Danny D. Reible

Contaminant fluxes from sediment due to tubificid oligochaete bioturbation

The release of the hydrophobic organic compounds pyrene, dibenzofuran and phenanthrene from bioturbated freshwater sediments was studied in laboratory microcosms. Initial Tubificid oligochaete densities of 0, 6700 and 2.67 × 104 individuals · m−2 were employed. Under oxygen saturated conditions, the difference between the contaminant fluxes from the high-density bioturbated microcosms and controls remained essentially constant at 37 and 70 ng · cm2−2 · d−1 for pyrene and phenanthrene, respectively, corresponding to effective mass transfer coefficients of 0.16 and 0.37 cm/y. Under hypoxic conditions, worm defecation on the sediment surface increased and led to significantly increased fluxes to a maximum of 380, 490 and 940 ng · cm−2 · d−1, for pyrene, phenanthrene and dibenzofuran, respectively. Average bioturbation fluxes in the high-density microcosms of 246, 258 and 310 ng · cm−2 · d−1 for the respective compounds corresponded to effective mass transfer coefficients of 1.7, 3.2, and 7.5 cm/yr. Initial release rates from medium-density microcosms (25% of high density) were typically half the release rate of the high-density microcosms, indicating greater organism activity per individual at the lower density. The increased flux with the more soluble compounds likely reflects more rapid release at the sediment surface and the increased importance of porewater pumping over sediment particle reworking for migration of these compounds.

Regional variation in water-related impacts of shale gas development and implications for emerging international plays.

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.

Assessing and Managing Contaminated Sediments: Part I, Developing an Effective Investigation and Risk Evaluation Strategy

Abstract This is the first of a two-part review of the current state-of-the-science pertaining to the assessment and management of contaminated sediments. The goal of this review is to introduce some of the major technical and policy issues stemming from the assessment and management of contaminated sediments, highlight a number of aspects of contaminated sediment assessment and management found to be successful, and, when appropriate, address the barriers that still exist for improving contaminated sediment management. In this paper, Part I, the many key elements of an effective investigation and risk evaluation strategy are reviewed, beginning with the development of a conceptual site model (CSM) and including a discussion of some of the key factors influencing the design of sediment investigations and ecological risk assessment of sediment-bound chemicals on aquatic biota. In Part II of this paper (Apitz et al. 2005), various approaches are reviewed for evaluating sediment risk and monitoring sediment remedy effectiveness. While many of the technical and policy issues described in this review are relevant to dredged material management, the focus of this paper is on sediment assessment for environmental management.

Passive sampling methods for contaminated sediments: Practical guidance for selection, calibration, and implementation

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.

ON THE ENRICHMENT OF HYDROPHOBIC ORGANIC COMPOUNDS IN FOG DROPLETS

Abstract The unusual degree of enrichment of hydrophobic organics in fogwater droplets reported by several investigators can be interpreted as a result of (a) the effects of temperature correction on the reported enrichment factors, (b) the effects of colloidal organic matter (both filterable and non-filterable) in fog water and (c) the effects of the large air-water interfacial adsorption of neutral hydrophobic organics on the tiny fog droplets. The enrichment factor was directly correlated to the hydrophobicity (or the activity coefficient in water) of the compounds, as indicated by their octanol-water partition constants. Compounds with large octanol-water partition coefficients (high activity coefficients in water) showed the largest enrichment. Available experimental data on the adsorption of hydrophobic compounds at the air-water interface and on colloidal organic carbon were used to show that the large specific air-water interfacial areas of fog droplets contribute significantly to the enrichment factor.

Diffusion models of environmental transport

Environmental Transport Modeling Introduction Outline Preliminaries Equilibrium Between Environmental Tables Diffusion and the Diffusion Coefficient Surface Mass Transfer Coefficient Mass Balance and Transport Equations Diffusion in a Semi-Infinite Soil/Sediment System Introduction Analysis Summary Numerical Evaluation Development Diffusion in a Finite Layer Soil/Sediment Bed Introduction Analysis Summary Numerical Evaluation Development Diffusion in a Two-Layer Composite Soil/Sediment Bed Introduction Analysis Summary Numerical Evaluation Development Diffusion in a Three-Layer Composite Soil/Sediment Bed Introduction Analysis Summary Numerical Evaluation Development Advection-Diffusion Models Introduction Analysis Summary Numerical Evaluation Development Volatile Liquid Evaporation and Diffusion Through a Soil/Sediment Bed Introduction Analysis Summary Numerical Evaluation Development Diffusion in Systems with Time Dependent Soil-Air Partition Coefficients Introduction Mathematical Analysis Analysis Summary Variable Transformation on a Variety of Time Dependent Air-Soil Partition Coefficient Functions Development Miscellaneous Transport Models Constant Flux, Volatile Liquid Evaporation with Uniform Initial Liquid Saturation Appendices Error Function Laplace Transformation Roots of Transcendental Equations Predicting the Diffusion Coefficient in Vapor Predicting the Diffusion Coefficient in Liquid Sample Calculations of Models Using Mathcad(TM) 7

Development and Placement of a Sorbent-Amended Thin Layer Sediment Cap in the Anacostia River

Incorporating materials into sediment caps that can sequester contaminants will greatly improve their ability to isolate contaminants in the underlying sediments from the rest of the aquatic environment. For highly sorptive media a thin layer (cm) may be sufficient, but accurately placing a thin layer (cm) of material over submerged contaminated sediment is difficult. A reactive core mat (RCM) was designed to accurately place a 1.25 cm thick sorbent (coke) layer in an engineered sediment cap. In April 2004, twelve 3.1 m × 31 m sections of RCM were placed in the Anacostia River, Washington, D.C., and overlain with a 15 cm layer of sand to secure it and provide a habitat for benthic organisms to colonize without compromising the integrity of the cap. Placement of the RCM did not cause significant sediment re-suspension or impact site hydrology. The RCM is an inexpensive and effective method to accurately deliver thin layers of difficult to place, high value, sorptive media into sediment caps. The approach can also be used to place granular reactive media that can degrade or mineralize contaminants.

Predicting bioavailability of PAHs and PCBs with porewater concentrations measured by solid‐phase microextraction fibers

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.

Comparison of polymeric samplers for accurately assessing PCBs in pore waters.

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 polymers 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.

Sequestering Agents for Active Caps—Remediation of Metals and Organics

This research evaluated organoclays, zeolites, phosphates, and a biopolymer as sequestering agents for inorganic and organic contaminants. Batch experiments were conducted to identify amendments and mixtures of amendments for metal and organic contaminant removal and retention. Contaminant removal was evaluated by calculating partitioning coefficients. Metal retention was evaluated by desorption studies in which residue from the removal studies was extracted with 1 M MgCl2 solution. The results indicated that phosphate amendments, some organoclays, and the biopolymer, chitosan, were very effective sequestering agents for metals in fresh and salt water. Organoclays were very effective sorbents for phenanthrene, pyrene, and benzo(a)pyrene. Partitioning coefficients for the organoclays were 3000–3500 L g−1 for benzo(a)pyrene, 400–450 L g−1 for pyrene, and 50–70 L g−1 for phenanthrene. Remediation of sites with a mixture of contaminants is more difficult than sites with a single contaminant because metals and organic contaminants have different fate and transport mechanisms in sediment and water. Mixtures of amendments (e.g., organoclay and rock phosphate) have high potential for remediating both organic and inorganic contaminants under a broad range of environmental conditions, and have promise as components in active caps for sediment remediation.