Field methods for amending marine sediment with activated carbon and assessing treatment effectiveness.

Previous laboratory studies have shown reductions in PCB bioavailability for sediments amended with activated carbon (AC). Here we report results on a preliminary pilot-scale study to assess challenges in scaling-up for field deployment and monitoring. The goals of the preliminary pilot-scale study at Hunters Point Shipyard (San Francisco, USA) were to (1) test the capabilities of a large-scale mixing device for incorporating AC into sediment, (2) develop and evaluate our field assessment techniques, and (3) compare reductions in PCB bioavailability found in the laboratory with well-mixed systems to those observed in the field with one-time-mixed systems. In this study we successfully used a large-scale device to mix 500kg of AC into a 34.4m(2) plot to a depth of 1ft, a depth that includes the majority of the biologically active zone. Our results indicate that after 7 months of AC-sediment contact in the field, the 28-day PCB bioaccumulation for the bent-nosed clam, Macoma nasuta, field-deployed to this AC-amended sediment was approximately half of the bioaccumulation resulting from exposure to untreated sediment. Similar PCB bioaccumulation reductions were found in laboratory bioassays conducted on both the bivalve, M. nasuta and the estuarine amphipod, Leptocheirus plumulosus, using sediment collected from the treated and untreated field plots one year after the AC amendment occurred. To further understand the long-term effectiveness of AC as an in situ treatment strategy for PCB-contaminated sediments under field conditions, a 3-year comprehensive study is currently underway at Hunters Point that will compare the effectiveness of two large-scale mixing devices and include both unmixed and mixed-only control plots.

Microscale analytical methods for the quantitative detection of PCBs and PAHs in small tissue masses.

Microscale methods (MM) were evaluated and compared to traditional methods (TM) for measuring polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) in spiked and standard reference fish and mussel tissues. MMs are advantageous because they use small tissue masses (ca. 100mg), and maintain sensitivity through reducing final extract volume (traditionally 1 ml) by an order of magnitude or more (40 microl-PCBs; 100 microl-PAHs). Procedural losses occurred in the MMs' combined cleanup/primary evaporation step (19% PAHs; 6% PCBs), and the final extract concentration (14% PAHs; 22% PCBs). The PAH MM performed comparably to the TM. Although most PCBs had recoveries >50%, the PCB MM generally yielded lower recoveries than the TM. Average method detection limits were 0.6 microg/kg (TM) and 1.0 microg/kg (MM) for PCBs and 25.7 microg/kg (TM) and 27.7 microg/kg (MM) for PAHs. MMs described for PCB and PAH tissue samples are potentially viable alternatives to TMs, and could lead to cost savings in bioaccumulation/toxicity tests.

Effects of dose and particle size on activated carbon treatment to sequester polychlorinated biphenyls and polycyclic aromatic hydrocarbons in marine sediments.

Recent laboratory studies show that mixing activated carbon with contaminated sediment reduces the chemical and biological availability of hydrophobic organic contaminants. In this study, we test the effects of varying the activated carbon dose and particle size in reducing the aqueous availability of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) and the uptake of PCBs by two benthic organisms. We mixed PCB- and PAH-contaminated sediment from Hunters Point Naval Shipyard, San Francisco Bay (CA, USA), for one month with activated carbon, at doses of 0.34, 1.7, and 3.4% dry mass basis. We found that increasing the carbon dose increased the effectiveness in reducing PCB bioaccumulation. In 56-d uptake tests with the benthic organisms Neanthes arenaceodentata and Leptocheirus plumulosus, PCB bioaccumulation was reduced by 93 and 90%, respectively, with 3.4% carbon. Increasing the dose also increased the effectiveness in reducing PCB and PAH aqueous concentrations and uptake by semipermeable membrane devices and quiescent flux of PCBs to overlying water. Decreasing activated carbon particle size increased treatment effectiveness in reducing PCB aqueous concentration, and larger-sized activated carbon (400-1,700 microm) was ineffective with a contact period of one month. We invoke a numerical model based on intraparticle diffusion in sediment and activated carbon particles to help interpret our experimental results. This model was useful in explaining the trends for the effect of activated carbon dose and particle size on PCB aqueous concentrations in well-mixed systems.

Addition of activated carbon to sediments to reduce PCB bioaccumulation by a polychaete (Neanthes arenaceodentata) and an amphipod (Leptocheirus plumulosus).

This work examines the effects of adding coke or activated carbon on the bioavailability of polychlorinated biphenyls (PCBs) in contaminated sedimentfrom South Basin at Hunters Point, San Francisco Bay. We show with 28-day sediment exposure tests that PCB bioaccumulation in a polychaete (Neanthes arenaceodentata) is reduced by 82% following 1-month contact of sediment with activated carbon and by 87% following 6-months contact of sediment with activated carbon. PCB bioaccumulation in an amphipod (Leptocheirus plumulosus) is reduced by 70% following 1-month contact of sediment with activated carbon and by 75% after 6-months contact of sediment with activated carbon. Adding coke had a negligible effect on reducing PCB bioaccumulation, probably because of the low specific surface area and the slow kinetics of PCB diffusion intothe solid coke particles. Reductions in congener bioaccumulation with activated carbon were inversely related to congener Kow, suggesting that the efficacy of activated carbon is controlled by the mass-transfer rate of PCBs from sediment and into activated carbon. We find that reductions in aqueous PCB concentrations in equilibrium with the sediment were similar to reductions in PCB bioaccumulation. While no lethality was observed following activated carbon addition, growth rates were reduced by activated carbon for the polychaete, but not for the amphipod, suggesting the need for further study of the potential impacts of activated carbon on exposed communities. The study suggests that treatment of the biologically active layer of contaminated sediments with activated carbon may be a promising in-situ technique for reducing the bioavailability of sediment-associated PCBs and other hydrophobic organic compounds.

Addition of carbon sorbents to reduce PCB and PAH bioavailability in marine sediments: physicochemical tests.

The addition of activated carbon as particulate sorbent to the biologically active layer of contaminated sediment is proposed as an in-situ treatment method to reduce the chemical and biological availability of hydrophobic organic contaminants (HOCs) such as polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs). We report results from physicochemical experiments that assess this concept. PCB- and PAH-contaminated sediment from Hunters Point Naval Shipyard, San Francisco Bay, CA, was contacted with coke and activated carbon for periods of 1 and 6 months. Sediment treated with 3.4 wt % activated carbon showed 92% and 84% reductions in aqueous equilibrium PCB and PAH concentrations, 77% and 83% reductions in PCB and PAH uptake by semipermeable membrane devices (SPMD), respectively, and reductions in PCB flux to overlying water in quiescent systems up to 89%. Adding coke to contaminated sediment did not significantly decrease aqueous equilibrium PCB concentrations nor PCB or PAH availability in SPMD measurements. Coke decreased PAH aqueous equilibrium concentrations by 38-64% depending on coke dose and particle size. The greater effectiveness of activated carbon as compared to coke is attributed to its much greater specific surface area and a pore structure favorable for binding contaminants. The results from the physicochemical tests suggest that adding activated carbon to contaminated field sediment reduces HOC availability to the aqueous phase. The benefit is manifested relatively quickly under optimum contact conditions and improves in effectiveness with contact time from 1 to 6 months. Activated carbon application is a potentially attractive method for in-situ, nonremoval treatment of marine sediment contaminated with HOCs.