Amy M.P. Oen

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.

Bioaccumulation of native polycyclic aromatic hydrocarbons from sediment by a polychaete and a gastropod: freely dissolved concentrations and activated carbon amendment.

The present paper describes a study on the bioaccumulation of native polycyclic aromatic hydrocarbons (PAHs) from three harbors in Norway using the polychaete Nereis diversicolor and the gastropod Hinia reticulata. First, biota-sediment accumulation factors (BSAFs) were measured in laboratory bioassays using the original sediments. Median BSAFs were 0.004 to 0.01 kg organic carbon/kg lipid (10 PAHs and 6 organism-sediment combinations), which was a factor of 89 to 240 below the theoretical BSAF based on total sediment contents (which is approximately one). However, if BSAFs were calculated on the basis of measured freely dissolved PAH concentrations in the pore water (measured with polyoxymethylene passive samplers), it appeared that these BSAFfree values agreed well with the measured BSAFs, within a factor of 1.7 to 4.3 (median values for 10 PAHs and six organism-sediment combinations). This means that for bioaccumulation, freely dissolved pore-water concentrations appear to be a much better measure than total sediment contents. Second, we tested the effect of 2% (of sediment dry wt) activated carbon (AC) amendments on BSAE The BSAFs were significantly reduced by a factor of six to seven for N. diversicolor in two sediments (i.e., two of six organism-sediment combinations), whereas no significant reduction was observed for H. reticulata. This implies that either site-specific evaluations of AC amendment are necessary, using several site-relevant benthic organisms, or that the physiology of H. reticulata caused artifactually high BSAF values in the presence of AC.

In Situ Measurement of PCB Pore Water Concentration Profiles in Activated Carbon-Amended Sediment Using Passive Samplers

Vertical pore water profiles of in situ PCBs were determined in a contaminated mudflat in San Francisco Bay, CA, 30 months after treatment using an activated carbon amendment in the upper layer of the sediment. Pore water concentrations were derived from concentrations of PCBs measured in two passive samplers; polyethylene (PE, 51 μm thick) and polyoxymethylene (POM, 17 μm thick) at different sediment depths. To calculate pore water concentrations from PCB contents in the passive samplers, an equilibrium approach and a first-order uptake model were applied, using five performance reference compounds to estimate pore water sampling rates. Vertical pore water profiles showed good agreement among the measurement and calculation methods with variations within a factor of 2, which seems reasonable for in situ measurements. The close agreements of pore water estimates for the two sampler materials (PE and POM) and the two methods used to translate uptake in samplers to pore water concentrations demonstrate the robustness and suitability of the passive sampling approach. The application of passive samplers in the sediment presents a promising method for site monitoring and remedial treatment evaluation of sorbent amendment or capping techniques that result in changes of pore water concentrations in the sediment subsurface.

Sorption of organic compounds to fresh and field-aged activated carbons in soils and sediments.

Activated carbon (AC) amendment to polluted sediment or soil is an emerging in situ treatment technique that reduces freely dissolved porewater concentrations and subsequently reduces the ecological and human health risk of hydrophobic organic compounds (HOCs). An important question is the capacity of the amended AC after prolonged exposure in the field. To address this issue, sorption of freshly spiked and native HOCs to AC aged under natural field conditions and fresh AC amendments was compared for one soil and two sediments. After 12-32 months of field aging, all AC amendments demonstrated effectiveness for reducing pore water concentrations of both native (30-95%) and spiked (10-90%) HOCs compared to unamended sediment or soil. Values of K(AC) for field-aged AC were lower than freshly added AC for spiked HOCs up to a factor of 10, while the effect was less for native HOCs. The different behavior in sorbing native HOCs compared to freshly spiked HOCs was attributed to differences in the sorption kinetics and degree of competition for sorption sites between the contaminants and pore-clogging natural organic matter. The implications of these findings are that amended AC can still be effective in sorbing additional HOCs some years following amendment in the field. Thus, a certain level of long-term sustainability of this remediation approach is observed, but conclusions for decade-long periods cannot be drawn solely based on the present study.

Assessment of field‐related influences on polychlorinated biphenyl exposures and sorbent amendment using polychaete bioassays and passive sampler measurements

Field-related influences on polychlorinated biphenyl (PCB) exposure were evaluated by employing caged deposit-feeders, Neanthes arenaceodentata, along with polyoxymethylene (POM) samplers using parallel in situ and ex situ bioassays with homogenized untreated or activated carbon (AC) amended sediment. The AC amendment achieved a remedial efficiency in reducing bioaccumulation by 90% in the laboratory and by 44% in the field transplants. In situ measurements showed that PCB uptake by POM samplers was greater for POM placed in the surface sediment compared with the underlying AC amendment, suggesting that tidal exchange of surrounding material with similar PCB availability as untreated sediment was redeposited in the cages. Polychlorinated biphenyls bioaccumulation with caged polychaetes from untreated sediment was half as large under field conditions compared with laboratory conditions. A biodynamic model was used to confirm and quantify the different processes that could have influenced these results. Three factors appeared most influential in the bioassays: AC amendment significantly reduces bioavailability under laboratory and field conditions; sediment deposition within test cages in the field partially masks the remedial benefit of underlying AC-amended sediment; and deposit-feeders exhibit less PCB uptake from untreated sediment when feeding is reduced. Ex situ and in situ experiments inevitably show some differences that are associated with measurement methods and effects of the environment. Parallel ex situ and in situ bioassays, passive sampler measurements, and quantifying important processes with a model can tease apart these field influences.

How quality and quantity of organic matter affect polycyclic aromatic hydrocarbon desorption from Norwegian harbor sediments

The desorption behavior of phenanthrene, pyrene, and benzo[a]pyrene was investigated for three Norwegian harbor sediments and their respective particle size fractions using the Tenax desorption method. Rate constants for rapidly, slowly, and very slowly desorbing fractions were on the order of 10(-1), 10(-2) to 10(-4), and 10(-4) to 10(-6)/h, respectively. Relatively small amounts were present in the rapidly desorbing fractions (F(rapid): < 6% for phenanthrene, 3-19% for pyrene, and 1-12% for benzo[a]pyrene). With the exception of benzo[a]pyrene, these F(rapid) values were generally lower than median F(rapid) values obtained from more than 100 literature values for native polycyclic aromatic hydrocarbons (PAHs) (22% for phenanthrene, 29% for pyrene, and 8% for benzo[a]pyrene). To understand which parameters influence PAH desorption, relations between desorption behavior and the sediment characteristics were investigated. A significant positive correlation was found between the extent of slow and very slow desorption and the ratios of black carbon to total organic carbon, as well as the temperature at which 50 and 90%, respectively, of the organic matter was oxidized, as obtained from oxidation-only Rock Eval analysis. Thus, black carbon-bound PAHs probably desorb slowly and very slowly. Furthermore, significant positive correlations between desorption behavior and the average particle size were observed, which could be explained by retarded intraparticle diffusion.

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.

Influence of historical industrial epochs on pore water and partitioning profiles of polycyclic aromatic hydrocarbons and polychlorinated biphenyls in Oslo Harbor, Norway, sediment cores

Contaminant levels in urban harbor sediments vary with contaminant emission levels, sedimentation rates, and sediment resuspension processes such as propeller wash. Levels of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) are decreasing in many urban harbors, as heavily contaminated sediments that accumulated during past decades are being buried by less-contaminated sediments. However, PAHs and PCBs remain a concern in areas where burial is slow or resuspension processes re-expose heavily contaminated older layers. Chronostratigraphic sediment core studies typically characterize contaminant level histories by using total sediment concentrations, C(sed) , and do not determine the freely dissolved porewater concentrations, C(pw) , which provide a better measure of bioavailability. Here both C(sed) and C(pw) profiles were established for PAHs and PCBs in dated sediment cores from diverse areas of Oslo Harbor, Norway. Sediment-porewater partitioning profiles were established alongside profiles of various sorbing carbonaceous phases, including total organic carbon (TOC), black carbon, and diverse carbonaceous geosorbents identified by petrographic analysis. Stratigraphic trends in carbonaceous phases and C(sed) could be associated with different industrial epochs: hydropower (post-1960, approximately), manufactured gas (∼1925-1960), coal (∼1910-1925), and early industry (∼1860-1910). Partitioning was highly variable and correlated best with the TOC. Hydropower-epoch sediments exhibit decreasing C(sed) with time and a relatively strong sorption capacity compared with the manufactured-gas epoch. Sediments from the manufactured-gas epoch exhibit substantial PAH and metal contamination, large amounts of coke and char, and a low sorption capacity. Reexposure of sediments of this epoch increases risks to local benthic species. Implications on natural recovery as a sediment management strategy are discussed.

Strategic Framework for Managing Sediment Risk at the Basin and Site-Specific Scale

Publisher Summary This chapter presents strategic framework for managing sediment risk at the basin and site-specific scale. The excerpts are from the regulations made and implemented in European Union. Effective and sustainable management strategies focus on the entire sediment cycle, rather than on one site at a time. The mission of SedNet is to be a European network for environmentally, socially and economically viable practices of sediment management at the river basin scale. One of the main aims of SedNet is to develop a document containing recommendations in the form of guidance and key-solutions for integrated, sustainable sediment management (SSM), from local to river basin scale (SSM Guide). Second, in line with the new regulatory focus of the Water Framework Directive (WFD), SedNet addresses river basin-wide management and basin-wide sediment management, in particular. Third, although most guidance documents have been generated for specific aspects of sediment management, such as dredged material disposal or environmental management a basin-scale approach must integrate various sediment goals and provide a universal framework.

Sediment Management Objectives and Risk Indicators

Publisher Summary This chapter discusses different aspects of social and societal driving forces and objectives in sediment risk management and introduces indicators as triggers for selecting management options on a site-specific basis, as well as on a larger scale. The guiding risk management objective is to reduce risk posed by contaminated sediments to humans and ecological receptors to a level deemed tolerable by society and to control and monitor sediment quality and ensure public communication, with the final aim of complying with the European Water Framework Directive (WFD) and Habitats Directive. This comprehensive statement implies a number of factors: (1) The principal issue of the management objective is risk reduction. (2) Controlling and monitoring are part of risk management. (3) Desirable levels of risk are determined by society – this implies that, e.g. environmental protection limits may not be enforced if the stakeholders opt against it. (4) Public communication and involvement is an essential part of risk management strategies, because not only this is legally required by various European Conventions, but also because experience shows that risk tolerance decreases with limited access to information and with the feeling of being powerless and controlled by external forces. Therefore, meeting regulatory criteria is one of four specific objectives relevant to sediment risk management, in addition to maintaining economic viability, ensuring environmental quality and development of the natural environment, and securing quality of human life.