Barbara Beckingham

Field-Scale Reduction of PCB Bioavailability with Activated Carbon Amendment to River Sediments

Remediation of contaminated sediments remains a technological challenge because traditional approaches do not always achieve risk reduction goals for human health and ecosystem protection and can even be destructive for natural resources. Recent work has shown that uptake of persistent organic pollutants such as polychlorinated biphenyls (PCBs) in the food web is strongly influenced by the nature of contaminant binding, especially to black carbon surfaces in sediments. We demonstrate for the first time in a contaminated river that application of activated carbon to sediments in the field reduces biouptake of PCBs in benthic organisms. After treatment with activated carbon applied at a dose similar to the native organic carbon of sediment, bioaccumulation in freshwater oligochaete worms was reduced compared to preamendment conditions by 69 to 99%, and concentrations of PCBs in water at equilibrium with the sediment were reduced by greater than 93% at all treatment sites for up to three years of monitoring. By comparing measured reductions in bioaccumulation of tetra- and penta-chlorinated PCB congeners resulting from field application of activated carbon to a laboratory study where PCBs were preloaded onto activated carbon, it is evident that equilibrium sorption had not been achieved in the field. Although other remedies may be appropriate for some highly contaminated sites, we show through this pilot study that PCB exposure from moderately contaminated river sediments may be managed effectively through activated carbon amendment in sediments.

Respiratory succession and community succession of bacterioplankton in seasonally anoxic estuarine waters.

ABSTRACT Anoxia occurs in bottom waters of stratified estuaries when respiratory consumption of oxygen, primarily by bacteria, outpaces atmospheric and photosynthetic reoxygenation. Once water becomes anoxic, bacterioplankton must change their metabolism to some form of anaerobic respiration. Analysis of redox chemistry in water samples spanning the oxycline of Chesapeake Bay during the summer of 2004 suggested that there was a succession of respiratory metabolism following the loss of oxygen. Bacterial community doubling time, calculated from bacterial abundance (direct counts) and production (anaerobic leucine incorporation), ranged from 0.36 to 0.75 day and was always much shorter than estimates of the time that the bottom water was anoxic (18 to 44 days), indicating that there was adequate time for bacterial community composition to shift in response to changing redox conditions. However, community composition (as determined by PCR-denaturing gradient gel electrophoresis analysis of 16S rRNA genes) in anoxic waters was very similar to that in surface waters in June when nitrate respiration was apparent in the water column and only partially shifted away from the composition of the surface community after nitrate was depleted. Anoxic water communities did not change dramatically until August, when sulfate respiration appeared to dominate. Surface water populations that remained dominant in anoxic waters were Synechococcus sp., Gammaproteobacteria in the SAR86 clade, and Alphaproteobacteria relatives of Pelagibacter ubique, including a putative estuarine-specific Pelagibacter cluster. Populations that developed in anoxic water were most similar (<92% similarity) to uncultivated Firmicutes, uncultivated Bacteroidetes, Gammaproteobacteria in the genus Thioalcalovibrio, and the uncultivated SAR406 cluster. These results indicate that typical estuarine bacterioplankton switch to anaerobic metabolism under anoxic conditions but are ultimately replaced by different organisms under sulfidic conditions.

Comparison of Sedimentary PAHs in the Rivers of Ammer (Germany) and Liangtan (China): Differences between Early- and Newly-Industrialized Countries

As a proxy to trace the impact of anthropogenic activity, sedimentary polycyclic aromatic hydrocarbons (PAHs) are compared between the early industrialized and newly industrialized countries of Germany and China, respectively. Surface sediment samples in the Ammer River of Germany and the Liangtan River of China were collected to compare concentration levels, distribution patterns, and diagnostic plots of sedimentary PAHs. Total concentrations of 16 PAHs in Ammer sediments were significantly higher by a factor of ~4.5 than those in Liangtan. This contrast agrees with an extensive literature survey of PAH levels found in Chinese versus European sediments. Distribution patterns of PAHs were similar across sites in the Ammer River, whereas they were highly varied in the Liangtan River. Pyrogenic sources dominated in both cases. Strong correlations of the sum of 16 PAHs and PAH groups with TOC contents in the Liangtan River may indicate coemission of PAHs and TOC. Poor correlations of PAHs with TOC in the Ammer River indicate that other factors exert stronger influences. Sedimentary PAHs in the Ammer River are primarily attributed to input of diffuse sources or legacy pollution, while sediments in the Liangtan River are probably affected by ongoing point source emissions. Providing further evidence of a more prolonged anthropogenic influence are the elevated black carbon fractions in sedimentary TOC in the Ammer compared to the Liangtan. This implies that the Liangtan River, like others in newly industrialized regions, still has a chance to avoid legacy pollution of sediment which is widespread in the Ammer River and other European waterways.

Evaluation of biochars and activated carbons for in situ remediation of sediments impacted with organics, mercury, and methylmercury.

In situ amendment of activated carbon (AC) to sediments can effectively reduce the bioavailability of hydrophobic organic contaminants. While biochars have been suggested as low-cost and sustainable alternatives to ACs, there are few comparative sorption data especially for mercury (Hg) and methylmercury (MeHg) at the low porewater concentrations in sediments. Here we compare the ability of a wide range of commercially available and laboratory synthesized ACs and biochars to sorb PAHs, PCBs, DDTs, inorganic Hg, and MeHg at environmentally relevant concentrations. Compared to natural organic matter, sorption capacity for most organic compounds was at least 1-2 orders of magnitude higher for unactivated biochars and 3-4 orders of magnitude higher for ACs which translated to sediment porewater PCB concentration reductions of 18-80% for unactivated biochars, and >99% for ACs with 5% by weight amendment to sediment. Steam activated carbons were more effective than biochars in Hg sorption and translated to modeled porewater Hg reduction in the range of 94-98% for sediments with low native Kd and 31-73% for sediments with high native Kd values for Hg. Unactivated biochars were as effective as the steam activated carbons for MeHg sorption. Predicted reductions of porewater MeHg were 73-92% for sediments with low native Kd and 57-86% for sediment with high native K(d). ACs with high surface areas therefore are likely to be effective in reducing porewater concentrations of organics, Hg, and MeHg in impacted sediments. Unactivated biochars had limited effectiveness for organics and Hg but can be considered when MeHg exposure is the primary concern.

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.

Turbidity as a proxy for total suspended solids (TSS) and particle facilitated pollutant transport in catchments

Transport of hydrophobic organic pollutants in rivers is mainly coupled to transport of suspended particles. Turbidity measurements are often used to assess the amount of suspended solids in water. In this study, a monitoring campaign is presented where the total concentration of polycyclic aromatic hydrocarbons (PAHs), the amount of total suspended solids (TSS), and turbidity was measured in water samples from five neighboring catchments in southwest Germany. Linear correlations of turbidity and TSS were obtained which were in close agreement to the literature data. From linear regressions of turbidity versus total PAH concentrations in water, mean concentrations of PAH on suspended particles could be calculated and these varied by catchment. These values furthermore comprise a robust measure of the average sediment quality in a given catchment. Since in the catchments investigated in this study, PAH concentrations on suspended particles were stable over a large turbidity range (1–114 Nephelometric Turbidity Units), turbidity could be used as a proxy for total PAHs and likely other highly hydrophobic organic pollutants in river water if the associated correlations are established. Based on that, online monitoring of turbidity (e.g., by optical backscattering sensors) seems very promising to determine annual pollutant fluxes.

Magnetite impregnation effects on the sorbent properties of activated carbons and biochars

This paper discusses the sorbent properties of magnetic activated carbons and biochars produced by wet impregnation with iron oxides. The sorbents had magnetic susceptibilities consistent with theoretical predictions for carbon-magnetite composites. The high BET surface areas of the activated carbons were preserved in the synthesis, and enhanced for one low surface area biochar by dissolving carbonates. Magnetization decreased the point of zero charge. Organic compound sorption correlated strongly with BET surface areas for the pristine and magnetized materials, while metal cation sorption did not show such a correlation. Strong sorption of the hydrophobic organic contaminant phenanthrene to the activated carbon or biochar surfaces was maintained following magnetite impregnation, while phenol sorption was diminished, probably due to enhanced carbon oxidation. Copper, zinc and lead sorption to the activated carbons and biochars was unchanged or slightly enhanced by the magnetization, and iron oxides also contributed to the composite metal sorption capacity. While a magnetic biochar with 219 ± 3.7 m(2)/g surface area nearly reached the very strong organic pollutant binding capacity of the two magnetic activated carbons, a magnetic biochar with 68 ± 2.8 m(2)/g surface area was the best metal sorbent. Magnetic biochars thus hold promise as more sustainable alternatives to coal-derived magnetic activated carbons.

Biological responses to activated carbon amendments in sediment remediation.

Sorbent amendment with activated carbon (AC) is a novel in situ management strategy for addressing human and ecological health risks posed by hydrophobic organic chemicals (HOCs) in sediments and soils. A large body of literature shows that AC amendments can reduce bioavailability of sediment-associated HOCs by more than 60-90%. Empirically derived biodynamic models can predict bioaccumulation in benthic invertebrates within a factor of 2, allowing for future scenarios under AC amendment to be estimated. Higher AC dose and smaller AC particle size further reduce bioaccumulation of HOCs but may induce stress in some organisms. Adverse ecotoxicity response to AC exposure was observed in one-fifth of 82 tests, including changes in growth, lipid content, behavior, and survival. Negative effects on individual species and benthic communities appear to depend on the characteristics of the sedimentary environment and the AC amendment strategy (e.g., dose and particle size). More research is needed to evaluate reproductive end points, bacterial communities, and plants, and to link species- and community-level responses to amendment. In general, the ability of AC to effectively limit the mobility of HOCs in aquatic environments may outshine potential negative secondary effects, and these outcomes must be held in comparison to traditional remediation approaches.

Integrated monitoring of particle associated transport of PAHs in contrasting catchments.

Water quality of rivers depends often on the degree of urbanization and the population density in the catchment. This study shows results of a monitoring campaign of total concentration of polycyclic aromatic hydrocarbons (PAHs) and suspended particles in water samples in adjacent catchments in Southern Germany with similar geology and climate but different degrees of urbanization. Defined linear relationships between total concentrations of PAHs in water and the amount of suspended solids were obtained indicating predominance of particle-facilitated transport. The slopes of these regressions correspond to the average contamination of suspended particles (C(sus)) and thus comprise a very robust measure of sediment pollution in a river. For the first time, we can show that C(sus) is distinct in the different catchments and correlates to the degree of urbanization represented by the number of inhabitants per total flux of suspended particles.

Observations of limited secondary effects to benthic invertebrates and macrophytes with activated carbon amendment in river sediments

Amendment of activated carbon to sediments has been shown to effectively reduce the bioavailability of hydrophobic organic contaminants, but concerns have been raised about the potential toxicological impacts of administering a strong sorbent into sediments. The present study provides a summary of several investigations carried out as part of a pilot-scale study in a river to understand the secondary effects of activated carbon added to reduce the bioavailability of sediment-associated polychlorinated biphenyls. While some previous laboratory amendment studies have found reduced lipid content in freshwater worms exposed to activated carbon-treated sediments, the authors did not observe an impact with fine-granular activated carbon-amended sediments aged in the field. Benthic community studies did not find differences between control and activated carbon-treated field sites over 3 yr of postapplication monitoring. Laboratory studies with submerged aquatic plants indicated reduced growth in sediments amended with ≥5% activated carbon, which was attributed to volume dilution of nutritional sediment or bulk density changes and was also observed when the sediment was amended with biochar and inert perlite. Since in situ sorbent amendment is likely to be implemented in depositional sediment environments, potential negative impacts will likely be short-term if the treated site is slowly covered with new sediment over time. Overall suitability of activated carbon amendment for a site will depend on balancing ecosystem and human health benefits from contaminant bioavailability reduction with any potential negative impacts expected under field conditions.