Bioturbation and dissolved organic matter enhance contaminant fluxes from sediment treated with powdered and granular activated carbon.

Sediment amendment with activated carbon (AC) is a promising technique for in situ sediment remediation. To date it is not clear whether this technique sufficiently reduces sediment-to-water fluxes of sediment-bound hydrophobic organic chemicals (HOCs) in the presence of bioturbators. Here, we report polychlorobiphenyl (PCB) pore water concentrations, fluxes, mass transfer coefficients, and survival data of two benthic species, for four treatments: no AC addition (control), powdered AC addition, granular AC addition and addition and subsequent removal of GAC (sediment stripping). AC addition decreased mass fluxes but increased apparent mass transfer coefficients because of dissolved organic carbon (DOC) facilitated transport across the benthic boundary layer (BBL). In turn, DOC concentrations depended on bioturbator activity which was high for the PAC tolerant species Asellus aquaticus and low for AC sensitive species Lumbriculus variegatus. A dual BBL resistance model combining AC effects on gradients, DOC facilitated transport and biodiffusion was evaluated against the data and showed how the type of resistance differs with treatment and chemical hydrophobicity. Data and simulations illustrate the complex interplay between AC and contaminant toxicity to benthic organisms and how differences in species tolerance affect mass fluxes from sediment to the water column.

In situ treatment with activated carbon reduces bioaccumulation in aquatic food chains.

In situ activated carbon (AC) amendment is a new direction in contaminated sediment management, yet its effectiveness and safety have never been tested on the level of entire food chains including fish. Here we tested the effects of three different AC treatments on hydrophobic organic chemical (HOC) concentrations in pore water, benthic invertebrates, zooplankton, and fish (Leuciscus idus melanotus). AC treatments were mixing with powdered AC (PAC), mixing with granular AC (GAC), and addition-removal of GAC (sediment stripping). The AC treatments resulted in a significant decrease in HOC concentrations in pore water, benthic invertebrates, zooplankton, macrophytes, and fish. In 6 months, PAC treatment caused a reduction of accumulation of polychlorobiphenyls (PCB) in fish by a factor of 20, bringing pollutant levels below toxic thresholds. All AC treatments supported growth of fish, but growth was inhibited in the PAC treatment, which was likely explained by reduced nutrient concentrations, resulting in lower zooplankton (i.e., food) densities for the fish. PAC treatment may be advised for sites where immediate ecosystem protection is required. GAC treatment may be equally effective in the longer term and may be adequate for vulnerable ecosystems where longer-term protection suffices.

Modeling trade-off between PAH toxicity reduction and negative effects of sorbent amendments to contaminated sediments.

Adding activated carbon (AC) to contaminated sediment has been suggested as an effective method for sediment remediation. AC binds chemicals such as polycyclic aromatic hydrocarbons (PAHs), thus reducing the toxicity of the sediment. Negative effects of AC on benthic organisms have also been reported. Here, we present a conceptual model to quantify the trade-off, in terms of biomass changes, between the advantageous PAH toxicity reduction and the negative effects of AC on populations of benthic species. The model describes population growth, incorporates concentration-effect relationships for PAHs in the pore water and for AC, and uses an equilibrium sorption model to estimate PAH pore water concentrations as a function of AC dosage. We calibrated the model using bioassay data and analyzed it by calculating isoclines of zero population growth for two species. For the sediment evaluated here, the results show that AC may safely protect the benthic habitat against considerable sediment PAH concentrations as long as the AC dosage remains below 4%.

Long-term recovery of benthic communities in sediments amended with activated carbon.

Using activated carbon (AC) for sediment remediation may have negative effects on benthic communities. To date, most AC effect studies were short-term and limited to single species laboratory tests. Here, we studied the effects of AC on the recolonization of benthic communities. Sediment from an unpolluted site was amended with increasing levels of AC, placed in trays and randomly embedded in the original site, which acted as a donor system for recolonization of benthic species. After 3 and 15 months, the trays were retrieved and benthic organisms identified. A positive trend with AC was detected for species abundance after 3 months, whereas after 15 months a negative trend with AC was detected for Lumbriculidae and Pisidiidae. On the community level, statistical analyses showed a considerable recovery in terms of species diversity and abundance in 3 months and full recovery of the community after 15 months. This was explained from migration of individuals from the donor system, followed by further migration and reproduction of the species in the next year. AC treatments explained 3% of the variance in the community data. This work suggests that AC community effects are mild as long as AC levels are not too high (1-4%).

Ecotoxicological effects of activated carbon amendments on macroinvertebrates in nonpolluted and polluted sediments.

Amendment of contaminated sediment with activated carbon (AC) is a remediation technique that has demonstrated its ability to reduce aqueous concentrations of hydrophobic organic compounds. The application of AC, however, requires information on possible ecological effects, especially effects on benthic species. Here, we provide data on the effects of AC addition on locomotion, ventilation, sediment avoidance, mortality, and growth of two benthic species, Gammarus pulex and Asellus aquaticus , in clean versus polycyclic aromatic hydrocarbon (PAH) contaminated sediment. Exposure to PAH was quantified using 76 µm polyoxymethylene passive samplers. In clean sediment, AC amendment caused no behavioral effects on both species after 3-5 days exposure, no effect on the survival of A. aquaticus , moderate effect on the survival of G. pulex (LC(50) = 3.1% AC), and no effects on growth. In contrast, no survivors were detected in PAH contaminated sediment without AC. Addition of 1% AC, however, resulted in a substantial reduction of water exposure concentration and increased survival of G. pulex and A. aquaticus by 30 and 100% in 8 days and 5 and 50% after 28 days exposure, respectively. We conclude that AC addition leads to substantial improvement of habitat quality in contaminated sediments and outweighs ecological side effects.

Kinetics of hydrophobic organic contaminant extraction from sediment by granular activated carbon.

Ex situ solid phase extraction with granular activated carbon (GAC) is a promising technique to remediate contaminated sediments. The methods' efficiency depends on the rate by which contaminants are transferred from the sediment to the surface of GAC. Here, we derive kinetic parameters for extraction of polycyclic aromatic hydrocarbons (PAH) from sediment by GAC, using a first-order multi-compartment kinetic model. The parameters were obtained by modeling sediment-GAC exchange kinetic data following a tiered model calibration approach. First, parameters for PAH desorption from sediment were calibrated using data from systems with 50% (by weight) GAC acting as an infinite sink. Second, the estimated parameters were used as fixed input to obtain GAC uptake kinetic parameters in sediment slurries with 4% GAC, representing the ex situ remediation scenario. PAH uptake rate constants (kGAC) by GAC ranged from 0.44 to 0.0005 d(-1), whereas GAC sorption coefficients (KGAC) ranged from 10(5.57) to 10(8.57) L kg(-1). These values are the first provided for GAC in the presence of sediment and show that ex situ extraction with GAC is sufficiently fast and effective to reduce the risks of the most available PAHs among those studied, such as fluorene, phenanthrene and anthracene.

Extraction of sediment-associated polycyclic aromatic hydrocarbons with granular activated carbon.

Addition of activated carbon (AC) to sediments has been proposed as a method to reduce ecotoxicological risks of sediment-bound contaminants. The present study explores the effectiveness of granular AC (GAC) in extracting polycyclic aromatic hydrocarbon (PAH) from highly contaminated sediments. Four candidate GAC materials were screened in terms of PAH extraction efficiency using single-step 24-h GAC extractions, with traditional 24-h Tenax extraction as a reference. Subsequently, sorption of native PAHs to the best performing GAC 1240W (0.45-1.70 mm) was studied for sediment only and for GAC-sediment mixtures at different GAC-sediment weight ratios, using 76-µm polyoxymethylene (POM) passive samplers. Granular AC sorption parameters for PAHs were determined by subtracting the contribution of PAH sorption to sediment from PAH sorption to the GAC-sediment mixture. It appears that the binding of PAHs and the effectiveness of GAC to reduce sediment porewater concentrations were highly dependent on the GAC-sediment mixing ratio and hydrophobicity of the PAH. Despite the considerable fouling of GAC by organic matter and oil, 50 to 90% of the most available PAH was extracted by the GAC during a 28-d contact time, at a dose as low as 4%, which also is a feasible dose in field-scale applications aimed at cleaning the sediment by GAC addition and removal.

In situ remediation of contaminated sediments using carbonaceous materials.

Carbonaceous materials (CM), such as activated carbons or biochars, have been shown to significantly reduce porewater concentrations and risks by binding hydrophobic organic compounds (HOCs) present in aquatic sediments. In the present study, the authors review the current state-of-the-art use of CM as an extensive method for sediment remediation, covering both technical and ecological angles. The review addresses how factors such as CM type, particle size and dosage, sediment characteristics, and properties of contaminants affect the effectiveness of CM amendment to immobilize HOCs in aquatic sediments. The authors also review the extent to which CM may reduce bioaccumulation and toxicity of HOCs and whether CM itself has negative effects on benthic species and communities. The review is based on literature and datasets from laboratory as well as field trials with CM amendments. The presence of phases such as natural black carbon, oil, or organic matter in the sediment reduces the effectiveness of CM amendments. Carbonaceous material additions appear to improve the habitat quality for benthic organisms by reducing bioavailable HOC concentrations and toxicity in sediment. The negative effects of CM itself on benthic species, if any, have been shown to be mild. The beneficial effects of reducing toxicity at low CM concentrations most probably outweigh the mild negative effects observed at higher CM concentrations.

In situ sorption of hydrophobic organic compounds to sediment amended with activated carbon.

Contaminated sediments can be remediated by adding carbonaceous materials (CM), e.g. activated carbons (AC). Here, we analyze published datasets from AC amendment trials to identify variation in the effectiveness of AC in reducing porewater concentrations of hydrophobic organic contaminants (HOCs). The analysis uses a model that separates the contribution of HOC sorption to AC by parameterzing the sorption contributions by amorphous organic matter and black carbon (BC). It appears that sorption to BC increased with LogK(OW), whereas sorption to AC showed a relatively narrow range of affinity properties with a median Freundlich LogK(F,)(AC) value of 7.2 (µg/kg(AC))/(µg/L)(n) (IQR = 7.0-7.5) for polychlorinated biphenyls (PCBs) and 8.6 (IQR = 8.3-8.8) for polycyclic aromatic hydrocarbons (PAHs). Estimated Freundlich exponents were n(F,)(AC) = 0.74 for PCBs and 0.82 for PAH. Sorption to AC was stronger than to BC for chemicals below LogK(OW) = 6.3-6.6. For HOC risk reduction this is favorable, because chemicals with low K(OW) show generally higher bioavailable concentrations.

Community effects of carbon nanotubes in aquatic sediments.

Aquatic sediments form an important sink for manufactured nanomaterials, like carbon nanotubes (CNT) and fullerenes, thus potentially causing adverse effects to the aquatic environment, especially to benthic organisms. To date, most nanoparticle effect studies used single species tests in the laboratory, which lacks ecological realism. Here, we studied the effects of multiwalled CNT (MWCNT) contaminated sediments on benthic macroinvertebrate communities. Sediment was taken from an unpolluted site, cleaned from invertebrates, mixed with increasing levels of MWCNTs (0, 0.002, 0.02, 0.2 and 2g/kg dry weight), transferred to trays and randomly relocated in the original unpolluted site, which now acted as a donor system for recolonization by benthic species. After three months of exposure, the trays were regained, organic (OC) and residual carbon (RC) were measured, and benthic organisms and aquatic macrophytes were identified. ANOVA revealed a significantly higher number of individuals with increasing MWCNT concentrations. The Shannon index showed no significant effect of MWCNT addition on biodiversity. Multivariate statistics applied to the complete macroinvertebrate dataset, did show effects on the community level. Principal Component Analysis (PCA) showed differences in taxa composition related to MWCNT levels indicating differences in sensitivity of the taxa. Redundancy Analysis (RDA) revealed that MWCNT dose, presence of macrophytes, and spatial distribution explained 38.3% of the total variation in the data set, of which MWCNT dose contributed with 18.9%. Still, the net contribution of MWCNT dose was not statistically significant, indicating that negative community effects are not likely to occur at environmentally relevant future CNT concentrations in aquatic sediments.