer capping method in this study was AC mixed with clay.

Temporal trends in dioxins (polychlorinated dibenzo-p-dioxin and dibenzofurans) and dioxin-like polychlorinated biphenyls in Baltic herring (Clupea harengus).

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyl (dl-PCBs) concentrations in Baltic herring (Clupea harengus) have been relatively stable since the mid to late 1990s. It is unclear why concentrations in Baltic herring are not following the observed decreases in other environmental matrices. Here, changes in long-term temporal trends in Baltic herring were examined. A number of biological variables were examined alongside the temporal trends to investigate whether fish biology e.g., growth (length, weight, age), lipid content, reproductive phase or fishing date may provide an explanation for the temporal trends observed. Significant (p<0.05) decreasing trends were observed for PCDD/F toxic equivalents (TEQPCDD/F) at three of the four sites (lipid weight (lw) and wet weight (ww), Swedish west coast lw only); however, other TEQ values e.g., TEQPCDD, TEQPCDF, TEQdl-PCB, TEQPCDD/F+dl-PCB were inconsistent, decreasing at some sites but not others. In the most recent 10 years of data, fewer significant decreases were seen overall. Over the examined time period, significant decreases (Bothnian Bay, p<0.01, southern Baltic Proper, p<0.02) and increases (Swedish west coast, p<0.02) in lipid content, growth dilution or lack thereof, and significant changes in age were observed. However herring were not randomly selected which biases this result. Continual efforts to decrease PCDD/F and dl-PCB emissions and to locate/reduce hotspots are necessary, while bearing in mind that herring biology may be impeding faster decreases of these chemicals.

Eelpout (Zoarces viviparus) in marine environmental monitoring.

The implementation of the EU Marine Strategy Framework Directive necessitates the development of common criteria and methodological standards for marine environmental monitoring and assessment across Europe. Eelpout (Zoarces viviparus) is proposed as a key indicator organism in the Baltic and North Sea regions. This benthic fish species is widely used in ecotoxicological studies and as a bioindicator of local pollution due to its stationary behavior. Eelpout is included in the environmental monitoring program of several Baltic States, covering both chemical and biological effects measurements, and samples have been archived in environmental specimen banks for >15 years. A method for evaluating the frequency of larval aberrations has been suggested as a standardized assessment tool. The large scientific knowledge-base and considerable experience of long-term chemical and biological effects monitoring and specimen banking, make eelpout a suitable species for the assessment of Good Environmental Status in the Baltic and North Seas.

Effects of the antibiotic ciprofloxacin on the bacterial community structure and degradation of pyrene in marine sediment.

The ecological consequences of antibiotics in the aquatic environment have been an issue of concern over the past years due to the potential risk for negative effects on indigenous microorganisms. Microorganisms provide important ecosystem services, such as nutrient recycling, organic matter mineralization and degradation of pollutants. In this study, effects of exposure to the antibiotic ciprofloxacin on the bacterial diversity and pollutant degradation in natural marine sediments were studied using molecular methods (T-RFLP) in combination with radiorespirometry. In a microcosm experiment, sediment spiked with (14)C-labelled pyrene was exposed to five concentrations of ciprofloxacin (0, 20, 200, 1000 and 2000 microgL(-1)) in a single dose to the overlying water. The production of (14)CO(2) (i.e. complete mineralization of pyrene) was measured during 11 weeks. Sediment samples for bacterial community structure analysis were taken after 7 weeks. Results showed a significant dose-dependent inhibition of pyrene mineralization measured as the total (14)CO(2) production. The nominal EC(50) was calculated to 560 microgL(-1), corresponding to 0.4 microg/kg d.w. sediment. The lowest effect concentration on the bacterial community structure was 200 microgL(-1), which corresponds to 0.1 microg/kg d.w. sediment. Our results show that antibiotic pollution can be a potential threat to both bacterial diversity and an essential ecosystem service they perform in marine sediment.

Bioturbation-driven release of organic contaminants from Baltic Sea sediments mediated by the invading polychaete Marenzelleria neglecta.

Baltic Sea sediments are among the world's most polluted regarding eutrophication and contamination. Eutrophication-induced hypoxia has caused depletion of bioturbating macrofauna in vast areas, producing laminated sediments. We investigated if reoxygenation and colonization by the invading deep-burrowing polychaete Marenzelleria neglecta may cause an augmented contaminant release from Baltic Sea sediments. Intact laminated sediment cores were exposed either to in situ hypoxia, reoxygenation, or reoxygenation combined with bioturbating M. neglecta. The release fluxes of particle-associated (N(Pat)) and dissolved (N(Diss)) PCBs and chlorinated pesticide residues (POPs) were quantified (GC-ECD) after 85 d along with contaminant concentrations in sediment and biota. Lavoisier-based mass transfer coefficients (Kf) were calculated from N(Diss). Sediment contaminant concentrations were high (sigmaPCB7: 42-52 ng g(sediment)(-1) dw) due to emissions from Stockholm. N(Diss) always exceeded N(Part) by an order of magnitude. Bioturbation enhanced N(Diss) and Kf from hypoxic sediments 0.7-3 times while reoxygenation alone had no significant effect. M. neglecta accumulated low amounts of contaminants but significantly stimulated aquatic release of bioavailable sequestered contaminants. Bioturbation should be included in aquatic contaminant fate models. We advise to consider quiescent pollutant sources and possible ecological shifts when aiming to restore eutrophicated aquatic environments.