Espen Eek

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.

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.

Use of Life Cycle Assessments To Evaluate the Environmental Footprint of Contaminated Sediment Remediation

Ecological and human risks often drive the selection of remedial alternatives for contaminated sediments. Traditional human and ecological risk assessment (HERA) includes assessing risk for benthic organisms and aquatic fauna associated with exposure to contaminated sediments before and after remediation as well as risk for human exposure but does not consider the environmental footprint associated with implementing remedial alternatives. Assessment of environmental effects over the whole life cycle (i.e., Life Cycle Assessment, LCA) could complement HERA and help in selecting the most appropriate sediment management alternative. Even though LCA has been developed and applied in multiple environmental management cases, applications to contaminated sediments and marine ecosystems are in general less frequent. This paper implements LCA methodology for the case of the polychlorinated dibenzo-p-dioxins and -furans (PCDD/F)-contaminated Grenland fjord in Norway. LCA was applied to investigate the environmental footprint of different active and passive thin-layer capping alternatives as compared to natural recovery. The results showed that capping was preferable to natural recovery when analysis is limited to effects related to the site contamination. Incorporation of impacts related to the use of resources and energy during the implementation of a thin layer cap increase the environmental footprint by over 1 order of magnitude, making capping inferior to the natural recovery alternative. Use of biomass-derived activated carbon, where carbon dioxide is sequestered during the production process, reduces the overall environmental impact to that of natural recovery. The results from this study show that LCA may be a valuable tool for assessing the environmental footprint of sediment remediation projects and for sustainable sediment management.

The contribution of urban runoff to organic contaminant levels in harbour sediments near two Norwegian cities

The main aim of the present study was to compare the quality of particle emissions (urban runoff and settling particles in rivers and harbours) to the quality of top-layer bed sediments, for two Norwegian harbours (Oslo and Drammen). A sub-aim was to investigate whether non-industrial urban runoff contributed to the organotin load of sediments, apart from leaching from ship hulls. Time-integrated samples of stormwater runoff were obtained in an innovative manner, by sampling man-holes in the stormwater system. Settling particles were sampled with sediment traps. The study focused on PAHs, PCBs and organotin compounds. Contaminant levels were generally a factor of 2-10 (PAHs) and 3-30 (TBT) lower in emitted riverine and runoff particles than in top-layer bed sediments, except for PCBs in Oslo harbour (only 20-30% lower). Significant levels of tributyltin (TBT; median 140mug/kg) were shown in runoff particles, showing that TBT can also be emitted via urban sources, since the sampled man-holes were not in areas where dry-docking activities take place. Possible land-based TBT sources include long-lasting house paint and use of TBT as PVC stabilizer and timber preservative. Since there are ongoing emissions into the two studied harbour areas, it is concluded that the addition of an actively sorbing capping material such as activated carbon might be the best remediation alternative.

Diffusion of PAH and PCB from contaminated sediments with and without mineral capping; measurement and modelling

A novel laboratory microcosm test was developed to measure the diffusion of native PAHs and PCBs from sediments in the presence and absence of a capping layer. Diffusive flux of 15 PAHs and 7 PCBs from uncapped sediment from Oslo harbour was 3.8+/-0.9 microg m(-2)d(-1) and 0.010+/-0.003 microg m(-2)d(-1), respectively. The flux from sediments capped with 1cm mineral cap (crushed limestone or crushed gneiss (0-2mm)), observed during the first 410 d, was 3.5-7.3% of the flux from uncapped sediments. By measuring freely dissolved pore water concentrations of 10 PAHs the flux in the microcosm was modelled with steady state and transient diffusion models. The measured flux from uncapped sediment was 27-290% of modelled steady state flux. Good agreement was also found between the measured flux of pyrene from capped sediment and the flux modelled with the transient model when fitting only with the distribution coefficients for pyrene between the cap material and water (Kd_pyr). Fitted Kd_pyr, (210 and 23 l kg(-1) for limestone and gneiss, respectively) was in the same order of magnitude as K(d) calculated from organic carbon content in the cap materials (68 and 14 l kg(-1) respectively). Calculation of the efficiency of a hypothetical cap with 10 cm diffusion path shows that the increased diffusion path length alone can yield a flux reduction >99% through a strong increase in the stagnant diffusive boundary layer from <1 to 100mm.

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.

Field measurement of diffusional mass transfer of HOCs at the sediment-water interface.

The sediment to water diffusive flux of PAHs and PCBs was measured under field conditions with a novel infinite-sink benthic flux chamber that deployed semipermeable membrane devices (SPMD) as a sorbing material. Fluxes were measured before and after in situ capping of sediments in Oslo Harbour with clean clay. The fluxes of native pyrene and PCB 52 from uncapped contaminated sediment measured with the flux chamber were 0.3-1.6 microg m(-2) d(-1) and 2-8 ng m(-2) d(-1), respectively. Fluxes from the capped sediment were reduced by 93-97%. The in situ measured fluxes were compared to fluxes independently calculated from freely dissolved concentrations in pore water and overlying water, measured using equilibrium passive samplers, diffusive boundary layer (DBL) thickness, measured by an alabaster dissolution method and literature values of diffusion coefficients. Measured fluxes from the uncapped sediment agreed well with calculated fluxes, the median of the ratio of the measured flux over the calculated flux was 0.9 with an inter quartile range of 0.5-1.6.

Sorption of PAHs and PCBs to activated carbon: Coal versus biomass-based quality

The addition of activated carbon (AC) is an increasingly popular method for pollutant immobilization, and the AC material can be made of biomass or coal/fossil feedstock. The aim of the present study was to investigate whether there are differences between pollutant sorption to biomass and coal-based AC in the presence and absence of sediment. Through N(2) and CO(2) adsorption to probe surface area and pore size it was shown that the biomass-based AC had a stronger dominance of narrow pores in the size range 3.5-15Å than the anthracite-based material. In the absence of sediment, sorption isotherms for the probe compounds pyrene and PCB-101 showed stronger sorption for the biomass-based AC (logarithmic Freundlich coefficients 8.15 for pyrene; 9.91 for PCB-101) than for the anthracite-based one (logarithmic Freundlich coefficients 7.20 and 9.70, respectively). In the presence of sediment, the opposite trend was observed, with the stronger sorption for anthracite-based AC. Thus, the presence of competing and/or pore-blocking sediment constituents reduces sorption to a larger extent for biomass-derived AC (factor of 5 for pyrene to almost 100 for PCB-101) than for anthracite-based AC (no reduction for pyrene to factor of 5 for PCB-101). This difference is tentatively attributed to the difference in pore size distribution, narrow pores being more prone to clogging, and could have implications for remediation feasibility with AC from different sources.

In situ sediment treatment using activated carbon: a demonstrated sediment cleanup technology

This paper reviews general approaches for applying activated carbon (AC) amendments as an in situ sediment treatment remedy. In situ sediment treatment involves targeted placement of amendments using installation options that fall into two general approaches: 1) directly applying a thin layer of amendments (which potentially incorporates weighting or binding materials) to surface sediment, with or without initial mixing; and 2) incorporating amendments into a premixed, blended cover material of clean sand or sediment, which is also applied to the sediment surface. Over the past decade, pilot- or full-scale field sediment treatment projects using AC—globally recognized as one of the most effective sorbents for organic contaminants—were completed or were underway at more than 25 field sites in the United States, Norway, and the Netherlands. Collectively, these field projects (along with numerous laboratory experiments) have demonstrated the efficacy of AC for in situ treatment in a range of contaminated sediment conditions. Results from experimental studies and field applications indicate that in situ sequestration and immobilization treatment of hydrophobic organic compounds using either installation approach can reduce porewater concentrations and biouptake significantly, often becoming more effective over time due to progressive mass transfer. Certain conditions, such as use in unstable sediment environments, should be taken into account to maximize AC effectiveness over long time periods. In situ treatment is generally less disruptive and less expensive than traditional sediment cleanup technologies such as dredging or isolation capping. Proper site-specific balancing of the potential benefits, risks, ecological effects, and costs of in situ treatment technologies (in this case, AC) relative to other sediment cleanup technologies is important to successful full-scale field application. Extensive experimental studies and field trials have shown that when applied correctly, in situ treatment via contaminant sequestration and immobilization using a sorbent material such as AC has progressed from an innovative sediment remediation approach to a proven, reliable technology. Integr Environ Assess Manag 2015; 11:195–207.

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.