Jonas S. Gunnarsson

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.

Bioturbation-Driven Release of Buried PCBs and PBDEs from Different Depths in Contaminated Sediments

Bioturbation can remobilize previously buried contaminants, leading to an increased exposure of aquatic biota. The remobilization of buried polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) from three different sediment depth layers (2.0-2.5 cm, 5.0-5.5 cm, and 10.0-10.5 cm) was studied in a laboratory experiment with two benthic macrofauna species, the amphipod Monoporeia affinis and the polychaete Marenzelleria spp. Remobilization of PCBs and PBDEs was significantly higher in the presence of Marenzelleria spp. than in M. affinis treatments and controls (without macrofauna). The highest remobilization occurred from the most shallow layers (2.0-2.5 cm > 5.0-5.5 cm > 10.0-10.5 cm), but contaminants were remobilized due to bioturbation from layers down to at least 10 cm. Congeners with lower hydrophobicity were remobilized to a higher extent than more hydrophobic congeners. The contaminant distribution between the particulate and the dissolved phase in the water column depended on hydrophobicity and burial depth of the contaminant, with congeners from deeper layers displaying an increased distribution to the particulate phase. Release fluxes and sediment-to-water mass transfer coefficients (MTCs) show that bioturbation by the polychaete Marenzelleria spp. can lead to a significant remobilization of buried contaminants from Baltic Sea sediments.

Capping Efficiency of Various Carbonaceous and Mineral Materials for In Situ Remediation of Polychlorinated Dibenzo-p-dioxin and Dibenzofuran Contaminated Marine Sediments : Sediment-to-Water Fluxes and Bioaccumulation in Boxcosm Tests

The efficiency of thin-layer capping in reducing sediment-to-water fluxes and bioaccumulation of polychlorinated dibenzo-p-dioxins and dibenzofurans, hexachlorobenzene, and octachlorostyrene was investigated in a boxcosm experiment. The influence of cap thickness (0.5-5 cm) and different cap materials was tested using a three-factor experimental design. The cap materials consisted of a passive material (coarse or fine limestone or a marine clay) and an active material (activated carbon (AC) or kraft lignin) to sequester the contaminants. The cap thickness and the type of active material were significant factors, whereas no statistically significant effects of the type of passive material were observed. Sediment-to-water fluxes and bioaccumulation by the two test species, the surface-dwelling Nassarius nitidus and the deep-burrowing Nereis spp., decreased with increased cap thickness and with addition of active material. Activated carbon was more efficient than lignin, and a ~90% reduction of fluxes and bioaccumulation was achieved with 3 cm caps with 3.3% AC. Small increases in fluxes with increased survival of Nereis spp. indicated that bioturbation by Nereis spp. affected the fluxes.

Effects of eutrophication on contaminant cycling in marine benthic systems

Abstract Effects of inputs of organic matter were studied on bioavailability and cycling of hydrophobic organic contaminants (HOCs) in benthic ecosystems of the Baltic and Kattegat Seas. In laboratory experiments, effects of microalgae additions were studied on the bioaccumulation of HOCs (PCBs and PAHs) by the blue mussel Mytilus edulis, the brittle star Amphiura filiformis, and the polychaete Nereis diversicolor. Contrary to the equilibrium partitioning theory, bioaccumulation was proportional to the concentrations of algae and organic carbon. This was attributed to the high nutritional quality of the algal organic carbon and suggests that feeding rather than equilibrium partitioning governed bioaccumulation in these species. In the field, annual mass fluxes of PCBs in blue mussels and in brittle stars were estimated, as well as contaminant transfer to higher trophic levels. Our results suggest that: i) Eutrophication processes may contribute to increase HOC accumulation in benthic species. ii) Temporal variation in the quantity and quality of organic carbon needs to be considered when assessing contamination of benthic systems. iii) Macrofaunal feeding activities are important for the benthic-pelagic coupling of HOCs. iv) Bioturbation enhances the release of HOCs from sediment to overlying water.

Large-scale field study on thin-layer capping of marine PCDD/F-contaminated sediments in Grenlandfjords, Norway: physicochemical effects.

A large-scale field experiment on in situ thin-layer capping was carried out in the polychlorinated dibenzodioxin and dibenzofuran (PCDD/F) contaminated Grenlandsfjords, Norway. The main focus of the trial was to test the effectiveness of active caps (targeted thickness of 2.5 cm) consisting of powdered activated carbon (AC) mixed into locally dredged clean clay. Nonactive caps (targed thickness of 5 cm) consisting of clay without AC as well as crushed limestone were also tested. Fields with areas of 10,000 to 40,000 m(2) were established at 30 to 100 m water depth. Auxiliary shaken laboratory batch experiments showed that 2% of the applied powdered AC substantially reduced PCDD/F porewater concentrations, by >90% for tetra-, penta- and hexa-clorinated congeners to 60-70% for octachlorinated ones. In-situ AC profiles revealed that the AC was mixed into the sediment to 3 to 5 cm depth in 20 months. Only around 25% of the AC was found inside the pilot fields. Sediment-to-water PCDD/F fluxes measured by in situ diffusion chambers were significantly lower at the capped fields than at reference fields in the same fjord, reductions being largest for the limestone (50-90%) followed by clay (50-70%), and the AC + clay (60%). Also reductions in overlying aqueous PCDD/F concentrations measured by passive samplers were significant in most cases (20-40% reduction), probably because of the large size of the trial fields. The AC was less effective in the field than in the laboratory, probably due to prolonged sediment-to-AC mass transfer times for PCDD/Fs and field factors such as integrity of the cap, new deposition of contaminated sediment particles, and bioturbation. The present field data indicate that slightly thicker layers of limestone and dredged clay can show as good physicochemical effectiveness as thin caps of AC mixed with clay, at least for PCDD/Fs during the first two years after cap placement.

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.

Meiofauna reduces bacterial mineralization of naphthalene in marine sediment

The role of sediment-living meiofauna, benthic invertebrates smaller than 1000 μm such as nematodes and ostracods, on the mineralization of naphthalene, a common polycyclic aromatic hydrocarbon (PAH) in marine sediments, was studied in microcosms using radiorespirometry. A method to extract live meiofauna was developed and used in order to experimentally manipulate meiofauna abundance and group diversity. Higher abundances of meiofauna were found to significantly decrease naphthalene mineralization. Furthermore, a change in the bacterial community composition (studied using terminal restriction fragment length polymorphism) was also observed in presence of higher meiofauna abundance, as well as a lower number of cultivable naphthalene-degrading bacteria. The reduced mineralization of naphthalene and the altered bacterial community composition in the presence of increased meiofauna abundance is likely the result of top-down control by meiofauna. This study shows that higher abundances of meiofauna can significantly decrease the microbial mineralization of PAHs such as naphthalene and also significantly modify the bacterial community composition in natural marine sediments.

Influences of sedimentary organic matter quality on the bioaccumulation of 4‐nonylphenol by estuarine amphipods

Nonylphenol (NP) is a moderately persistent, hydrophobic chemical with endocrine-disrupting and acute narcotic effects in aquatic biota. Concern exists about the ultimate fate of NP in aquatic ecosystems and the potential for bioaccumulation by benthic biota from the sediment with the potential for further transfer to higher trophic levels. Our goals were to determine if benthic amphipods bioaccumulate significant amounts of NP from sediment and to determine how additions of organic matter influence NP bioaccumulation by amphipods. Estuarine sediment was spiked with 14C-NP and enriched with two types of organic carbon (OC) sources of different nutritional qualities. Macrophytic algae (Ulva species) were used as a labile and nutritious OC source. Wood lignins were used as a refractory and low-nutrition OC source. Nonylphenol bioaccumulation was measured in Eohaustorius estuarius, Grandidierella japonica, and Corophium salmonis after 16 d of exposure. Nonylphenol accumulation was inversely proportional to OC quantity, but was unaffected by OC nutritional quality. Significant differences were found in the accumulation patterns between the three amphipod species. Mean biota-sediment accumulation factors ranged from 8.1 to 33.9 in E. estuarius, from 4.6 to 17.2 in G. japonica, and averaged 7.1 in male C. salmonis and 16.0 in female C. salmonis. These accumulation factors indicate that estuarine amphipods could constitute an important source of NP to higher trophic levels, such as juvenile fish.

Interactions between eutrophication and contaminants. I. Principles, experimental design and synthesis

Abstract In marine environments influenced by human activities, the sea-bed is a major recipient of both contaminants and organic matter. Deposition and recycling of contaminants from bottom sediments may be affected by the eutrophication status of the area. Contaminants and eutrophication factors may also interact to affect bioaccumulation as well as the growth, health and reproduction of benthic organisms. Consequently, from an environmental management point of view, these interactions should be considered when decisions are made about input of contaminants and organic matter to the aquatic environment. In order to elucidate interaction patterns between eutrophication and contaminants, radio-labelled contaminants were applied in a large scale experiment performed at Marine Research Station Solbergstrand, situated by the Oslofjord, Norway. The continous flow through experiment was performed in glass aquaria containing three sediment-dwelling species ( Abra alba, Nereis diversicolor and Amphiura filiformis ) placed in marine clay sediments. Blue mussels ( Mytilus edulis ) were kept in separate downstream aquaria and exposed to the out-flowing water from the sediment aquaria. In 12 contaminated aquaria the sediment was spiked with 203 Hg (0.23 mg Hg kg −1 dry sediment), 109 Cd (5 mg Cd kg −1 ) and 14 C-benzo[ a ]pyrene (1 mg BaP kg −1 ). In 12 organically enriched aquaria, phytoplankton (2 mg C kg −1 dry sediment) was initially mixed into the sediment and two months later another batch corresponding to 20 g C m −2 was added to the aquaria. Finally, the concentration of oxygen was continuously lowered from 7–9 mg O 2 l −1 in 12 well-oxygenated aquaria to 2.4–3.5 mg O 2 l −1 in 12 low-oxic aquaria by purging the source water with nitrogen. Allowing three replicate aquaria for each treatment, all combinations of the two levels (high/low) of the three factors (contaminants, oxygen availability and carbon load) could be tested in a factorial design using 24 aquaria. Sulphide ion activies were continuously recorded by Ag|AgS electrodes in the sediments and overlying water, and redox potentials were measured by Pt-electrodes inserted in the sediment. There were only minor changes in redox and sulphide potentials during the experimental period. Also, mortalities of the test species were negligible in all aquaria. After an experimental period of three months, the concentration of contaminants was quantified in sediments, porewater and biota using beta/gamma emission from the isotopes. Effects of the treatments on sediment-dwelling invertebrates were assessed using growth ( Nereis, Abra and Amphiura ), arm regeneration ( Amphiura ) and biomarker responses. In this paper (paper I) the principles and hypotheses for studying interactions between organic loading and contaminants are outlined as well as the experimental design. The results from the experiment are presented in three separate papers (papers II–IV) elsewhere in this volume. A short synthesis is presented in this paper, comparing the conclusions from the individual studies.

Influence of contaminant burial depth on the bioaccumulation of PCBs and PBDEs by two benthic invertebrates (Monoporeia affinis and Marenzelleria spp.)

The bioaccumulation of buried polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) added to specific depths in sediment (2.0-2.5, 5.0-5.5 and 10.0-10.5cm) was studied in two infaunal species with similar feeding habits (surface deposit-feeders) but different bioturbation modes. The deep-burrowing polychaetes Marenzelleria spp. (Mz) displayed up to 36 times higher tissue concentrations of buried (spiked) contaminants than the surface-dwelling biodiffusing amphipod Monoporeia affinis. The differences in bioaccumulation were most pronounced for less hydrophobic contaminants due to the bioirrigating activity of Mz. Contaminants buried at shallow depths displayed higher accumulation than more deeply buried contaminants. In contrast, the bioaccumulation of unspiked (native) contaminants with a uniform vertical distribution in the sediment was similar between the species. For Mz, the BSAFs increased with increased K(OW) for the uniformly distributed contaminants, but decreased for the buried contaminants, which indicates that the dominant uptake routes of the buried contaminants can differ from the uniformly distributed contaminants. The surface sediment concentration of buried contaminants increased in Mz treatments, showing that Mz bioturbation can remobilize historically buried contaminants to the biologically active surface layer and increase the exposure for surface-dwelling species.