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Biomonitoring at contaminated sites undergoing clean-up, including Superfund sites, often use bioaccumulation of anthropogenic contaminants by field-deployed organisms as a metric of remedial effectiveness. Bioaccumulation studies are unable to assess the equilibrium status of the organisms relative to the contaminants to which they are exposed. Establishing equilibrium provides a reproducible benchmark upon which scientific and management decisions can be based (e.g., comparison to human dietary consumption criteria). Unlike bioaccumulating organisms, passive samplers can be assessed for their equilibrium status. In this investigation, over a three-year period, we compared the bioaccumulation of selected polychlorinated biphenyls (PCBs) by mussels in water column deployments at the New Bedford Harbor Superfund site (New Bedford, MA, USA) to co-deployed passive samplers. Based on comparisons to the calculated passive sampler equilibrium concentrations, the mussels were not at equilibrium, and the subsequent analysis focused on evaluating approaches for estimating equilibrium bioaccumulation. In addition, a limited evaluation of metal bioaccumulation by the exposed mussels and a metal passive sampler was performed. In general, mussel and passive sampler accumulation of PCBs was significantly correlated; however, surprisingly, agreement on the magnitude of accumulation was optimal when bioaccumulation and passive sampler uptake were not corrected for non-equilibrium conditions. A subsequent comparison of four approaches for estimating equilibrium mussel bioaccumulation using octanol-water and triolein-water partition coefficients (K

Urban estuaries receive large volumes of effluents from municipal wastewater treatment facilities containing numerous contaminants, such as pharmaceuticals residues. Water was sampled for 16 highly prescribed pharmaceuticals at 17 sites along the Long Island Sound (LIS) estuary located in the Northeastern U.S. Pharmaceutical concentrations were highest in western LIS, ranging from non-detect to 71 ng L−1 and declining steadily eastward, while river samples from four major tributaries ranged from non-detect to 83 ng L−1. Two tracers, sucralose and caffeine, accurately predicted pharmaceutical behavior in LIS while only sucralose was effective at the river sites. Sucralose also tracked well with the salinity gradient in LIS, exhibiting conservative behavior along the transect. Attenuation factors were determined for measurable pharmaceuticals and compared against sucralose to estimate the magnitude of decline in concentrations that may be attributable to in situ degradation and partitioning. The results demonstrate sucralose's effectiveness as a tracer of wastewater-borne contaminants under estuarine conditions.

Of the thousands of per- and polyfluoroalkyl substances (PFAS) in the environment, few have been investigated in detail. In this study, we analyzed 36 legacy and emerging PFAS in multiple seabird tissues collected from individuals from Massachusetts Bay, Narragansett Bay and the Cape Fear River Estuary. PFOS was the dominant compound across multiple tissues, while long-chain perfluorinated carboxylic acids (PFCAs) dominated in brain (mean = 44% of total concentrations). Emerging perfluoroalkyl ether acids (PFEAs)-Nafion byproduct-2 and PFO5DoDA - were detected in greater than 90% of tissues in birds obtained from a nesting region downstream from a major fluorochemical production site. Compound ratios, relative body burden calculations, and electrostatic surface potential calculations were used to describe partitioning behavior of PFEAs in different tissues. Novel PFEAs preferentially partition into blood compared to liver, and were documented in brain for the first time. PFO5DoDA showed a reduced preference for brain compared to PFCAs and Nafion BP2. These results suggest future monitoring efforts and toxicological studies should focus on novel PFAS and long-chain PFCAs in multiple tissues beyond liver and blood, while exploring the unique binding mechanisms driving uptake of multi-ether PFEAs.

Narragansett Bay is representative of New England, USA urbanized estuaries, with colonization in the early 17th century, and development into industrial and transportation centers in the late 18th and early 20th century. Increasing nationwide population and lack of infrastructure maintenance led to environmental degradation, and then eventual improvement after implementation of contaminant control and sewage treatment starting in the 1970s. Benthic macroinvertebrate community structure was expected to respond to these environmental changes. This study assembled data sets from the 1950s through 2010s to examine whether quantitative aggregate patterns in the benthic community corresponded qualitatively to stressors and management actions in the watershed. In Greenwich Bay and Providence River, patterns of benthic response corresponded to the decline and then improvement in sewage treatment at the Fields Point wastewater treatment plant. In Mount Hope Bay, the benthos corresponded to changes in bay fish populations due to thermal discharge from the Brayton Point power plant. The benthos of the Upper West Passage corresponded to climatic changes that caused regime shifts in the plankton and fish communities. Future work will examine the effects of further environmental improvements in the face of continued climatic changes and population growth.

The deployment of aqueous film forming foams (AFFF) used for firefighting during emergencies and training often releases per- and polyfluoroalkyl substances (PFAS) into the environment. In October 2018, first responders in Providence, RI, USA applied an AFFF during a fuel spill. Due to the proximity of the incident to the upper reaches of Narragansett Bay (NB), an unknown quantity of gasoline and AFFF entered the estuary via surface runoff and stormwater drains. Water samples near the spill were collected approximately 15 hours after the incident and analyzed for 24 PFAS. Minor increases in measured PFAS concentrations were observed relative to pre- and post-spill samples at monitoring sites near the incident, except 6:2-fluorotelomer sulfonate (6:2-FTS) that peaked post-spill (max 311 ng/L). After performing the total oxidizable precursor (TOP) assay on water samples and the AFFF concentrate, significant increases in perfluorocarboxylic acids (PFCAs) were observed. One compound, 6:2 fluorotelomer mercaptoalkylamido sulfonate (6:2-FTSAS), was identified as a major component of the AFFF used. Peak areas of 6:2-FTSAS and the degradation product 6:2-FTSAS-sulfoxide corresponded to observed increases in the TOP assay results and were useful as tracers of AFFF in surrounding waters. Elevated levels of PFAS at the time of sampling were limited to a confined area of the Providence River due to river flow and tidal action. Observed concentrations were also compared to hydrodynamic model results, and results confirmed rapid dissipation of AFFF components with distance from the spill. However, modeled results did not capture possible secondary releases of AFFF from local municipal stormwater and sewer infrastructure, as observational data suggest. The multiple lines of evidence of PFAS present in surface waters permitted a better assessment of the potential environmental impacts from products such as AFFF for which the chemical composition is largely unknown.

Per- and polyfluoroalkyl substances (PFAS) are anthropogenic, globally distributed chemicals. Legacy PFAS, including perfluorooctane sulfonate (PFOS), have been regularly detected in marine fauna but little is known about their current levels or the presence of novel PFAS in seabirds. We measured 36 emerging and legacy PFAS in livers from 31 juvenile seabirds from Massachusetts Bay, Narragansett Bay, and the Cape Fear River Estuary (CFRE), USA. PFOS was the major legacy perfluoroalkyl acid present, making up 58% of concentrations observed across all habitats (range: 11 – 280 ng/g). Novel PFAS were confirmed in chicks hatched downstream of a fluoropolymer production site in the CFRE - a perfluorinated ether sulfonic acid (Nafion byproduct-2; range: 1 – 110 ng/g) and two perfluorinated ether carboxylic acids (PFO(4)DA and PFO(5)DoDA; PFO(5)DoDA range: 5 – 30 ng/g). PFOS was inversely associated with phospholipid content in livers from CFRE and Massachusetts Bay individuals, while δ(13)C, an indicator of marine vs. terrestrial foraging, was positively correlated with some long-chain PFAS in CFRE chick livers. These results detail concentrations of legacy and novel PFAS across different marine ecosystems along the US Atlantic East Coast. There is also an indication that seabird phospholipid dynamics are negatively impacted by PFAS, which should be further explored given the importance of lipids for seabirds.

Increased consumption and improper disposal of prescription medication, such as beta (β)-blockers, contribute to their introduction into waterways and may pose threats to non-target aquatic organisms. There has been rising concern about the impacts of these prescription drugs on coastal ecosystems, especially because wastewater treatment plants are not designed to eliminate them from the discharge. Few studies have characterized the sublethal effects of β-blocker exposures in marine invertebrates. The overall aim of our research is to identify cellular responses of two commercially important filter-feeding marine bivalves, hard clams (Mercenaria mercenaria) and Eastern oysters (Crassostrea virginica), upon exposures to two β-blocker drugs, propranolol and metoprolol. In vitro exposures with bivalve digestive gland and gill tissues were conducted where tissues were separately exposed to each drug for 24 h. Tissue samples were analyzed for cellular damage (lysosomal membrane destabilization and lipid peroxidation), total antioxidant capacity, and glutathione-s-transferase activity. Elevated damage and changes in enzyme activities were noted in the exposed tissues at environmentally relevant concentrations. Differences in species and tissue sensitivities and responses to exposures were also observed. These studies enhance our understanding of the potential impacts of prescription medication on coastal organisms. Additionally, this work demonstrates that filter-feeders may serve as good model organisms to examine the effects of unintended environmental exposures to β-blockers. These studies are part of our ongoing work aimed at evaluation of sublethal biomarkers of pharmaceutical exposures and identification of key events that can contribute to the development of adverse outcome pathways (AOPs).

It is well known that copper (Cu) is toxic to marine organisms. We measured and compared the acute toxicity of several forms of Cu (including nanoCu) amended into a marine sediment with mysids and amphipods. For all the forms of Cu tested, toxicity, measured as the median lethal concentration, ranged from 708 to > 2400 mg Cu/kg (dry sediment) for mysids and 258 to 1070 mg Cu/kg (dry sediment) for amphipods. Environ Toxicol Chem 2018;37:2677-2681. © 2018 SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

The widespread use of pharmaceuticals by human populations results in their sustained discharge to surface waters via wastewater treatment plants (WWTPs). In this study, 16 highly prescribed pharmaceuticals were quantified along a 250 km transect of the Hudson River Estuary and New York Harbor to describe their sources and spatial patterns. Sampling was conducted over two dry weather periods in May and July 2016, at 72 sites which included mid-channel and nearshore sites, as well as locations influenced by tributaries and WWTP outfalls. The detection frequency of the study pharmaceuticals was almost identical between the May and July sampling periods at 55% and 52%, respectively. Six pharmaceuticals were measurable at 92% or more of the sites during both sampling periods, illustrating their ubiquitous presence throughout the study area. Individual pharmaceutical concentrations were highly variable spatially, ranging from non-detect to 3810 ng/L during the study. Major factors controlling concentrations were proximity and magnitude of WWTP discharges, inputs from tributaries and tidal mixing. Two compounds, sucralose and caffeine, were evaluated as tracers to identify wastewater sources and assess pharmaceutical behavior. Sucralose was useful in identifying wastewater inputs to the river and concentrations showed excellent correlations with numerous pharmaceuticals in the study. Caffeine-sucralose ratios showed potential in identifying discharges of untreated wastewater occurring during a combined sewage overflow event. Many of the study pharmaceuticals were present throughout the Hudson River Estuary as a consequence of sustained wastewater discharge. Whereas some concentrations were above published effects levels, a more complete risk assessment is needed to understand the potential for ecological impacts due to pharmaceuticals in the Hudson River Estuary.

The widespread use of copper nanomaterials (CuNMs) as antibacterial and antifouling agents in consumer products increases the risk for metal contamination and adverse effects in aquatic environments. Information gaps exist on the potential toxicity of CuNMs in marine environments. We exposed field-collected marine meio- and macrobenthic communities to sediments spiked with micronized copper azole (MCA) using a novel method that brings intact benthic cores into the laboratory and exposes the organisms via surface application of sediments. Treatments included field and laboratory controls, 3 spiked sediments: low-MCA (51.9 mg/kg sediment), high-MCA (519 mg/kg sediment), and CuSO4 (519 mg/kg sediment). In addition, single-species acute testing was performed with both MCA and CuSO4. Our results indicate that meio- and macrofaunal assemblages exposed to High-MCA and CuSO4 treatments differed significantly from both the laboratory control and the low-MCA treatments. Differences in macrofauna were driven by decreases in 3 Podocopa ostracod species, the bivalve Gemma gemma, and the polychaetes Exogone verugera and Prionospio heterobranchia relative to the laboratory control. Differences in the meiofaunal community are largely driven by nematodes. The benthic community test results were more sensitive than the single-species test results. Findings of this investigation indicate that CuNMs represent a source of risk to marine benthic communities comparable to that of dissolved Cu. Environ Toxicol Chem 2017;9999:1–14. Published 2017 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

Salem, MA, located north of Boston, has a rich, well-documented history dating back to settlement in 1626 CE, but the associated anthropogenic impacts on Salem Sound are poorly constrained. This project utilized dated sediment cores from the sound to assess the proxy record of anthropogenic alterations to the system and compared the proxy records to the known history. Proxies included bulk stable isotopes of organic matter, magnetic susceptibility, and trace metal concentrations. Our data reveal clear changes in organic matter composition and concentration associated with land use changes and twentieth century sewage disposal practices. Further, metals data correspond with local industrial activity, particularly the historic tanning industry in Peabody, MA. Although conservation practices of past decades have improved the state of Salem Sound, the stratigraphic record demonstrates that the environment is still affected by anthropogenic influences, and has not attained conditions consistent with pre-anthropogenic baseline. The approach and results of this study are applicable to coastal embayments that are being assessed for remediation, especially those with scant historic or monitoring data.

The behavior and fate of pharmaceutical ingredients in coastal marine ecosystems are not well understood. To address this, the spatial and temporal distribution of 15 high-volume pharmaceuticals were measured over a 1-yr period in Narragansett Bay (RI, USA) to elucidate factors and processes regulating their concentration and distribution. Dissolved concentrations ranged from below detection to 313 ng/L, with 4 pharmaceuticals present at all sites and sampling periods. Eight pharmaceuticals were present in suspended particulate material, ranging in concentration from below detection to 44 ng/g. Partitioning coefficients were determined for some pharmaceuticals, with their range and variability remaining relatively constant throughout the study. Normalization to organic carbon content provided no benefit, indicating other factors played a greater role in regulating partitioning behavior. Within the upper bay, the continuous influx of wastewater treatment plant effluents resulted in sustained, elevated levels of pharmaceuticals. A pharmaceutical concentration gradient was apparent from this zone to the mouth of the bay. For most of the pharmaceuticals, there was a strong relationship with salinity, indicating conservative behavior within the estuary. Short flushing times in Narragansett Bay coupled with pharmaceuticals' presence overwhelmingly in the dissolved phase indicate that most pharmaceuticals will be diluted and transported out of the estuary, with only trace amounts of several compounds sequestered in sediments. The present study identifies factors controlling the temporal and spatial dynamics of dissolved and particulate pharmaceuticals; their partitioning behavior provides an increased understanding of their fate, including bioavailability in an urban estuary. Environ Toxicol Chem 2017;36:1846-1855. Published 2016 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

Narragansett Bay is an urban estuary that historically has been impacted by long-term discharge of sanitary wastewater (WW) effluents. High-density water sampling was conducted in Narragansett Bay, RI, USA, in an effort to understand the distribution and behavior of sucralose, an artificial sweetener that has shown utility as a sanitary wastewater tracer. Water samples were collected at sixty-seven sites and analyzed for sucralose, whose performance was compared to other tracers present in wastewater effluents. Concentrations of sucralose were much higher than the other tracers measured, carbamazepine and caffeine, ranging from 18 to 3180 ng/L and corresponded well with salinity (r2 = 0.88), demonstrating conservative behavior throughout the Bay. Mapped interpolation data using an empirical bayesian kriging model clearly show the spatial trends of WW and how estuarine processes influence dilution and dispersion throughout the Bay. These findings provide further evidence of the efficacy of sucralose as a wastewater tracer in large urban estuaries where continuous high-volume discharge of WW occur.

The Pawtuxet River in Rhode Island, USA has a long history of industrial activity and pollutant discharges. Metal contamination of the river sediments are well documented and historically exceeded toxicity thresholds for a variety of organisms. The Pawtuxet River dam, a low-head dam at the mouth of the river, was removed in August 2011. The removal of the dam was part of an effort to restore the riverine ecosystem after centuries of anthropogenic impact. Sediment traps were deployed below the dam to assess changes in metal concentrations and fluxes (Ag, Cd, Cr, Cu, Ni, Pb, & Zn) from the river system into Pawtuxet Cove. Sediment traps were deployed for an average duration of 24 days each, and deployments continued for 15 months after the dam was removed. Metal concentrations in the trapped suspended particulate matter (SPM) dropped following dam removal (e.g. 460 mg/kg to 276 mg/kg for Zn) and remained below pre-removal levels for most of the study. However, particle bound metal fluxes rose immediately following dam removal (e.g. 1206 g/d to 4248 g/d for Zn). Changes in flux rates during the study period indicated that river volumetric flow rates acted as the primary mechanism controlling the flux of metals into Pawtuxet Cove and ultimately upper Narragansett Bay. While SPM metal concentrations initially dropped after removal of the dam, no discernable effect on the concentration or flux of the study metals exiting the river could be associated with removal of the Pawtuxet River dam. This article is protected by copyright. All rights reserved

Greenwich Bay is an urbanized embayment of Narragansett Bay potentially impacted by multiple stressors. The present study identified the important stressors affecting Greenwich Bay benthic fauna. First, existing data and information were used to confirm that the waterbody was impaired. Second, the presence of source, stressor, and effect were established. Then linkages between source, stressor, and effect were developed. This allows identification of probable stressors adversely affecting the waterbody. Three pollutant categories were assessed: chemicals, nutrients, and suspended sediments. This weight of evidence approach indicated that Greenwich Bay was primarily impacted by eutrophication-related stressors. The sediments of Greenwich Bay were carbon enriched and low dissolved oxygen concentrations were commonly seen, especially in the western portions of Greenwich Bay. The benthic community was depauperate, as would be expected under oxygen stress. Although our analysis indicated that contaminant loads in Greenwich Bay were at concentrations where adverse effects might be expected, no toxicity was observed, as a result of high levels of organic carbon in these sediments reducing contaminant bioavailability. Our analysis also indicated that suspended sediment impacts were likely nonexistent for much of the Bay. This analysis demonstrates that the diagnostic procedure was useful to organize and assess the potential stressors impacting the ecological well-being of Greenwich Bay. This diagnostic procedure is useful for management of waterbodies impacted by multiple stressors. Environ Toxicol Chem 2017;36:449-462. © 2016 SETAC.

It is well known that copper (Cu) is toxic to marine organisms. We measured and compared the acute toxicity of several forms of Cu (including nanoCu) amended into a marine sediment with mysids and amphipods. For all the forms of Cu tested, toxicity, measured as the median lethal concentration, ranged from 708 to2400 mg Cu/kg (dry sediment) for mysids and 258 to 1070 mg Cu/kg (dry sediment) for amphipods. Environ Toxicol Chem 2018;37:2677-2681. © 2018 SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

Polybrominated diphenyl ethers (PBDEs) are “emerged” contaminants that were produced and used as flame retardants in numerous consumer and industrial applications for decades until banned. They remain ubiquitously present in the environment today. Here, a unique set of >200 biotic samples from the Antarctic was analyzed for PBDEs, including phytoplankton, krill, fish, and fur seal milk, spanning several sampling seasons over 14 years. PBDE-47 and -99 were the dominant congeners determined in all samples, constituting >60% of total PBDEs. A temporal trend was observed for ∑7PBDE concentrations in fur seal milk, where concentrations significantly increased (R2 = 0.57, p < 0.05) over time (2000–2014). Results for krill and phytoplankton also suggested increasing PBDE concentrations over time. Trends of PBDEs in fur seal milk of individual seals sampled 1 or more years apart showed no clear temporal trends. Overall, there was no indication of PBDEs decreasing in Antarctic biota yet, whereas numerous studies have reported decreasing trends in the northern hemisphere. Similar PBDE concentrations in perinatal versus nonperinatal milk implied the importance of local PBDE sources for bioaccumulation. These results indicate the need for continued assessment of contaminant trends, such as PBDEs, and their replacements, in Antarctica.

Benzotriazoles (BZTs) are used in a broad range of commercial and industrial products, particularly as metal corrosion inhibitors and as ultraviolet (UV) light stabilizer additives in plastics and polymers. In this study, dated sediment cores from two east coast estuaries were analyzed for commonly used BZTs. In Narragansett Bay, UV stabilizing BZTs (UV-BZTs) were present at high levels from 1961 on, reflecting their patent date, local production and long-term preservation in sediment. In Salem Sound, UV-BZTs were present at concentrations consistent with other coastal marine locations not influenced by BZT production. Anticorrosive BZTs (AC-BZTs) were found in both cores, with the highest levels reported to date present in Narragansett Bay, indicating sorption to, and preservation in, sediments. This study revealed that both classes of BZTs have remained structurally intact over time in coastal sediment cores, demonstrating their resistance to degradation and persistence in environmental compartments.

Seismic, pollen, stable isotope and lithologic stratigraphies of Sluice Pond, northeastern Massachusetts, were investigated to reconstruct local climate conditions from the latest Pleistocene to present. We present a new lake-level curve, constrained largely by acoustic reflectors and well-dated sediment cores from the deep basin and margin of the lake. Bulk δ34S data from the basin core provide valuable information regarding anoxia and water-column stratification. The lake-level history is corroborated with pollen-based, transfer-function-derived reconstructions of temperature and precipitation from the basin core. The lower stratigraphy reveals a time of cold/dry climate from ca. 11.7–8.2 ka BP (1 ka = 1,000 cal yr), with a minor lake-level increase centered at ca. 11.0 ka BP. An increase in regional temperature/moisture is apparent in sediments younger than 8.2 ka BP. A warm/dry climate is reconstructed from ca. 5.1–3.5 ka BP, concomitant with the well-established regional Tsuga (eastern hemlock) minimum. Sediments deposited since 3.5 ka BP reveal a general deepening of the pond and organic-rich conditions, with another minor dry episode from ca. 2.0–1.3 ka BP. Uppermost sediments record anthropogenic disturbance. The hydroclimate variability inferred from the Sluice Pond sediment record is consistent with previous reconstructions of lake level and vegetation in the southern portion of the northeastern US. It is not, however, consistent with reconstructions from locations farther north, many of which possess evidence of a dry period ca. 9.0–5.0 ka BP. The likely explanation for this discrepancy lies in air mass distribution associated with the position and amplitude of the circumpolar vortex throughout the Holocene. This new record of Holocene regional hydroclimate variability adds to the spatial coverage of existing reconstructions, and helps constrain forcings associated with such variability.

One application of nanocopper is as a wood-preserving pesticide in pressure-treated lumber. Recent research has shown that pressure-treated lumber amended with micronized copper azole (MCA), which contains nanosized copper, releases copper under estuarine and marine conditions. The form of copper released (i.e., ionic, nanocopper [1-100 nm in size]) is not fully understood but will affect the bioavailability and toxicity of the metal. In the present study, multiple lines of evidence, including size fractionation, ion-selective electrode electrochemistry, comparative toxicity, and copper speciation were used to determine the form of copper released from lumber blocks and sawdust. The results of all lines of evidence supported the hypothesis that ionic copper was released from MCA lumber and sawdust, with little evidence that nanocopper was released. For example, copper concentrations in size fractionations of lumber block aqueous leachates including unfiltered, 0.1 μm, and 3 kDa were not significantly different, suggesting that the form of copper released was in the size range operationally defined as dissolved. These results correlated with the ion-selective electrode data which detects only ionic copper. In addition, comparative toxicity testing resulted in a narrow range of median lethal concentrations (221-257 μg/L) for MCA lumber blocks and CuSO4 . We conclude that ionic copper was released from the nanocopper pressure-treated lumber under estuarine and marine conditions. Environ Toxicol Chem 2018;37:1969-1979. Published 2018 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

Little is known about the release of metal engineered nanomaterials (ENMs) from consumer goods, including lumber treated with micronized copper. Micronized copper is a recent form of antifouling wood preservative containing nanosized copper particles for use in pressure-treated lumber. The present study investigated the concentrations released and the release rate of total copper over the course of 133 d under freshwater, estuarine, and marine salinity conditions (0, 1, 10, and 30‰) for several commercially available pressure-treated lumbers: micronized copper azole (MCA) at 0.96 and 2.4 kg/m3 , alkaline copper quaternary (ACQ) at 0.30 and 9.6 kg/m3 , and chromated copper arsenate (CCA) at 40 kg/m3 . Lumber was tested as blocks and as sawdust. Overall, copper was released from all treated lumber samples. Under leaching conditions, total release ranged from 2 to 55% of the measured copper originally in the lumber, with release rate constants from the blocks of 0.03 to 2.71 (units per day). Generally, measured release and modeled equilibrium concentrations were significantly higher in the estuarine conditions compared with freshwater or marine salinities, whereas rate constants showed very limited differences between salinities. Furthermore, organic carbon was released during the leaching and demonstrated a significant relationship with released copper concentrations as a function of salinity. The results indicate that copper is released into estuarine/marine waters from multiple wood treatments including lumber amended with nanoparticle-sized copper. Environ Toxicol Chem 2018;37:1956-1968. Published 2018 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

Modeling the magnitude and distribution of sediment-bound pollutants in estuaries is often limited by incomplete knowledge of the site and inadequate sample density. To address these modeling limitations, a decision-support tool framework was conceived that predicts sediment contamination from the sub-estuary to broader estuary extent. For this study, a Random Forest (RF) model was implemented to predict the distribution of a model contaminant, triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol) (TCS), in Narragansett Bay, Rhode Island, USA. TCS is an unregulated contaminant used in many personal care products. The RF explanatory variables were associated with TCS transport and fate (proxies) and direct and indirect environmental entry. The continuous RF TCS concentration predictions were discretized into three levels of contamination (low, medium, and high) for three different quantile thresholds. The RF model explained 63% of the variance with a minimum number of variables. Total organic carbon (TOC) (transport and fate proxy) was a strong predictor of TCS contamination causing a mean squared error increase of 59% when compared to permutations of randomized values of TOC. Additionally, combined sewer overflow discharge (environmental entry) and sand (transport and fate proxy) were strong predictors. The discretization models identified a TCS area of greatest concern in the northern reach of Narragansett Bay (Providence River sub-estuary), which was validated with independent test samples. This decision-support tool performed well at the sub-estuary extent and provided the means to identify areas of concern and prioritize bay-wide sampling.

A challenge in environmental passive sampling is determining when equilibrium is achieved between the sampler, target contaminants, and environmental phases. A common approach is the use of performance reference compounds (PRCs) to estimate target contaminant sampling rates and indicate degree of sampler equilibrium. One logistical issue associated with using PRCs is their sometimes exorbitant cost. To address PRC expense, this investigation 1) compared the performance of inexpensive PRCs (deuterated PAHs) and expensive PRCs ((13) C-labeled PCBs) to estimate dissolved PCB concentrations in freshwater and marine deployments, and 2) evaluated the use of smaller quantities of PRC relative to regular amounts used for estimating dissolved PAH and PCB concentrations. Saltwater and freshwater site average differences between total dissolved PCB concentrations calculated using the 2 classes of PRCs was 34 pg/L (20%) and 340 pg/L (51%), respectively, and in some deployments, statistical differences in PCB concentrations generated by the 2 types of PRCs were detected. However, no statistical differences were detected between total dissolved PAH and PCB for the 3 quantities of PRCs. In both investigations, individual dissolved PCB congeners and PAH compounds demonstrated comparable behavior as those expressed as total PCB or PAH dissolved concentrations. This research provides evidence that in some applications passive sampling using inexpensive and smaller quantities of PRCs can yield cost savings of approximately 75%. This approach appears most promising in the marine water column and when focusing on dissolved concentrations of low and medium molecular weight congeners or total PCBs.

Combustion-derived aerosols in the marine boundary layer have been poorly studied, especially in remote environments such as the open Atlantic Ocean. The tropical Atlantic has the potential to contain a high concentration of aerosols, such as black carbon, due to the African emission plume of biomass and agricultural burning products. Atmospheric particulate matter samples across the tropical Atlantic boundary layer were collected in the summer of 2010 during the southern hemispheric dry season when open fire events were frequent in Africa and South America. The highest black carbon concentrations were detected in the Caribbean Sea and within the African plume, with a regional average of 0.6 μg m−3 for both. The lowest average concentrations were measured off the coast of South America at 0.2 to 0.3 μg m−3. Samples were quantified for black carbon using multiple methods to provide insights into the form and stability of the carbonaceous aerosols (i.e., thermally unstable organic carbon, soot like, and charcoal like). Soot-like aerosols composed up to 45% of the carbonaceous aerosols in the Caribbean Sea to as little as 4% within the African plume. Charcoal-like aerosols composed up to 29% of the carbonaceous aerosols over the oligotrophic Sargasso Sea, suggesting that non-soot-like particles could be present in significant concentrations in remote environments. To better apportion concentrations and forms of black carbon, multiple detection methods should be used, particularly in regions impacted by biomass burning emissions.

In this study, methods and approaches were developed and tested to assess changes in contaminant fluxes resulting from dam removal in a riverine system. Sediment traps and passive samplers were deployed to measure particulate and dissolved polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in the water column prior to and following removal of a small, low-head dam in the Pawtuxet River, an urbanized river located in Cranston, RI, USA. During the study, concentrations of particulate and dissolved PAHs ranged from 21.5 to 103 μg/g and from 68 to 164 ng/L, respectively. Overall, temporal trends of PAHs showed no increases in either dissolved or particulate phases following removal of the dam. Dissolved concentrations of PCBs were very low, remaining below 1.72 ng/L at all sites. Particulate PCB concentrations across sites and time showed slightly greater variability, ranging from 80 to 469 ng/g, but with no indication that dam removal influenced any increases. Particulate PAHs and PCBs were sampled continuously at the site located below the dam and did not show sustained increases in concentration resulting from dam removal. The employment of passive sampling technology and sediment traps was highly effective in monitoring the concentrations and flux of contaminants moving through the river system. Variations in river flow had no effect on the concentration of contaminants in the dissolved or particulate phases, but did influence the flux rate of contaminants exiting the river. Overall, dam removal did not cause measurable sediment disturbance or increase the concentration or fluxes of dissolved or particulate PAHs and PCBs. This is due in large part to low volumes of impounded sediment residing above the dam and highly armored sediments in the river channel, which limited erosion. Results from this study will be used to improve methods and approaches that assess the short- and long-term impacts ecological restoration activities such as dam removal have on the release and transport of sediment-bound contaminants.

The behavior and fate of nanoparticles (NPs) in the marine environment are largely unknown and potentially have important environmental and human health implications. The aggregation and fate of NPs in the marine environment are greatly influenced by their interactions with seawater and dissolved organic carbon (DOC). In the present study, the stability and aggregation of 30-nm-diameter silver nanoparticles (AgNPs) capped with citrate and polyvinylpyrrolidone (PVP; AgNP-citrate and AgNP-PVP) and 21-nm-diameter titanium dioxide (TiO(2)) NPs as affected by seawater salinity and DOC were investigated by measuring hydrodynamic diameters and zeta potentials. The added DOC (in humic acid form) stabilized the 3 types of NPs when the seawater salinities were ≤5 parts per thousand (ppt), but the stabilizing effect of DOC was reduced by a higher salinity (e.g., 30 ppt). In addition, AgNP-PVP was more stable than AgNP-citrate in seawater, indicating that surface capping agents and stabilization mechanisms govern the stability and aggregation of NPs. Statistical analysis showed that salinity is the most dominant influence on the stability and aggregation of AgNPs and TiO(2) NPs, followed by DOC. These findings expand our knowledge on the behavior of AgNPs and TiO2 NPs in seawater and indicate that the fate of these NPs will be primarily to aggregate in the water column, precipitate, and accumulate in sediments following release into the marine environment.

Ecotoxicological information for most contaminants is limited to a small number of taxa, and these are generally restricted to comparatively hardy organisms that are readily extractable from test media and easily identifiable. Advances in DNA sequencing can now provide a comprehensive view of benthic invertebrate diversity. The authors applied 454 pyrosequencing to examine the responses of benthic communities in microcosms exposed to sediments with elevated concentrations of triclosan, the endpoint being eukaryl communities that have successfully vertically migrated through the manipulated sediments. The biological communities associated with the 3 treatments (control triclosan, low triclosan [14 mg/kg], and high triclosan [180 mg/kg]) clustered into 3 groups: control/low (n = 6 controls and 4 low), moderate (n = 2 low), and high (n = 5 high). One sample was discarded as an outlier. The most pronounced change as a response to triclosan was the loss of number of metazoan operational taxonomic units (OTUs), indicative of the control/low and moderate groups, with this being most evident in the range of taxa associated with the classes Chromadorea and Bivalvia and the phylum Kinorhyncha. The authors also describe a range of other taxa that aided discrimination between the groups; compare findings with traditionally obtained meio- and macrofaunal communities obtained from the same experiment; and illustrate some of the advantages and limitations associated with both the molecular and traditional approaches. The described approach illustrates the capacity for amplicon sequencing to provide ecologically relevant information that can be used to strengthen an understanding of how sedimentary communities respond to a range of environmental stressors. Environ Toxicol Chem 2014;33:359–369. © 2014 SETAC

Contaminants enter marine and estuarine environments and pose a risk to human and ecological health. Recently, passive sampling devices have been utilized to estimate dissolved concentrations of contaminants of concern (COCs), such as polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). In the present study, the performance of 3 common passive samplers was evaluated for sampling PAHs and PCBs at several stations in the temperate estuary Narragansett Bay, Rhode Island, USA. Sampler polymers included polyethylene (PE), polydimethylsiloxane (PDMS)-coated solid-phase microextraction (SPME) fibers, and polyoxymethylene (POM). Dissolved concentrations of each contaminant were calculated using measured sampler concentrations adjusted for equilibrium conditions with performance reference compounds (PRCs) and chemical-specific partition coefficients derived in the laboratory. Despite differences in PE and POM sampler concentrations, calculated total dissolved concentrations ranged from 14 ng/L to 93 ng/L and from 13 pg/L to 465 pg/L for PAHs and PCBs, respectively. Dissolved concentrations of PAHs were approximately 3 times greater based on POM compared to PE, while dissolved concentrations of PCBs based on PE were approximately 3 times greater than those based on POM. Concentrations in SPME were not reported due to the lack of detectable chemical in the amount of PDMS polymer deployed. Continued research is needed to improve and support PE and POM use for the routine monitoring of COCs. For example, a better understanding of the use of PRCs with POM is critically needed.

Measuring dissolved concentrations of emerging contaminants, such as polybrominated diphenyl ethers (PBDEs) and triclosan, can be challenging due to their physicochemical properties resulting in low aqueous solubilities and association with particles. Passive sampling methods have been applied to assess dissolved concentrations in water and sediments primarily for legacy contaminants. Although the technology is applicable to some emerging contaminants, the use of passive samplers with emerging contaminants is limited. In the present study, the performance of 3 common passive samplers was evaluated for sampling PBDEs and triclosan. Passive sampling polymers included low-density polyethylene (PE) and polyoxymethylene (POM) sheets, and polydimethylsiloxane (PDMS)-coated solid-phase microextraction (SPME) fibers. Dissolved concentrations were calculated using measured sampler concentrations and laboratory-derived partition coefficients. Dissolved tri-, tetra-, and pentabrominated PBDE congeners were detected at several of the study sites at very low pg/L concentrations using PE and POM. Calculated dissolved water concentrations of triclosan ranged from 1.7 ng/L to 18 ng/L for POM and 8.8 ng/L to 13 ng/L for PE using performance reference compound equilibrium adjustments. Concentrations in SPME were not reported due to lack of detectable chemical in the PDMS polymer deployed. Although both PE and POM were found to effectively accumulate emerging contaminants from the water column, further research is needed to determine their utility as passive sampling devices for emerging contaminants. Environ Toxicol Chem 2013;32:2190–2196. © 2013 SETAC

In many coastal watersheds and ecosystems, rivers discharging to estuaries receive waters from domestic wastewater-treatment plants resulting in the release and distribution of pharmaceuticals to the marine environment. In the present study, 15 active pharmaceutical ingredients were measured regularly over 1 yr in the dissolved and particulate phases as they entered Narragansett Bay from the Pawtuxet River in Cranston (Rhode Island, USA). Of the active pharmaceutical ingredients measured, 14 were consistently present in the dissolved phase, with concentrations ranging from below detection to310 ng/L, whereas 8 were present in the particulate phase (0.2-18 ng/g). Partition coefficients (K

Sites throughout Boston Harbor were analyzed for caffeine to assess its utility as a tracer in identifying sources of sanitary wastewater. Caffeine ranged from 15ng/L in the outer harbor to a high of 185ng/L in the inner harbor. Inner harbor concentrations were a result of combined sewage overflow (CSO) events as well as illicit discharge of sanitary sewage into municipal storm drains. Comparing current results to data from 1998 to 1999 shows reductions in caffeine levels. Reductions are attributed to termination of effluent discharge to the harbor, declines in the number of CSOs and discharge volume along with efforts to eliminate illicit discharges. Spatial distributions of caffeine identified CSOs as major contemporary sources to the inner harbor. The findings further establish the utility of caffeine as a tracer for sanitary wastewater contamination in urban estuaries and demonstrate the efficacy of pollution reduction strategies undertaken in recent decades in Boston Harbor.

Adsorption of hydrophobic organic contaminants (HOCs) to black carbon is a well-studied phenomenon. One emerging class of engineered black carbon materials are single-walled carbon nanotubes (SWNTs). Little research has investigated the potential of SWNT to adsorb and sequester HOCs in complex environmental systems. This study addressed the capacity of SWNT, amended to polychlorinated biphenyl (PCB)-contaminated New Bedford Harbor (NBH) sediment, to reduce the toxicity and bioaccumulation of these HOCs to benthic organisms. Overall, SWNT amendments increased the survival of two benthic estuarine invertebrates, Americamysis bahia and Ampelisca abdita, and reduced the accumulation of PCBs to the benthic polychaete, Nereis virens. Reduction in PCB bioaccumulation by SWNT was independent of Kow. Further, passive sampling-based estimates of interstitial water concentrations indicated that SWNT reduced PCB bioavailability. Results from this study suggest that SWNT are a good adsorbent for PCBs and might be useful for remediation in the future once SWNT manufacturing technology improves and costs decrease.

Triclosan (5-chloro-2-[2,4-dichlorophenoxy]phenol) is a relatively new, commonly used antimicrobial compound found in many personal care products. Triclosan is toxic to marine organisms at the micrograms per liter level, can photodegrade to a dioxin, can accumulate in humans, and has been found to be stable in marine sediments for over 30 years. To determine the effects of triclosan on marine benthic communities, intact sediment cores were brought into the laboratory and held under flowing seawater conditions. A 2-cm layer of triclosan-spiked sediment was applied to the surface, and after a two-week exposure the meio- and macrofaunal communities were assessed for differences in composition relative to nonspiked cores. A high triclosan treatment (180 mg/kg dry wt) affected both the meio- and the macrobenthic communities. There were no discernible differences with a low-triclosan treatment (14 mg/kg dry wt). This exposure method is effective for testing the benthic community response to sediment contaminants, but improvements should be made with regard to the amount and method of applying the overlying sediment to prevent smothering of fragile benthic organisms. Environ. Toxicol. Chem. 2013;32:384–392. © 2012 SETAC

A slow-release, injectable implant method was developed for administering test chemicals to cunners Tautogolabrus adspersus. The implant is composed of a matrix of a test chemical homogenized in a mixture of Ethocel (Dow Chemical) and coconut oil. The effectiveness of a subcutaneous implant of this matrix in vivo was determined by tracing plasma concentrations of three separate chemicals (estradiol, ethynylestradiol, and atrazine) over time in treated male cunners. Release from the implant was determined based on the percentage of the implanted concentration of test chemical (plus metabolites) that was detected in fish plasma over a 1–2-week period after implantation. Circulating estrogen concentrations measured in plasma from two different cunners that received the estradiol implant were almost identical, indicating that there is a reasonably even distribution of test chemical within the Ethocel–coconut oil preparation and that individual variability may be minimal for release of test chemical f...

Triclosan is an antimicrobial compound that has been widely used in consumer products such as toothpaste, deodorant, and shampoo. Because of its widespread use, triclosan has been detected in various environmental media, including wastewater, sewage sludge, surface waters, and sediments. Triclosan is acutely toxic to numerous aquatic organisms, but very few studies have been performed on estuarine and marine benthic organisms. For whole sediment toxicity tests, the sediment-dwelling estuarine amphipod, Ampelisca abdita, and the epibenthic mysid shrimp, Americamysis bahia, are commonly used organisms. In the present study, median lethal concentration values (LC50) were obtained for both of these organisms using water-only and whole sediment exposures. Acute 96-h water-only toxicity tests resulted in LC50 values of 73.4 and 74.3 µg/L for the amphipod and mysid, respectively. For the 7-d whole sediment toxicity test, LC50 values were 303 and 257 mg/kg (dry wt) for the amphipod and mysid, respectively. Using equilibrium partitioning theory, these whole sediment values are equivalent to interstitial water LC50 values of 230 and 190 µg/L for the amphipod and mysid, respectively, which are within a threefold difference of the observed 96-h LC50 water-only values. Triclosan was found to accumulate in polychaete tissue in a 28-d bioaccumulation study with a biota-sediment accumulation factor of 0.23 kg organic carbon/kg lipid. These data provide some of the first toxicity data for triclosan with marine benthic and epibenthic species while also indicating a need to better understand the effects of other forms of sediment carbon, triclosan ionization, and organism metabolism of triclosan on the chemical's behavior and toxicity in the aquatic environment.

In this study, a reverse-phase HPLC method incorporating a ternary solvent system was developed to analyze most polar and non-polar chlorophylls and carotenoids present in phytoplankton. The method is based on an RP-C16-Amide column and provided excellent peak resolution of most taxonomically important pigments and an elution profile different than C8 or C18 columns provide. Analysis of mixed pigment standards, extracts of phytoplankton monocultures, and field samples showed that this method was able to resolve more than sixty pigments, ranging from very polar acidic chlorophylls to the non-polar hydrocarbon carotenes in less than 36 min. This included chlorophylls c1, c2 and c3, divinyl chlorophylls a and b, the carotenoids lutein and zeaxanthin and some recently discovered pigments. The ability of this method to resolve divinyl chl b from monovinyl chl b and divinyl chl a from monovinyl chl a is particularly important for the quantification and identification of the marine cyanobacteria Prochlorococcus spp. in oceanic waters. The described protocol is sensitive and reproducible and can be used to assess the distribution and dynamics of major phytoplankton groups in marine and freshwater ecosystems.

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. Environ. Toxicol. Chem. 2010;29:742–750. © 2009 SETAC

Polyethylene sampler uptake was compared to polychaete uptake to assess bioavailability of polychlorinated biphenyls (PCBs) from resuspended sediments. New Bedford Harbor (MA, U.S.) sediment contaminated with PCBs, was resuspended under four different water column oxidation conditions: resuspension alone, resuspension under aeration, resuspension under helium, and no resuspension (control). Residuals were tested for differences in PCB availability to the marine polychaete Nereis virens and to polyethylene (PE) passive samplers. Few significant differences between the four resuspension treatments were observed: under aeration, three of 23 PCBs analyzed showed significant increases in polychaete accumulation, while resuspension alone showed increased concentrations in PE samplers for nine of 23 PCBs. Otherwise, no differences were observed and overall we concluded that resuspension had no effect on residual PCB availability. The relationship between disequilibrium-corrected PE and lipid-normalized polychaete PCB concentrations was nearly 1:1 with a strong linear correlation (r2 = 0.877), demonstrating PCBs are taken up similarly into PE and lipid. On average, PE samplers suggested dissolved PCB concentrations 3.6 times greater than those calculated with lipid-water partitioning, though on a congener-specific basis this was only observed for lower chlorinated PCBs; for higher chlorinated PCBs, PE-water partitioning suggested lower dissolved concentrations than those based on lipid. Organic carbon (OC)-water and OC and black carbon combined (OC+BC)-water partitioning suggested average dissolved concentrations 29 and 10 times greater, respectively, than those estimated with lipid-water partitioning. This demonstrates that PE-measured porewater concentrations can provide a more reliable estimate of bioavailability than sediment geochemistry.

The distribution of Triclosan within the Hudson River Estuary can be explained by a balance among the overall effluent inputs from municipal sewage treatment facilities, dilution of Triclosan concentrations in the water column with freshwater and seawater inputs, removal of Triclosan from the water column by adsorption to particles, and loss to photodegradation. This study shows that an average water column concentration of 3+/-2 ng/l (in the lower Hudson River Estuary) is consistent with an estimate for dilution of average wastewater concentrations with seawater and calculated rates of adsorption of Triclosan to particles. An average Triclosan sediment concentration of 26+/-11 ng/g would be in equilibrium with the overlying water column if Triclosan has a particle-to-water partitioning coefficient of k(d) approximately 10(4), consistent with laboratory estimates.

In aquatic systems where metal contaminated sediments are present, the potential exists for metals to be released to the water column when sediment resuspension occurs. The release and partitioning behavior of sediment-bound heavy metals is not well understood during resuspension events. In this study, the release of Cd, Cu, Hg, Ni, Pb and Zn from sediments during resuspension was evaluated using reference sediments with known physical and chemical properties. Sediment treatments with varying quantities of acid volatile sulfide (AVS), total organic carbon (TOC), and different grain size distributions were resuspended under controlled conditions to evaluate their respective effects on dissolved metal concentrations. AVS had the greatest effect on limiting release of dissolved metals, followed by grain size and TOC. Predictions of dissolved concentrations of Cd, Ni, Pb and Zn were developed based on the formulated sediment Sigma(metal)/AVS ratios with Sigma(metal) being the total sediment metal concentration. Predicted values were compared to measured dissolved metal concentrations in contaminated field sediments resuspended under identical operating conditions. Metal concentrations released from the field sediments were low overall, in most cases lower than predicted values, reflecting the importance of other binding phases. Overall, results indicate that for sulfidic sediments, low levels of the study metals are released to the dissolved phase during short-term resuspension.

Estuaries and lakes are undergoing anthropogenic alterations as development and industry intensify in the modern world. Assessing the ecological health of such water bodies is difficult because accurate accounts of pre-anthropogenic estuarine/lacustrine conditions do not exist. Sediments preserved in water bodies provide archives of environmental changes that can be used to understand both natural and anthropogenic forcings. Here, a high-resolution, multi-proxy approach is used to reconstruct environmental conditions of the Pettaquamscutt River Estuary, Rhode Island, over the last millennium. Two specific time periods reveal anthropogenic alterations to sediment supply and water-column productivity. First, European land clearance at the end of the seventeenth century caused two decades of increased sediment transport through the watershed and increased primary productivity in the water column. Turbidity increases associated with increased water column biomass likely limited green sulfur bacteria that reside below the oxycline. The second anthropogenic effect began in the 1950s with increased residential development in the watershed. Evidence of resulting cultural eutrophication is apparent in both stable nitrogen isotope values as well as in productivity proxies. This effect is likely related to residential development in the watershed and the use of septic systems to treat human waste. These results demonstrate that true base-line conditions of the estuary have not occurred for over three centuries, and that anthropogenic effects can last on the order of decades. The Pettaquamscutt River record serves as a model for using high-resolution sediment records to better understand anthropogenic forcing to natural estuarine/lacustrine systems.

The Taunton River is a partially mixed tidal estuary in southeastern Massachusetts (USA) which has received significant contaminant inputs, yet little information exists on the history of discharge and the subsequent fate of these contaminants. Three sediment cores taken along a transect were analyzed, reconstructing the spatial and temporal trends of pollution in the estuary. A combination of radiometric dating, contaminant markers, and storm layers from major hurricanes were used to establish age models and sedimentation rates. Age estimates obtained from the different dating methods compared well, establishing an accurate history of contaminant release to the estuary. Polycyclic aromatic hydrocarbons (PAHs) were present in one core at depths corresponding to the early 1860s, earlier than previously established dates of introduction. Temporal and spatial trends of Cr, Cu, Hg and Pb indicated multiple sources of varying input to the river. Polychlorinated biphenyls (PCBs) were present in each of the cores from the 1930s onward, with elevated levels still present in surficial sediments at several sites. A unique organic compound, Topanol, which was produced locally was used as a tracer to track contaminant transport in the river. Tracer data indicates that contaminants are still being transported and deposited to surficial sediments at high concentrations well after their discharge. This reconstruction demonstrates the utility of using multiple dating proxies where often the sole use of radiometric dating techniques is not an option and provides insights into the fate of contaminants discharged decades ago but continue to represent environmental risks.

Benzotriazoles (BZTs) are a class of organic compounds that have been used as metal anticorrosive and ultraviolet stabilizer additives in a wide range of commercial and industrial applications. These chemicals have been in commercial production and use since the late 1950s with many compounds being produced at volumes exceeding one half million kilograms annually. Some BZT compounds exhibit behaviors characteristic of persistent organic pollutants, and emerging evidence indicates long-term preservation and persistence in sediments. Other BZTs associated with anticorrosion applications appear to be highly resistant to degradation, relatively water soluble, and toxic to aquatic organisms. A significant number of BZTs have been discovered in different environmental compartments at levels justifying further study for fate, transport, environmental persistence, and potential adverse effects. Consequently, BZTs should be considered contaminants of emerging concern in the environment with POP-like characteristics.

Ammonia occurs in marine waters including effluents, receiving waters, and sediment interstitial waters. At sufficiently high concentrations, ammonia can be toxic to aquatic species. Toxicity identification evaluation (TIE) methods provide researchers with tools for identifying aquatic toxicants. For identifying ammonia toxicity, there are several possible methods including pH alteration and volatilization, Ulva lactuca addition, microbial degradation, and zeolite addition. Zeolite addition has been used successfully in freshwater systems to decrease ammonia concentrations and toxicity for several decades. However, zeolite in marine systems has been used less because ions in the seawater interfere with zeolite's ability to adsorb ammonia. The objective of this study was to develop a zeolite method for removing ammonia from marine waters. To accomplish this objective, we performed a series of zeolite slurry and column chromatography studies to determine uptake rate and capacity and to evaluate the effects of salinity and pH on ammonia removal. We also assessed the interaction of zeolite with several toxic metals. Success of the methods was also evaluated by measuring toxicity to two marine species: the mysid Americamysis bahia and the amphipod Ampelisca abdita. Column chromatography proved to be effective at removing a wide range of ammonia concentrations under several experimental conditions. Conversely, the slurry method was inconsistent and variable in its overall performance in removing ammonia and cannot be recommended. The metals copper, lead, and zinc were removed by zeolite in both the slurry and column treatments. The zeolite column was successful in removing ammonia toxicity for both the mysid and the amphipod, whereas the slurry was less effective. This study demonstrated that zeolite column chromatography is a useful tool for conducting marine water TIEs to decrease ammonia concentrations and characterize toxicity.

The release of contaminants from sediments is an important problem facing environmental managers concerned with issues such as maintenance dredging, habitat restoration and dredge spoil placement. While there are laboratory methods to assess the remobilization of contaminants from resuspended sediments, little is known about how their operating characteristics influence a sediments response to resuspension. In this study, a particle entrainment simulator (PES) for resuspending sediments was evaluated by assessing variability among replicates and over operation time (12 h) for three estuarine sediments. These sediments varied in physical and chemical properties as well as the degree of metal contamination. Results showed that under identical resuspension conditions, there was low variability among sediment replicates. Sediment properties and the degree of metal contamination affected the magnitude and variation in water column parameters and contaminant release. Fine-grained sediments affected water column parameters, which stabilized over several hours of resuspension. While metal concentrations in the aqueous and particulate samples varied throughout operation, variation was highest for Cd and Ni. Compared to other methods used to evaluate the effects of sediment resuspension, the PES has operational advantages such as the ability to monitor water column conditions and resuspend sediment at specified energy levels. Overall, the PES provided reproducible conditions of resuspension effects among sediments varying in composition and contamination, demonstrating its value as a tool to evaluate contaminant mobility.

Periodically, marine sediments are subjected to physical processes which resuspend them into the water column, releasing previously sequestered metals. The role of resuspension energy and duration on release and subsequent redistribution of sediment bound metals was measured experimentally using a particle entrainment simulator. Two metal contaminated anoxic sediments with different physical and chemical characteristics were resuspended for 12 h at energies of 2 and 5 dynes cm(-2). Samples were taken at specified intervals, and the water column pH, Eh and dissolved oxygen levels were monitored continuously. Over time, metal concentrations increased in the particulate (nonfilterable > or = 1 microm) and filterable (< 1 microm) phases of the overlying water. In general, metal enrichment followed the Irving-Williams order of complex stability. Overall, the sediment's chemical and physical composition were major factors in determining the amount of metal released, more so than the level of resuspension energy applied. These results provide insight into how physical and chemical processes interact during sediment resuspension to release sediment bound metals and control their phase distribution in the water column.