Gijs D. Breedveld

The sorption and desorption of phosphate-P, ammonium-N and nitrate-N in cacao shell and corn cob biochars.

The sorption of PO4-P, NH4-N and NO3-N to cacao shell and corn cob biochars produced at 300-350°C was quantified. The biochars were used; (i) as received (unwashed), (ii) after rinsing with Millipore water and (iii) following leaching with Millipore water. In addition to sorption, desorption of PO4-P from the unwashed biochars was quantified. There was no sorption of PO4-P to either washed or rinsed biochars, but following leaching, both biochars adsorbed PO4-P and distribution coefficients (Kd L kg(-1)) were very similar for both materials (10(1.1±0.5) for cacao shell biochar and 10(1.0±0.2) for corn cob biochar). The BET surface area and micropore volume increased 80% and 60% for the cacao shell and corn cob biochars following leaching. After 60 d, 1483±45 mg kg(-1) and 172±1 mg kg(-1) PO4-P was released from the cacao shell and corn cob biochars. NH4-N was sorbed by both unwashed biochars, albeit weakly with Kd values around 10(2) L kg(-1). We speculate that NH4-N could bind via an electrostatic exchange with other cationic species on the surface of the biochar. There was no significant release or sorption of NO3-N from or to either of the biochars.

Field testing of equilibrium passive samplers to determine freely dissolved native polycyclic aromatic hydrocarbon concentrations

Equilibrium passive samplers are promising tools to determine freely dissolved aqueous concentrations (C(W,free)) of hydrophobic organic compounds. Their use in the field, however, remains a challenge. In the present study on native polycyclic aromatic hydrocarbons (PAHs) in Oslo Harbor, Norway, two different passive sampler materials, polyoxymethylene (POM; thickness, 55 microm [POM-55] and 500 microm [POM-500]) and polydimethylsiloxane (PDMS; thickness, 200 microm), were used to determine in the laboratory C(W,free) in sediment pore water (C(PW,free)), and the suitability of five passive samplers for determination of C(W,free) in overlying surface water was tested under field conditions. For laboratory determinations of C(PW,free), both POM-55 and PDMS turned out to be suitable. In the field, the shortest equilibrium times (approximately one month) were observed for POM-55 and PDMS (thickness, 28 microm) coatings on solid-phase microextraction fibers, with PDMS tubing as a good alternative. Low-density polyethylene (thickness, 100 microm) and POM-500 did not reach equilibrium within 119 d in the field. Realistic values were obtained for dissolved organic carbon-water partition coefficients in the field (approximately one log unit under log K(OW)), which strengthened the conclusion that equilibrium was established in field-exposed passive samplers. At all four stations, chemical activity ratios between pore water and overlying water were greater than one for all PAHs, indicating that the sediment was a PAH diffusion source and that sediment remediation may be an appropriate treatment for PAH contamination in Oslo Harbor.

Nutrient-limited biodegradation of PAH in various soil strata at a creosote contaminated site

The effects of nutrient addition on the in situ biodegradation of polycyclic aromatic hydrocarbons in creosote contaminated soil were studied in soil columns taken from various soil strata at a wood preserving plant in Norway. Three samples were used: one from the topsoil (0–0.5 m), one from an organic rich layer (2–2.5 m) and one from the sandy aquifer (4.5–5 m). The addition of inorganic nitrogen and phosphorous stimulated the degradation of polycyclic aromatic hydrocarbons (PAHs) in the top soil and the aquifer sand. These two soils, which differed strongly in contamination levels, responded similarly to nutrient addition with the corresponding degradation of 4-ring PAHs. The ratio between available nitrogen (N) and phosphorous (P) might explain the degree of degradation observed for the 4-ring PAHs. However, the degree of degradation of 3-ring PAHs did not significantly increase after nutrient addition. An increase in the respiration rate, after nutrient addition, could only be observed in the topsoil. In the aquifer sand, 4-ring PAH degradation was not accompanied by an increase in the respiration rate or the number of heterotrophic micro-organisms. PAH degradation in the organic layer did not respond to nutrient addition. This was probably due to the low availability of the contaminants for micro-organisms, as a result of sorption to the soil organic matter. Our data illustrate the need for a better understanding of the role of nutrients in the degradation of high molecular weight hydrocarbons for the successful application of bioremediation at PAH contaminated sites.

Persistence of the De-Icing Additive Benzotriazole at an Abandoned Airport

The environmental fate of many of the additives in the deicing agents used at airports is poorly understood. One and two years after deicing activities ceased, soil and groundwater samples were taken at an abandoned airport. Benzotriazole (BT), a corrosion and flame inhibitor, was found in low concentrations in soils along runways (mean 0.33 mg/kg), at a snow disposal site (0.66 mg/kg), as well as in sediments of a drainage ditch (13 mg/kg). Locally, high BT concentrations were found in the groundwater below the deicing pad, the regeneration plant and the snow disposal site (1.2 to 1100 μg/l). Methyl substituted triazoles or tolytriazoles (MeBT) were found in concentrations less than 10% of the BT concentration. Propylene glycol was not detected in soil samples and in only one of the groundwater samples. Microtox tests of the water samples revealed no acute toxic response, however a reduction in nitrification rate was observed (14–43%). The nitrification response could not be related directly to the BT concentration in the samples, although samples with a high BT concentration showed the largest reduction in nitrification rate. BT showed very little sorption in various soil matrices, only peat and compost with a high organic carbon content showed significant sorption. Sorption could be best described using a Freundlich isotherm. These results indicate a high mobility and possibly long persistence of BT in soil and groundwater, which may be attributed to the absence of microbial degradation of BT.

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.

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.

Assessing PAH and PCB emissions from the relocation of harbour sediments using equilibrium passive samplers

Large-scale dredging of contaminated sediments is taking place in the harbor of Oslo, Norway. The dredged sediment masses are transferred into a confined aquatic disposal facility (CAD) in a natural 70-m deep basin within the Oslofjord. Currently there is no established method to determine how much dissolved contaminants are released during relocation and deposition of these sediments. For this reason we tested the use of equilibrium passive samplers consisting of 55 microm thin polyoxymethylene (POM-55) for studying the release of freely dissolved and thus bioavailable PAHs and PCBs at the disposal site, and found this to be a suitable method. In order to use POM-55 for monitoring PCBs, it was necessary to measure their POM-55/water partition coefficients, which was also presented as part of this study. Elevated turbidity (average 4.1 mg l(-1)) was observed at one side of the basin where no natural sill exists. Analysis of POM-55 at this location before and after deposition revealed that there was an increase in freely dissolved concentrations (C(W,free)) during deposition by a factor 37.5 for PAHs and a factor of 2.9 for PCBs. In addition, during deposition phenanthrene-to-anthracene aqueous concentration ratios at this location (values of 3-4) were more similar to those of the deposited sediments (approximately 2) than to those of the CAD water prior to deposition (approximately 14). This was not observed for the other locations where a natural sill exists at approximately 30 m water depth. The POM-55 equilibrium passive samplers are here shown to be useful tools for measuring and understanding the dynamics involved in the release of dissolved contaminants during sediment relocation.

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.