This article provides practical guidance on the use of passive sampling methods (PSMs) that target the freely dissolved concentration (Cfree) for improved exposure assessment of hydrophobic organic chemicals in sediments. Primary considerations for selecting a PSM for a specific application include clear delineation of measurement goals for Cfree, whether laboratory-based “ex situ” and/or field-based “in situ” application is desired, and ultimately which PSM is best-suited to fulfill the measurement objectives. Guidelines for proper calibration and validation of PSMs, including use of provisional values for polymer–water partition coefficients, determination of equilibrium status, and confirmation of nondepletive measurement conditions are defined. A hypothetical example is described to illustrate how the measurement of Cfree afforded by PSMs reduces uncertainty in assessing narcotic toxicity for sediments contaminated with polycyclic aromatic hydrocarbons. The article concludes with a discussion of future research that will improve the quality and robustness of Cfree measurements using PSMs, providing a sound scientific basis to support risk assessment and contaminated sediment management decisions. Integr Environ Assess Manag 2014;10:210–223. © 2014 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals, Inc. on behalf of SETAC.

The work by Savant et al. [1987] is an interesting introduction to the understanding of convective transport within stable river dunes. The discussion that follows constitutes as a whole an effort to identify and explain the discrepancies existing between the results of the numerical model and the experimental dye trajectories displayed in Figure 6 of their paper by looking at several aspects of the physics of the problem.The flow field within the sand wave (hereafter termed the internal flow field) and the one above it (hereafter called the external flow field) are strongly connected. As a matter of fact, at the dune surface they interact rendering invalid the use of the Darcy equation in a narrow zone underlaying the perimeter of the bed form. Clearly, the Darcy equation is not compatible with the existence of a boundary layer region in the porous medium, since no shear term is associated with this law. However, as a first approximation it could be assumed that the internal flow field is determined exlusively by the pressure distribution generated by the stream turbulent flow field and that there are not major differences between pressure

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Assessing the hazard posed by sediments contaminated with hydrophobic organic compounds is difficult, because measuring the freely dissolved porewater concentrations of such low-solubility chemicals can be challenging, and estimating their sediment-water partition coefficients remains quite uncertain. We suggest that more accurate site assessments can be achieved by employing sampling devices in which polymers, with known polymer-water partition coefficients, are used to absorb the contaminants from the sediment. To demonstrate the current accuracy and limitations of this approach, we compared use of three polymers, polydimethylsiloxane, polyoxymethylene, and polyethylene, exposed to a single sediment in two modes, one in which they were exhaustively mixed (tumbled) with the sediment and the other in which they were simply inserted into a static bed (passive). Comparing porewater concentrations of specific polychlorinated biphenyl (PCB) congeners with results obtained using air bridges, we found the results for tumbled polymers agreed within 20%, and the passive sampling agreed within a factor of 2. In contrast, porewater estimates based on sediment concentrations normalized to f(OC)K(OC), the weight fraction of organic carbon times the organic-carbon normalized partition coefficient, averaged a factor of 7 too high. We also found good correlations of each polymer's uptake of the PCBs with bioaccumulation by the polychaete, Neanthes arenaceodentata. Future improvements of the passive sampling mode will require devices that equilibrate faster and/or have some means such as performance reference compounds to estimate mass transfer limitations for individual deployments.

The unconventional fossil fuel industry is expected to expand dramatically in coming decades as conventional reserves wane. Minimizing the environmental impacts of this energy transition requires a contextualized understanding of the unique regional issues that shale gas development poses. This manuscript highlights the variation in regional water issues associated with shale gas development in the U.S. and the approaches of various states in mitigating these impacts. The manuscript also explores opportunities for emerging international shale plays to leverage the diverse experiences of U.S. states in formulating development strategies that minimize water-related impacts within their environmental, cultural, and political ecosystem.

An active capping demonstration project in Washington, D.C., is testing the ability to place sequestering agents on contaminated sediments using conventional equipment and evaluating their subsequent effectiveness relative to conventional passive sand sediment caps. Selected active capping materials include: (1) AquaBlok TM , a clay material for permeability control; (2) apatite, a phosphate mineral for metals control; (3) coke, an organic sequestration agent; and (4) sand material for a control cap. All of the materials, except coke, were placed in 8,000-ft 2 test plots by a conventional clamshell method during March and April 2004. Coke was placed as a 1.25-cm layer in a laminated mat due to concerns related to settling of the material. Postcap sampling and analysis were conducted during the first, sixth, and eighteenth months after placement. Although postcap sampling is expected to continue for at least an additional 24 months, this article summarizes the results of the demonstration project and postcap sampling efforts up to 18 months.Conventional clamshell placement was found to be effective for placing relatively thin (six-inch) layers of active material. The viability of placing high-value or difficult-to-place material in a controlled manner was successfully demonstrated with the laminated mat. Postcap monitoring indicates that all cap materials effectively isolated contaminants, but it is not yet possible to differentiate between conventional sand and active cap layer performance. Monitoring of the permeability control layer indicated effective reductions in groundwater seepage rates through the cap, but also showed the potential for gas accumulation and irregular release. All of the cap materials show deposition of new contaminated sediment onto the surface of the caps, illustrating the importance of source control in maintaining sediment quality. © 2006 Wiley Periodicals, Inc. INTRODUCTIONIn situ containment of contaminated sediments is often achieved through capping, typically with a passive sand layer to physically separate contaminants from benthic receptors and to reduce the flux of contaminants to the overlying water. Sand provides excellent protection when contaminants are strongly sorbed to the solid phase and in the absence of rapid contaminant migration processes. Under some situations, however, such as high rates of groundwater seepage, achievement of the desired reductions in flux may require the use of a layer that can sequester or degrade contaminants.These types of caps are often termed active caps to differentiate from passive sand layers. A variety of active cap materials have been proposed that can provide advantages over sand for specific contaminants. Active cap materials that have been proposed include phosphate minerals for metals control, organoclays and sorbents such as activated carbon or coke for organic contaminant control, and clays for permeability control.The selection of an Yuewei ZhuActive Capping Demonstration in the Anacostia River, Washington, D.C. appropriate active...

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Bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) was measured in the deposit-feeding oligochaete Ilyodrilus templetoni exposed for 28 d to Anacostia River sediment (Washington, DC, USA) and to an initially uncontaminated sediment from Brown Lake (Vicksburg, MS, USA) sequentially diluted with 3 to 25% contaminated New Bedford Harbor sediment (New Bedford, MA, USA). The Anacostia River sediment studies represented exposure to a historically contaminated sediment with limited availability, whereas exposure to the other sediment included both the historically contaminated New Bedford Harbor sediment and fresh redistribution of contaminants into the Brown Lake sediments. Organism tissue concentrations did not correlate with bulk sediment concentrations in the Anacostia River sediment but did correlate with the sequentially diluted sediment. Porewater concentrations measured via disposable solid-phase microextraction fiber (SPME) with polydimethylsiloxane (PDMS), however, correlated well with organism uptake in all sediments. Bioaccumulation was predicted well by a linear relationship with the product of porewater concentration and compound octanol-water partition coefficient (Anacostia, slope = 1.08, r² = 0.76; sequentially diluted sediments, slope = 1.24, r² = 0.76). The data demonstrate that the octanol-water partition coefficient is a good indicator of the lipid-water partition coefficient and that porewater concentrations provide a more reliable indicator of bioaccumulation in the organism than sediment concentrations, even when the route of uptake is expected to be via sediment ingestion.