A longitudinal study of mercury exposure associated with consumption of freshwater fish from a reservoir in rural south central USA.

Methylmercury (MeHg) exposure through fish consumption is a worldwide health concern. Saltwater fish account for most dietary MeHg exposure in the general U.S. population, but less is known about seasonal variations in MeHg exposure and fish consumption among millions of freshwater anglers. This longitudinal study examined associations between MeHg exposure and fish consumption in a rural, low-income population relying on a freshwater reservoir (Oklahoma, USA) for recreational and subsistence fishing. We interviewed 151 participants, primarily anglers and their families, seasonally for one year using 90-day recall food frequency questionnaires to assess general and species-specific fish consumption, and tested hair biomarker samples for total mercury (THg hair). Mean THg hair was 0.27 µg/g (n=595, range: 0.0044-3.1 µg/g), with 4% of participants above U.S. EPA's guideline for women of childbearing age and children. Mean fish consumption was 58 g/d (95% CI: 49-67 g/d), within the range previously reported for recreational freshwater anglers and above the national average. Unlike the general U.S. population, freshwater species contributed the majority of fish consumption (69%) and dietary Hg exposure (60%) among participants, despite relatively low THg in local fish. THg hair increased with fish consumption, age, and education, and was higher among male participants and the lowest in winter. Our results suggest that future studies of anglers should consider seasonality in fish consumption and MeHg exposure and include household members who share their catch. Efforts to evaluate benefits of reducing Hg emissions should consider dietary patterns among consumers of fish from local freshwater bodies.

Assessing sources of human methylmercury exposure using stable mercury isotopes.

Seafood consumption is the primary route of methylmercury (MeHg) exposure for most populations. Inherent uncertainties in dietary survey data point to the need for an empirical tool to confirm exposure sources. We therefore explore the utility of Hg stable isotope ratios in human hair as a new method for discerning MeHg exposure sources. We characterized Hg isotope fractionation between humans and their diets using hair samples from Faroese whalers exposed to MeHg predominantly from pilot whales. We observed an increase of 1.75‰ in δ(202)Hg values between pilot whale muscle tissue and Faroese whalers' hair but no mass-independent fractionation. We found a similar offset in δ(202)Hg between consumed seafood and hair samples from Gulf of Mexico recreational anglers who are exposed to lower levels of MeHg from a variety of seafood sources. An isotope mixing model was used to estimate individual MeHg exposure sources and confirmed that both Δ(199)Hg and δ(202)Hg values in human hair can help identify dietary MeHg sources. Variability in isotopic signatures among coastal fish consumers in the Gulf of Mexico likely reflects both differences in environmental sources of MeHg to coastal fish and uncertainty in dietary recall data. Additional data are needed to fully refine this approach for individuals with complex seafood consumption patterns.

Temporal increase in organic mercury in an endangered pelagic seabird assessed by century-old museum specimens.

Methylmercury cycling in the Pacific Ocean has garnered significant attention in recent years, especially with regard to rising mercury emissions from Asia. Uncertainty exists concerning whether increases in anthropogenic emissions over time may have caused increased mercury bioaccumulation in the biota. To address this, we measured total mercury and, for a subset of samples, methylmercury (the bioaccumulated form of mercury) in museum feathers from an endangered seabird, the black-footed albatross (Phoebastria nigripes), spanning a 120-y period. We analyzed stable isotopes of nitrogen (δ(15)N) and carbon (δ(13)C) to control for temporal changes in trophic structure and diet. In post-1940 and -1990 feathers, we detected significantly higher mean methylmercury concentrations and higher proportions of samples exhibiting above deleterious threshold levels (∼ 40,000 ng · g(-1)) of methylmercury relative to prior time points, suggesting that mercury toxicity may undermine reproductive effort in the species. We also found higher levels of (presumably curator-mediated) inorganic mercury in older specimens of albatross as well as two nonpelagic species lacking historical exposure to bioavailable mercury, patterns suggesting that studies on bioaccumulation should measure methylmercury rather than total mercury when using museum collections. δ(15)N contributed substantially to models explaining the observed methylmercury variation. After simultaneously controlling for significant trends in δ(13)C over time and δ(15)N with methylmercury exposure, year remained a significant independent covariate with feather methylmercury levels among the albatrosses. These data show that remote seabird colonies in the Pacific basin exhibit temporal changes in methylmercury levels consistent with historical global and recent regional increases in anthropogenic emissions.

Prioritizing environmental risk of prescription pharmaceuticals.

Low levels of pharmaceutical compounds have been detected in aquatic environments worldwide, but their human and ecological health risks associated with low dose environmental exposure is largely unknown due to the large number of these compounds and a lack of information. Therefore prioritization and ranking methods are needed for screening target compounds for research and risk assessment. Previous efforts to rank pharmaceutical compounds have often focused on occurrence data and have paid less attention to removal mechanisms such as human metabolism. This study proposes a simple prioritization approach based on number of prescriptions and toxicity information, accounting for metabolism and wastewater treatment removal, and can be applied to unmeasured compounds. The approach was performed on the 200 most-prescribed drugs in the US in 2009. Our results showed that under-studied compounds such as levothyroxine and montelukast sodium received the highest scores, suggesting the importance of removal mechanisms in influencing the ranking, and the need for future environmental research to include other less-studied but potentially harmful pharmaceutical compounds.

Bioavailability assessment of a contaminated field sediment from Patrick Bayou, Texas, USA: toxicity identification evaluation and equilibrium partitioning.

Contaminated sediments are commonly found in urbanized harbors. At sufficiently high contaminant levels, sediments can cause toxicity to aquatic organisms and impair benthic communities. As a result, remediation is necessary and diagnosing the cause of sediment toxicity becomes imperative. In the present study, six sediments from a highly industrialized area in Patrick Bayou (TX, USA) were subjected to initial toxicity testing with the mysid, Americamysis bahia, and the amphipod, Ampelisca abdita. All sediments were toxic to the amphipods, while sites PB4A, PB6A, and PB9 were the only sites toxic to mysids. Due to its toxicity to both test organisms, site PB6A was chosen for a marine whole sediment phase I toxicity identification evaluation (TIE). Results of the TIE found toxicity to amphipods was primarily due to nonionic organic contaminants (NOCs), rather than cationic metals or ammonia. Causes of mysid toxicity in the TIE were less clear. An assessment of metal bioavailability using equilibrium partitioning (EqP) approaches supported the results of the TIE that cationic metals were not responsible for observed toxicity in PB6A for either organism. Toxic units (TU) calculated on measured concentrations of NOCs in the sediment yielded a total TU of 1.25, indicating these contaminants are contributing to the observed sediment toxicity. Using a combination of these TIE and EqP assessment tools, this investigation was capable of identifying NOCs as the likely class of contaminants causing acute toxicity to amphipods exposed to Patrick Bayou sediment. The cause of mysid toxicity was not definitively determined, but unmeasured NOCs are suspected.

Development and evaluation of reverse polyethylene samplers for marine phase II whole-sediment toxicity identification evaluations.

Marine and estuarine sediments accumulate contaminants and act as a sink for a wide range of toxic chemicals. As a result, the sediments themselves can become a source of contamination. At sufficient levels, contaminated sediments can cause benthic impairments and toxicity to marine organisms. Among the wide range of contaminants, nonionic organic contaminants (NOCs) are a primary cause of toxicity in marine sediments. Toxicity identification evaluations (TIEs) are used to characterize and identify chemicals causing toxicity in effluents, interstitial waters, and whole sediments using whole-organism endpoints. Phase I whole-sediment TIE methods for NOCs exist, but the development of phase II TIE methods for NOCs is a current research challenge. In the present study, the use of reverse polyethylene samplers (RePES) for phase II methods is examined. Various RePES designs were evaluated in an experimental design study with NOC chemical solutions. Based on equilibration time and proximity of measured NOC water concentrations in the reconstituted system to theoretical concentrations, a nontriolein design with loading of chemical solutions on the inside of the polyethylene tubing was chosen as most effective. A partitioning study demonstrated NOCs partitioned between the RePES and water as well as between the water and air, as expected using this nontriolein RePES design. Finally, a sediment toxicity study comparing the nontriolein RePES to contaminant-spiked sediments was conducted. The nontriolein RePES design was capable of successfully recreating the toxicity and water concentrations observed with the intact sediments.

Impact of mine waste on airborne respirable particulates in northeastern Oklahoma, United States.

Atmospheric dispersion of particles from mine waste is potentially an important route of human exposure to metals in communities close to active and abandoned mining areas. This study assessed sources of mass and metal concentrations in two size fractions of respirable particles using positive matrix factorization (U.S. Environmental Protection Agency [EPA] PMF 3.0). Weekly integrated samples of particulate matter (PM) 10 microm in aerodynamic diameter or less (PM10) and fine PM (PM2.5, or PM <2.5 microm in aerodynamic diameter) were collected at three monitoring sites, varying distances (0.5-20 km) from mine waste piles, for 58 consecutive weeks in a former lead (Pb) and zinc (Zn) mining region. Mean mass concentrations varied significantly across sites for coarse PM (PM10-PM2.5) but not PM2.5 particles. Concentrations of Pb and Zn significantly decreased with increasing distance from the mine waste piles in PM10-PM2.5 (P < 0.0001) and PM2.5 (P < 0.0005) fractions. Source apportionment analyses deduced five sources contributing to PM2.5 (mobile source combustion, secondary sulfates, mine waste, crustal/soil, and a source rich in calcium [Ca]) and three sources for the coarse fraction (mine waste, crustal/soil, and a Ca-rich source). In the PM2.5 fraction, mine waste contributed 1-6% of the overall mass, 40% of Pb, and 63% of Zn. Mine waste impacts were more apparent in the PM10-PM2.5 fraction and contributed 4-39% of total mass, 88% of Pb, and 97% of Zn. Percent contribution of mine waste varied significantly across sites (P < 0.0001) for both size fractions, with highest contributions in the site closest to the mine waste piles. Seasonality, wind direction, and concentrations of the Ca-rich source were also associated with levels of ambient aerosols from the mine waste source. Scanning electron microscopy results indicated that the PMF-identified mine waste source is mainly composed of Zn-Pb agglomerates on crustal particles in the PM10-PM2.5 fraction. In conclusion, the differential impacts of mine waste on respirable particles by size fraction and location should be considered in future exposure evaluations.

Mercury bioaccumulation and trophic transfer in sympatric snapper species from the Gulf of Mexico.

Consumption of marine fish is a major route of toxic methyl mercury (MeHg) exposure to ocean apex predators and human populations. Here we explore the influence of trophic structure on total mercury (Hg) accumulation in red snapper (RS, Lutjanus campechanus) and gray snapper (GS, Lutjanus griseus) from the coastal Louisiana region of the Gulf of Mexico, west of the Mississippi River. The objectives of this investigation were to: (1) determine the effectiveness of the use of offshore recreational fishing charter boats and marinas as sources of fish samples and (2) compare species differences in Hg bioaccumulation, trophic position, and carbon sources. Our data show that length-normalized Hg concentrations (> or = 97% as MeHg in tissue of both species) were 230% greater in GS in comparison to RS collected from the same general area. Stable C and N isotope signatures (delta15N and delta13C) indicate that GS occupy a slightly higher trophic position (approximately 30% of one trophic position higher) on the Gulf food web in comparison to RS and that GS appear to incorporate higher trophic positioned prey, continually and at smaller sizes. Mercury was strongly correlated with combined delta15N and delta13C in pooled species data, arguing that most of the substantial difference in Hg bioaccumulation between RS and GS can be explained by modest differences in their trophic position and, to a lesser degree, carbon sources, which had low variation and high overlap among species. These observations demonstrate that even minor to moderate differences in trophic position and food habits in sympatric species can create relatively large differences in bioaccumulation regimes and underscores the importance of quantitative characterization of trophic structure in marine MeHg bioaccumulation studies.

The precipitation of indium at elevated pH in a stream influenced by acid mine drainage.

Indium is an increasingly important metal in semiconductors and electronics and has uses in important energy technologies such as photovoltaic cells and light-emitting diodes (LEDs). One significant flux of indium to the environment is from lead, zinc, copper, and tin mining and smelting, but little is known about its aqueous behavior after it is mobilized. In this study, we use Mineral Creek, a headwater stream in southwestern Colorado severely affected by heavy metal contamination as a result of acid mine drainage, as a natural laboratory to study the aqueous behavior of indium. At the existing pH of ~3, indium concentrations are 6-29µg/L (10,000× those found in natural rivers), and are completely filterable through a 0.45µm filter. During a pH modification experiment, the pH of the system was raised to >8, and >99% of the indium became associated with the suspended solid phase (i.e. does not pass through a 0.45µm filter). To determine the mechanism of removal of indium from the filterable and likely primarily dissolved phase, we conducted laboratory experiments to determine an upper bound for a sorption constant to iron oxides, and used this, along with other published thermodynamic constants, to model the partitioning of indium in Mineral Creek. Modeling results suggest that the removal of indium from the filterable phase is consistent with precipitation of indium hydroxide from a dissolved phase. This work demonstrates that nonferrous mining processes can be a significant source of indium to the environment, and provides critical information about the aqueous behavior of indium.

Exposure Potential and Health Impacts of Indium and Gallium, Metals Critical to Emerging Electronics and Energy Technologies.

The rapid growth of new electronics and energy technologies requires the use of rare elements of the periodic table. For many of these elements, little is known about their environmental behavior or human health impacts. This is true for indium and gallium, two technology critical elements. Increased environmental concentrations of both indium and gallium create the potential for increased environmental exposure, though little is known about the extent of this exposure. Evidence is mounting that indium and gallium can have substantial toxicity, including in occupational settings where indium lung disease has been recognized as a potentially fatal disease caused by the inhalation of indium particles. This paper aims to review the basic chemistry, changing environmental concentrations, potential for human exposure, and known health effects of indium and gallium.

Statistical evaluation of biogeochemical variables affecting spatiotemporal distributions of multiple free metal ion concentrations in an urban estuary.

Free metal ion concentrations have been recognized as a better indicator of metal bioavailability in aquatic environments than total dissolved metal concentrations. However, our understanding of the determinants of free ion concentrations, especially in a metal mixture, is limited, due to underexplored techniques for measuring multiple free metal ions simultaneously. In this work, we performed statistical analyses on a large dataset containing repeated measurements of free ion concentrations of Cu, Zn, Pb, Ni, and Cd, the most commonly measured metals in seawater, at five inshore locations in Boston Harbor, previously collected using an in-situ equilibrium-based multi-metal free ion sampler, the 'Gellyfish'. We examined correlations among these five metals by season, and evaluated effects of 10 biogeochemical variables on free ion concentrations over time and location through multivariate regressions. We also explored potential clustering among the five metals through a principal component analysis. We found significant correlations among metals, with varying patterns over season. Our regression results suggest that instead of dissolved metals, pH, salinity, temperature and rainfall were the most significant determinants of free metal ion concentrations. For example, a one-unit decrease in pH was associated with a 2.2 (Cd) to 99 (Cu) times increase in free ion concentrations. This work is among the first to reveal key contributors to spatiotemporal variations in free ion concentrations, and demonstrated the usefulness of the Gellyfish sampler in routine sampling of free ions within metal mixtures and in generating data for statistical analyses.

Associations between metals in residential environmental media and exposure biomarkers over time in infants living near a mining-impacted site.

Infant exposures to metals are a concern for mining-impacted communities, although limited information is available to assess residential exposures over the first year of life. We measured lead (Pb), manganese, arsenic, and cadmium in indoor air, house dust, yard soil, and tap water from 53 infants' homes near the Tar Creek Superfund Site (Oklahoma, USA) at two time points representing developmental stages before and during initial ambulation (age 0-6 and 6-12 months). We measured infant metal biomarkers in: umbilical cord blood (n=53); 12- (n=43) and 24- (n=22) month blood; and hair at age 12 months (n=39). We evaluated cross-sectional and longitudinal associations between infant residential and biomarker concentrations. A doubling of mean dust Pb concentration was consistently associated with 36-49% higher 12-month blood Pb adjusting for cord blood Pb (P⩽0.05). Adjusted dust concentration explained 29-35% of blood Pb variance, and consistent associations with other media were not observed. Although concentrations in dust and blood were generally low, strong and consistent associations between dust and body burden suggest that house dust in mining-impacted communities may impact children's health. These relationships were observed at a young age, typically before blood Pb levels peak and when children's development may be particularly vulnerable to toxic insult.

Concentrations of lead and mercury in multimedia samples from homes near the former Clark Air Base, Philippines.

We measured lead and mercury in samples collected from 31 homes in communities near the former Clark Air Base, Philippines during May and October 2002. Sample media included water used for drinking and cooking, house dust and entryway soil. Composite samples of 15 food items purchased at local markets were also collected. Samples were analyzed for total lead (Pb) and total mercury (Hg) to evaluate the relative importance of each media to residential exposure concentrations in the community adjacent to Clark (Community A) versus a control community 5 km away (Community B). In general, we measured low (e.g. background) to undetectable levels of the target analytes in all media sampled with two important exceptions. First, the Hg concentrations we measured in canned mackerel composites, which were within the range reported for mackerel from other locations worldwide, may pose a risk to pregnant women who are frequent consumers (e.g. one or more cans per day). Second, we measured Pb above the USEPA residential screening concentration (400 mug/g) in dust and soil from two homes, illustrating the need for periodic residential lead monitoring in these and other communities in the Philippines. We found no significant difference between Communities A and B with respect to Pb and Hg concentrations in water or food, although we were not able to detect very low levels of Pb in most of the foods we sampled because of trace Pb contamination added during sample homogenization. Although the Pb levels we measured in dust and soil from Community A homes were higher on average than Community B homes, the levels in both communities were low (e.g. background) thus we did not investigate the difference further. To our knowledge, these are the first reported measurements of Pb in house dust in the Philippines. The concentrations of Pb we measured in house dust were significantly higher than those in entryway soil from both communities, adding empirical support to the assertion that yard soil should not be considered a proxy for house dust in exposure studies in the Philippines or elsewhere.

The Gellyfish: An in situ equilibrium-based sampler for determining multiple free metal ion concentrations in marine ecosystems.

Free metal ions are usually the most bioavailable and toxic metal species to aquatic organisms, but they are difficult to measure because of their extremely low concentrations in the marine environment. Many of the current methods for determining free metal ions are complicated and time-consuming, and they can only measure 1 metal at a time. The authors developed a new version of the "Gellyfish," an in situ equilibrium-based sampler, with significantly reduced equilibration time and the capability of measuring multiple free metal ions simultaneously. By calibrating the Gellyfish to account for its uptake of cationic metal complexes and validating them in multi-metal competition experiments, the authors were able to determine free metal ion concentrations previously collected over 10 mo at 5 locations in Boston Harbor for Cu, Zn, Pb, Ni, and Cd. This generated 1 of the largest free metal ion datasets and demonstrated the applicability of the Gellyfish as an easy-to-use and inexpensive tool for monitoring free ion concentrations of metal mixtures in marine ecosystems.

Use of receiver operating characteristic curves to evaluate sediment quality guidelines for metals.

Receiver operating characteristic (ROC) curves are commonly used in the biomedical field to assess the quality of a diagnostic test. The area under an ROC curve, which ranges from 0.5 to 1.0, is a measure of the overall effectiveness of a diagnostic test. These curves can be used to elucidate compromises in sensitivity (ability to correctly classify a toxic sample as toxic) and specificity (ability to correctly classify a nontoxic sample as nontoxic) associated with a given threshold. In this study, ROC curves were used to evaluate methods for estimating acute toxicity of metals in marine sediments. Differences in the effectiveness of speciation (comparisons of labile sulfides with simultaneously extracted metals) and total sediment concentration (such as the National Oceanographic and Atmospheric Administration Guidelines, Washington, DC) approaches were assessed by using a database of field and laboratory spiked sediments. Despite uncertainties associated with these methods, the areas under the ROC curves ranged from 0.84 to 0.89 for all approaches tested, with no significant differences between speciation and whole sediment approaches. Thresholds commonly used by environmental managers, although yielding high sensitivity, came at the expense of low specificity. Thresholds providing desirable trade-offs in sensitivity and specificity generally are higher than commonly used thresholds.

Importance of black carbon in distribution and bioaccumulation models of polycyclic aromatic hydrocarbons in contaminated marine sediments.

The roles and relative importance of nonpyrogenic organic carbon (NPOC) and black carbon (BC) as binding phases of polycyclic aromatic hydrocarbons (PAHs) were assessed by their ability to estimate pore water concentrations and biological uptake in various marine sediments. Sediment bioaccumulation tests were performed with the marine polychaete Nereis virens, using a polyethylene device to estimate pore water concentrations of PAHs. Using existing partitioning data for pyrene and phenanthrene, it was found that the traditional Equilibrium Partitioning model, which assumes all organic carbon is NPOC (EqP(OC)), overestimated the measured pore water concentrations in the test sediments by one to three orders of magnitude. Instead, the measured pore water concentrations were better predicted from a distribution scenario that uses both BC and NPOC (EqP(NPOc,BC)) When comparing actual worm body burdens of pyrene and phenanthrene with the two model estimates of worm tissue concentrations, the EqP(OC) model tended to overestimate actual body burdens by three orders of magnitude, while the EqP(NPOC,BC) model came much closer to the true body burden values. The observed distribution of PAHs in the test sediments was used to calculate BC partition coefficients for five PAHs, which were one to two orders of magnitude higher than their corresponding organic carbon-normalized distribution coefficients, or K(OC)s. Together, these results suggest that, in certain situations, adding black carbon to distribution models may be necessary to predict accurately the bioavailability of PAHs.

Bioavailability of hydrophobic organic compounds in thin-layered capped sediments.

The effect of a thin sand capping layer (7.5 cm) on the bioavailability of hydrophobic organic compounds (HOCs, i.e., PCBs and naphthalene) was studied using oligochaete worms, and the results compared to previously obtained bioavailability tests with a reactive core mat (RCM) cap. The study investigated the difference in HOC concentration in worms exposed to: (a) a grab sample of sediment used as sampled for PCBs and spiked for PAHs; (b) an initially clean mixture of sand and organic matter (biouptake layer) directly overlying the sediment; and (c) the biouptake layer placed on top of the RCM-capped sediment. Benchscale experiments were performed to induce pore fluid flux through the sediment and into the overlying layer(s). Principal component analysis (PCA) was used to assess PCB homolog group concentrations. Results indicate that the thin sand cap alone reduced the average bioavailability of PCBs by a factor of 100 compared to direct exposure, but had no effect on the bioavailability of naphthalene. However, worms exposed to the RCM-protected biouptake layer show virtually the same HOC concentrations as those in the background worm samples, indicating effective isolation by the RCM.

Sources and fates of heavy metals in a mining-impacted stream: temporal variability and the role of iron oxides.

Heavy metal contamination of surface waters at mining sites often involves complex interactions of multiple sources and varying biogeochemical conditions. We compared surface and subsurface metal loading from mine waste pile runoff and mine drainage discharge and characterized the influence of iron oxides on metal fate along a 0.9-km stretch of Tar Creek (Oklahoma, USA), which drains an abandoned Zn/Pb mining area. The importance of each source varied by metal; mine waste pile runoff contributed 70% of Cd, while mine drainage contributed 90% of Pb, and both sources contributed similarly to Zn loading. Subsurface inputs accounted for 40% of flow and 40-70% of metal loading along this stretch. Streambed iron oxide aggregate material contained highly elevated Zn (up to 27,000 µg g(-1)), Pb (up to 550 µg g(-1)) and Cd (up to 200 µg g(-1)) and was characterized as a heterogeneous mixture of iron oxides, fine-grain mine waste, and organic material. Sequential extractions confirmed preferential sequestration of Pb by iron oxides, as well as substantial concentrations of Zn and Cd in iron oxide fractions, with additional accumulation of Zn, Pb, and Cd during downstream transport. Comparisons with historical data show that while metal concentrations in mine drainage have decreased by more than an order of magnitude in recent decades, the chemical composition of mine waste pile runoff has remained relatively constant, indicating less attenuation and increased relative importance of pile runoff. These results highlight the importance of monitoring temporal changes at contaminated sites associated with evolving speciation and simultaneously addressing surface and subsurface contamination from both mine waste piles and mine drainage.

Benchscale Assessment of the Efficacy of a Reactive Core Mat to Isolate PAH-spiked Aquatic Sediments.

This paper describes the results of a benchscale testing program to assess the efficacy of a reactive core mat (RCM) for short term isolation and partial remediation of contaminated, subaqueous sediments. The 1.25 cm thick RCM (with a core reactive material such as organoclay with filtering layers on top and bottom) is placed on the sediment, and approximately 7.5 - 10 cm of overlying soil is placed on the RCM for stability and protection. A set of experiments were conducted to measure the sorption characteristics of the mat core (organoclay) and sediment used in the experiments, and to determine the fate of semi-volatile organic contaminants and non-reactive tracers through the sediment and reactive mat. The experimental study was conducted on naphthalene-spiked Neponset River (Milton, MA) sediment. The results show nonlinear sorption behavior for organoclay, with sorption capacity increasing with increasing naphthalene concentration. Neponset River sediment showed a notably high sorption capacity, likely due to the relatively high organic carbon fraction (14%). The fate and transport experiments demonstrated the short term efficiency of the reactive mat to capture the contamination that is associated with the post-capping period during which the highest consolidation-induced advective flux occurs, driving solid particles, pore fluid and soluble contaminants toward the reactive mat. The goal of the mat placement is to provide a physical filtering and chemically reactive layer to isolate contamination from the overlying water column. An important finding is that because of the high sorption capacity of the Neponset River sediment, the physical filtering capability of the mat is as critical as its chemical reactive capacity.

Passive sampling methods for contaminated sediments: risk assessment and management.

This paper details how activity-based passive sampling methods (PSMs), which provide information on bioavailability in terms of freely dissolved contaminant concentrations (Cfree ), can be used to better inform risk management decision making at multiple points in the process of assessing and managing contaminated sediment sites. PSMs can increase certainty in site investigation and management, because Cfree is a better predictor of bioavailability than total bulk sediment concentration (Ctotal ) for 4 key endpoints included in conceptual site models (benthic organism toxicity, bioaccumulation, sediment flux, and water column exposures). The use of passive sampling devices (PSDs) presents challenges with respect to representative sampling for estimating average concentrations and other metrics relevant for exposure and risk assessment. These challenges can be addressed by designing studies that account for sources of variation associated with PSMs and considering appropriate spatial scales to meet study objectives. Possible applications of PSMs include: quantifying spatial and temporal trends in bioavailable contaminants, identifying and evaluating contaminant source contributions, calibrating site-specific models, and, improving weight-of-evidence based decision frameworks. PSM data can be used to assist in delineating sediment management zones based on likelihood of exposure effects, monitor remedy effectiveness, and, evaluate risk reduction after sediment treatment, disposal, or beneficial reuse after management actions. Examples are provided illustrating why PSMs and freely dissolved contaminant concentrations (Cfree ) should be incorporated into contaminated sediment investigations and study designs to better focus on and understand contaminant bioavailability, more accurately estimate exposure to sediment-associated contaminants, and better inform risk management decisions. Research and communication needs for encouraging broader use are discussed.