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Microplastics (MP) are distributed throughout ecosystems and settle into sediments where they may threaten benthic communities; however, methods for quantifying MP in sediments have not been standardized. This study compares two methods for analyzing MP in sediments, including extraction and identification, and provides recommendations for improvement. Two laboratories processed sediment samples using two methods, referred to as "core" and "augmentation", and identified particles with visual microscopy and spectroscopy. Using visual microscopy, the augmentation method yielded mean recoveries (78%) significantly greater than the core (47%) (p = 0.03), likely due to the use of separatory funnels in the former. Spectroscopic recovery of particles was lower at 42 and 54% for the core and augmentation methods, respectively. We suspect the visual identification recoveries are overestimations from erroneous identification of non-plastic materials persisting post-extraction, indicating visual identification alone is not an accurate method to identify MP, particularly in complex matrices like sediment. However, both Raman and FTIR proved highly accurate at identifying recovered MP, with 96.7% and 99.8% accuracy, respectively. Low spectroscopic recovery of spiked particles indicates that MP recovery from sediments is lower than previously assumed, and MP may be more abundant in sediments than current analyses suggest. To our knowledge, likely due to the excessive time/labor-intensity associated with MP analyses, this is the first interlaboratory study to quantify complete method performance (extraction, identification) for sediments, with regards to capabilities and limitations. This is essential as regulatory bodies move toward long-term environmental MP monitoring.

As contaminant exposures in aquatic ecosystems continue to increase, the need for streamlining research efforts in environmental toxicology using predictive frameworks also grows. One such framework is the adverse outcome pathway (AOP). An AOP framework organizes and utilizes toxicological information to connect measurable molecular endpoints to an adverse outcome of regulatory relevance via a series of events at different levels of biological organization. Molecular endpoints or biomarkers are essential to develop AOPs and are valuable early warning signs of the toxicity of pollutants, including contaminants of emerging concern. Ecological risk-assessment approaches using tools such as biomarkers and AOPs benefit from identification of molecular targets conserved across species. Bivalve models are useful in such approaches and integral to our understanding of ecological and human health risks associated with contaminant exposures. We discuss the value of using biomarker approaches in bivalve models to meet the demands of twenty-first-century toxicology. Environ Toxicol Chem 2020;39:1472-1484. © 2020 SETAC.

Quantum dots (QDs) are engineered semiconductor nanocrystals with unique fluorescent, quantum confinement, and quantum yield properties, making them valuable in a range of commercial and consumer imaging, display, and lighting technologies. Production and usage of QDs are increasing, which increases the probability of these nanoparticles entering the environment at various phases of their life cycle. This review discusses the major types and applications of QDs, their potential environmental exposures, fates, and adverse effects on organisms. For most applications, release to the environment is mainly expected to occur during QD synthesis and end-product manufacturing since encapsulation of QDs in these devices prevents release during normal use or landfilling. In natural waters, the fate of QDs is controlled by water chemistry, light intensity, and the physicochemical properties of QDs. Research on the adverse effects of QDs primarily focuses on sublethal endpoints rather than acute toxicity, and the differences in toxicity between pristine and weathered nanoparticles are highlighted. A proposed oxidative stress adverse outcome pathway framework demonstrates the similarities among metallic and carbon-based QDs that induce reactive oxygen species formation leading to DNA damage, reduced growth, and impaired reproduction in several organisms. To accurately evaluate environmental risk, this review identifies critical data gaps in QD exposure and ecological effects, and provides recommendations for future research. Future QD regulation should emphasize exposure and sublethal effects of metal ions released as the nanoparticles weather under environmental conditions. To date, human exposure to QDs from the environment and resulting adverse effects has not been reported.

Nanoplastics (NPs) are present in food, soil, water, air, and personal care products, resulting in concern regarding exposure and potential adverse effects. NPs principally arise from the degradation of larger-sized plastic particles. The uptake and effects of NPs in humans are not yet known. However, recent laboratory studies have documented the uptake and adverse effects of NPs from the cellular to the community level. As NPs are in the size range of particles that can be absorbed by cells, research on these materials should be accelerated to properly assess their potential risks.

Graphene is a 2-dimensional nanomaterial with unique mechanical, thermal, electrical, and optical properties. With increasing applications of graphene-family nanomaterials (GFNs) in electronics, biomedicine, and surface coatings, concern for their impacts on aquatic ecosystems is rising. Current information on the toxicity of GFNs, including graphene oxide, is scarce. Filter-feeding bivalves, such as eastern oysters, are good models for nanomaterial exposure studies. We present results from a 72-h static renewal oyster study using 1 and 10 mg/L graphene oxide, which, to our knowledge, is the first report on in vivo effects of graphene oxide exposures in marine bivalves. Water samples were analyzed for graphene oxide concentration and size assessments. Gill and digestive gland tissues were evaluated for lipid peroxidation and glutathione-S-transferase (GST) activity. In addition, gill sections were fixed for histopathological analyses. Elevated lipid peroxidation was noted in oysters exposed to 10 mg/L graphene oxide. No significant changes in GST activity were observed, but reduced total protein levels were found in digestive gland tissues of exposed oysters at both concentrations. Loss of mucous cells, hemocytic infiltration, and vacuolation were observed in gills of exposed oysters. The results indicate that short-term graphene oxide exposures can induce oxidative stress and epithelial inflammation and adversely affect overall oyster health. Further investigations regarding the fate and sublethal effects of graphene oxide are critical to understanding the risks associated with a rapidly growing graphene consumer market. Environ Toxicol Chem 2019;38:820-830. Published 2019 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 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.

Achieving sustainable agricultural productivity and global food security are two of the biggest challenges of the new millennium. Addressing these challenges requires innovative technologies that can uplift global food production, while minimizing collateral environmental damage and preserving the resilience of agroecosystems against a rapidly changing climate. Nanomaterials with the ability to encapsulate and deliver pesticidal active ingredients (AIs) in a responsive (for example, controlled, targeted and synchronized) manner offer new opportunities to increase pesticidal efficacy and efficiency when compared with conventional pesticides. Here, we provide a comprehensive analysis of the key properties of nanopesticides in controlling agricultural pests for crop enhancement compared with their non-nanoscale analogues. Our analysis shows that when compared with non-nanoscale pesticides, the overall efficacy of nanopesticides against target organisms is 31.5% higher, including an 18.9% increased efficacy in field trials. Notably, the toxicity of nanopesticides toward non-target organisms is 43.1% lower, highlighting a decrease in collateral damage to the environment. The premature loss of AIs prior to reaching target organisms is reduced by 41.4%, paired with a 22.1% lower leaching potential of AIs in soils. Nanopesticides also render other benefits, including enhanced foliar adhesion, improved crop yield and quality, and a responsive nanoscale delivery platform of AIs to mitigate various pressing biotic and abiotic stresses (for example, heat, drought and salinity). Nonetheless, the uncertainties associated with the adverse effects of some nanopesticides are not well-understood, requiring further investigations. Overall, our findings show that nanopesticides are potentially more efficient, sustainable and resilient with lower adverse environmental impacts than their conventional analogues. These benefits, if harnessed appropriately, can promote higher crop yields and thus contribute towards sustainable agriculture and global food security.

Plastic pollution in marine systems degrades over time through numerous weathering processes. Microplastics (MPs) are small (

Microplastics are small plastic particles found ubiquitously in marine environments. In this study, a hybridized method was developed for the extraction of microplastics (45-1000 μm) from sediments using sodium bromide solution for density separation. Method development was tested using spiked microplastics as internal standards. The method was then used to extract microplastics from sediments in Narragansett Bay, Rhode Island, USA. Suspect microplastics were analyzed with Raman spectroscopy. Microplastic abundance ranged from 40 particles/100 g sediment to 4.6 million particles/100 g sediment (wet weight). Cellulose acetate fibers were the most abundant microplastic. These results are some of the first data for microplastics in Rhode Island sediments.

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 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.

Engineered nanomaterials (ENM) are a growing aspect of the global economy, and their safe and sustainable development, use, and eventual disposal requires the capability to forecast and avoid potential problems. This review provides a framework to evaluate the health and safety implications of ENM releases into the environment, including purposeful releases such as for antimicrobial sprays or nano-enabled pesticides, and inadvertent releases as a consequence of other intended applications. Considerations encompass product life cycles, environmental media, exposed populations, and possible adverse outcomes. This framework is presented as a series of compartmental flow diagrams that serve as a basis to help derive future quantitative predictive models, guide research, and support development of tools for making risk-based decisions. After use, ENM are not expected to remain in their original form due to reactivity and/or propensity for hetero-agglomeration in environmental media. Therefore, emphasis is placed on characterizing ENM as they occur in environmental or biological matrices. In addition, predicting the activity of ENM in the environment is difficult due to the multiple dynamic interactions between the physical/chemical aspects of ENM and similarly complex environmental conditions. Others have proposed the use of simple predictive functional assays as an intermediate step to address the challenge of using physical/chemical properties to predict environmental fate and behavior of ENM. The nodes and interactions of the framework presented here reflect phase transitions that could be targets for development of such assays to estimate kinetic reaction rates and simplify model predictions. Application, refinement, and demonstration of this framework, along with an associated knowledgebase that includes targeted functional assay data, will allow better de novo predictions of potential exposures and adverse outcomes.

The possibility of graphene oxide (GO) exposure to the environment has spurred several studies investigating the fate of this nanoparticle (NP). However, there is currently little or no data on the fate of GO in estuarine and marine waters. This study investigated the aggregation, sedimentation, and transformation of GO in saline waters, considering the roles of salinity (0-50 ‰), light (visible light and solar irradiation), and aging, among others. The attachment efficiency of GO reached unity at 1.33 ‰. The sedimentation rate of GO increased with salinity up to 10 ‰ after which it decreased due to formation of ramified GO agglomerates and media density. On the basis of the sedimentation rate determined at 30 ‰ (0.121 m/d), the residence time of GO agglomerates in the euphotic zone of typical open oceans will exceed 500 days. Aging in the presence of visible light increased the relative abundance of the GO's aromatic (C-C/C=C) fraction, reducing the NP. Reduction of GO in visible light was confirmed via UV-vis and Raman spectroscopic techniques. Reduction of GO was faster under solar irradiation. This study demonstrates that when introduced into saline waters, GO will undergo a range of transformations affecting its fate and potential effects to aquatic organisms.

One of the key components for environmental risk assessment of engineered nanomaterials (ENMs) is data on bioaccumulation potential. Accurately measuring bioaccumulation can be critical for regulatory decision-making regarding material hazard and risk, and for understanding the mechanism of toxicity. This perspective provides expert guidance for performing ENM bioaccumulation measurements across a broad range of test organisms and species. To accomplish this aim, we critically evaluated ENM bioaccumulation within three categories of organisms: single-celled species, multicellular species excluding plants, and multicellular plants. For aqueous exposures of suspended single-celled and small multicellular species, it is critical to perform a robust procedure to separate suspended ENMs and small organisms to avoid overestimating bioaccumulation. For many multicellular organisms, it is essential to differentiate between the ENMs adsorbed to external surfaces or in the digestive tract and the amount absorbed across epithelial tissues. For multicellular plants, key considerations include how exposure route and the role of the rhizosphere may affect the quantitative measurement of uptake, and that the efficiency of washing procedures to remove loosely attached ENMs to the roots is not well understood. Within each organism category, case studies are provided to illustrate key methodological considerations for conducting robust bioaccumulation experiments for different species within each major group. The full scope of ENM bioaccumulation measurements and interpretations are discussed including conducting the organism exposure, separating organisms from the ENMs in the test media after exposure, analytical methods to quantify ENMs in the tissues or cells, and modeling the ENM bioaccumulation results. One key finding to improve bioaccumulation measurements was the critical need for further analytical method development to identify and quantify ENMs in complex matrices. Overall, the discussion, suggestions, and case studies described herein will help improve the robustness of ENM bioaccumulation studies.

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

Kyiv is Ukraine’s capital and largest city. Home to 3 million people, this area has a rich history of agriculture and industry. The Dnieper River is Ukraine’s largest river and it passes through the center of Kyiv. Little information on emerging and legacy compounds or their toxicity exists for this area. Water and biota were sampled for PAHs, PCBs, metals and emerging contaminants including pharmaceuticals, personal care products and newer synthetic pesticides. The effects of surface waters in the Dnieper were evaluated using the Ames, chronic and acute daphnia and a ciliate (Colpoda stennii) assay. Elevated concentrations of legacy contaminants were found in fish samples indicating that these compounds are bioavailable. Concentrations of legacy and emerging contaminants were found in seven stations near the municipal water treatment plant (MWTP) and receiving waters of the Dnieper River. The MWTP appeared to remove some of the emerging contaminants, however the legacy compounds (PCBs and PAHs) were not affected by the MWTP and appeared to be more wide spread indicating a number of sources to the Dnieper River. Acute and chronic toxicity were associated with the influent and effluent of the MWRP, however mutagenicity was noted in surface waters throughout the Dnieper River including upstream of the MWTP. This study provides the first snapshot of possible human health and ecological risks associated with surface waters of the Dnieper. More research on seasonal changes and sources of toxicity, mutagenicity and contaminants would aid in completing a more comprehensive risk assessment of surface waters of the Dnieper River.

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.

An increase in production of commercial products containing graphene-family nanomaterials (GFNs) has led to concern over their release into the environment. The fate and potential ecotoxicological effects of GFNs in the environment are currently unclear, partially due to the limited analytical methods for GFN measurements. In this review, the unique properties of GFNs that are useful for their detection and quantification are discussed. The capacity of several classes of techniques to identify and/or quantify GFNs in different environmental matrices (water, soil, sediment, and organisms), after environmental transformations, and after release from a polymer matrix of a product is evaluated. Extraction and strategies to combine methods for more accurate discrimination of GFNs from environmental interferences as well as from other carbonaceous nanomaterials are recommended. Overall, a comprehensive review of the techniques available to detect and quantify GFNs are systematically presented to inform the state of the science, guide researchers in their selection of the best technique for the system under investigation, and enable further development of GFN metrology in environmental matrices. Two case studies are described to provide practical examples of choosing which techniques to utilize for detection or quantification of GFNs in specific scenarios. Because the available quantitative techniques are somewhat limited, more research is required to distinguish GFNs from other carbonaceous materials and improve the accuracy and detection limits of GFNs at more environmentally relevant concentrations.

Little is known about environmental biodegradability or biotransformations of single-walled carbon nanotubes (SWNT). Because of their strong association with aquatic organic matter, detailed knowledge of the ultimate fate and persistence of SWNT requires investigation of possible biotransformations (i.e., biodegradation) in environmental media. In the present study, [14C]SWNT were utilized to track biodegradation over 6 mo by pure liquid culture of the fungus Trametes versicolor and mixed bacterial isolates from field-collected sediment or aerated wastewater treatment plant sludge. The mixed cultures were chosen as more environmentally relevant media where SWNT will likely be deposited under both aerobic and anaerobic conditions. Activity of [14C] was assessed in solid, aqueous, and 14CO2 gaseous phases to determine amounts of intact SWNT, partially soluble SWNT degradation products, and mineralized SWNT, respectively, during the 6 mo of the experiment. Mass balances based on radiocarbon activity were approximately 100% over 6 mo, and no significant degradation of SWNT was observed. Approximately 99% of the [14C] activity remained in the solid phase, 0.8% in the aqueous phase, and less than 0.1% was mineralized to 14CO2, regardless of culture type. These results suggest that SWNT are not readily biodegraded by pure fungal cultures or environmental microbial communities, and are likely persistent in environmental media. Environ Toxicol Chem 2014;9999:1–5. © 2014 SETAC

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.

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 CuSO(4) (519 mg/kg sediment). In addition, single-species acute testing was performed with both MCA and CuSO(4.) Our results indicate that meio- and macrofaunal assemblages exposed to High-MCA and CuSO(4) 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.

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

Since its discovery in 2004, graphene has been used in a wide variety of fields including biomedicine, electronics, filtration materials, and surface coatings. The rapidly expanding consumer market for graphene family nanomaterials (GFNs), such as graphene oxide (GO), raises concern regarding their environmental toxicity. The aim of this study was to evaluate the effects of GO exposures in a marine filter-feeding bivalve (Crassostrea virginica) using sublethal biomarker approaches that can contribute to the development of an adverse outcome pathway (AOP). A 14-day study was conducted to identify tissue-specific molecular markers of GO toxicity using a static renewal design. Elevated lipid peroxidation and changes in glutathione-s-transferase (GST) activities were observed in gills and digestive gland tissues of the GO-exposed oysters. These cellular changes were noted for 2.5 and 5 mg/L GO exposures in seawater. Based on our results, reactive oxygen species (ROS)-induced oxidative damage is identified as a key event in the proposed AOP. Additionally, detoxification enzymes, such as GST, are thought to be involved in stress signaling leading to adverse effects on cellular health. This study is a part of our two-tier approach towards the identification of short- and long-term effects of GO exposures. This work, together with our previous 72 h exposure, represents the application of biomarker-based investigations in the process of AOP development for graphene family nanomaterials.

Currently, 2 approaches are available for performing environmental diagnostics on samples like municipal and industrial effluents, interstitial waters, and whole sediments to identify anthropogenic contaminants causing toxicological effects. One approach is toxicity identification evaluation (TIE), which was developed primarily in North America to determine active toxicants to whole-organism endpoints. The second approach is effects-directed analysis (EDA), which has origins in both Europe and North America. Unlike TIE, EDA uses primarily in vitro endpoints with an emphasis on organic contaminants as the cause of observed toxicity. The 2 approaches have fundamental differences that make them distinct techniques. In EDA, the sophisticated and elegant fractionation and chemical analyses performed to identify the causes of toxicity with a high degree of specificity often compromise contaminant bioavailability. In contrast, in TIE, toxicant bioavailability is maintained and is considered critical to accurately identifying the causes of environmental toxicity. However, maintaining contaminant bioavailability comes with the cost of limiting, at least until recently, the use of the types of sophisticated fractionation and elegant chemical analyses that have resulted in the high specificity of toxicant diagnosis performed in EDA. The present study provides an overview of each approach and highlights areas where the 2 approaches can complement one another and lead to the improvement of both.

As the use of single-walled carbon nanotubes (SWNTs) increases over time, so does the potential for environmental release. This research aimed to determine the toxicity, bioavailability, and bioaccumulation of SWNTs in marine benthic organisms at the base of the food chain. The toxicity of SWNTs was tested in a whole sediment exposure with the amphipod Ampelisca abdita and the mysid Americamysis bahia. In addition, SWNTs were amended to sediment and/or food matrices to determine their bioavailability and bioaccumulation through these routes in A. abdita, A. bahia, and the estuarine amphipod Leptocheirus plumulosus. No significant mortality to any species via sediment or food matrices was observed at concentrations up to 100 ppm. A novel near-infrared fluorescence spectroscopic method was utilized to measure and characterize the body burdens of pristine SWNTs in nondepurated and depurated organisms. We did not detect SWNTs in depurated organisms but quantified them in nondepurated A. abdita fed SWNT-amended algae. After a 28-d exposure to [14C]SWNT-amended sediment (100 µg/g) and algae (100 µg/g), [14C]SWNT was detected in depurated and nondepurated L. plumulosus amphipods at 0.50 µg/g and 5.38 µg/g, respectively. The results indicate that SWNTs are bioaccessible to marine benthic organisms but do not appear to accumulate or cause toxicity. Environ Toxicol Chem 2013;32:1270–1277. © 2013 SETAC

To understand their fate and transport in estuarine systems, the aggregation, sedimentation and dissolution of CdSe quantum dots (QDs) in seawater were investigated. Hydrodynamic size increased from 40–60 nm to >1 mm within one hour in seawater, and the aggregates were highly polydispersed. Their sedimentation rates in seawater were measured to be 4–10 mm/day. Humic acid (HA), further increased their size and polydispersity, and slowed sedimentation. Light increased their dissolution and release of dissolved Cd. The ZnS shell also slowed release of Cd ions. With sufficient light, HA increased the dissolution of QDs, while with low light, HA alone did not change their dissolution. The benthic zone in estuarine systems is the most probable long-term destination of QDs due to aggregation and sedimentation. The bioavailability of was evaluated using the mysid Americamysis bahia. The 7-day LC50s of particulate and dissolved QDs were 290 and 23 μg (total Cd) /L, respectively. For mysids, the acute toxicity appears to be from Cd ions; however, research on the effects of QDs should be conducted with other organisms where QDs may be lodged in critical tissues such as gills or filtering apparatus, and Cd ions may be released and delivered directly to those tissues.

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

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.

During the Soviet era, Ukraine was an important industrial and agricultural region of the Soviet Union. This industrial and agricultural activity resulted in contamination of Ukraine's estuaries with legacy anthropogenic pollutants. Investigations on the toxicological effects of this estuarine contamination have been limited. For this research, we measured the toxicity of contaminated sediments from four Ukrainian estuaries to several aquatic organisms over 3 years. Sediment chemical analyses and whole sediment toxicity identification evaluations (TIEs) were also performed to determine the classes of contaminants contributing to toxicity. Toxic sediments were observed in several of the Ukrainian estuaries and chemical analyses of the sediments demonstrated anthropogenic contaminants were widely distributed. Contaminants were also detected in macrobenthic organisms collected from the sediments. Several lines of evidence, including TIEs, indicated hydrophobic organic chemicals (HOCs) were contributing substantially to observed toxicity. This information can guide environmental managers to prioritize portions of the estuaries requiring remediation.

Eutrophication (i.e., nutrient enrichment, organic enrichment, and oxygen depletion) is one of the most common sources of impairment in Clean Water Act 303(d)-listed waters in the United States. Although eutrophication can eventually cause adverse effects to the benthos, it may be difficult to diagnose. Sediment organic carbon (OC) content has been used as an indicator of enrichment in sediments, but the amount of surface area available for carbon adsorption must be considered. We investigated the utility of the relationship between OC and sediment grain size as an indicator of eutrophication. Data from the U.S. Environmental Protection Agency's Environmental Monitoring and Assessment Program was used to test this relationship. However, anthropogenic contaminants are also capable of causing adverse effects to the benthos and often co-occur with elevated levels of OC. Contaminant analysis and toxicity tests were not consistently related to enrichment status as defined by relationship between total OC and grain size. Although variability in response occurred, reflecting the variance in the water column factors (dissolved oxygen, chlorophyll a, and nutrients) and limited sample sizes, the data supported the hypothesis that sites designated as enriched were eutrophied. Dissolved oxygen levels were reduced at enriched sites, whereas chlorophyll a and nutrients were higher at enriched sites. This suggests that the relationship of OC to grain size can be used as a screening tool to diagnose eutrophication. Environ. Toxicol. Chem. 2011; 30:538–547. © 2010 SETAC

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

Sediment toxicity identification and evaluation (TIE) methods are relatively simple laboratory methods designed to identify specific toxicants or classes of toxicants in sediments; however, the question of whether the same toxicant identified in the laboratory is causing effects in the field remains unanswered. The objective of our study was to determine if laboratory TIE methods accurately reflect field effects. A TIE performed on sediments collected from the Elizabeth River (ER) in Virginia identified polycyclic aromatic hydrocarbons (PAHs) as the major toxicants. Several lines of evidence indicated PAHs were the major toxic agents in the field, including elevated PAH concentrations in ER sediments, comet assay results from in situ caged Merceneria merceneria, and chemical analyses of exposed M. merceneria, which indicated high PAH concentrations in the bivalve tissue. Our final evidence was the response from test organisms exposed to ER sediment extracts and then ultraviolet (UV) radiation. UV radiation caused a toxic diagnostic response unique to PAHs. The aggregation of these various lines of evidence supports the conclusion that PAHs were the likely cause of effects in laboratory- and field-exposed organisms, and that laboratory-based TIE findings reflect causes of field impairment

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.

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.

Sediment toxicity in silty marine harbor sediments is frequently dominated by ammonia or sulfide, leaving the adverse effects of persistent toxic substances unnoticed. To investigate the latter, we subjected interstitial water from three contaminated silty sediments to toxicity identification evaluation (TIE) phase I manipulations and tested for toxicity with four bioassays: the amphipod Corophium volutator (survival as an endpoint), the sea urchin Psammechinus miliaris (fertilization, embryo development) and the bacterium Vibrio fischeri (bioluminescence inhibition). The graduated pH manipulations identified the prominent toxicity of ammonia in the amphipod and sea urchin embryo tests, and also sulfide toxicity in the bacterium test. In two of the three samples tested with the amphipods, sea urchin embryos and bacteria, a small but significant reduction in interstitial water toxicity was achieved by removing persistent compounds through C 18 solid phase extraction. EDTA chelation resulted in a slight detoxification of the interstitial water for the amphipods and sea urchin embryos, but this was not related to any measured trace metals. Despite the presence of toxic levels of ammonia and sulfide in the harbor sediments, we established the adverse biological effects of persistent constituents by means of the TIE manipulations and in vivo interstitial water bioassays.

We obtained a water sample containing broken pieces of a tropical coral reef decor that was suspected of causing fish toxicity in a major aquarium. A toxicity identification and evaluation (TIE) was performed using three species: a mysid shrimp, Americamysis bahia; inland silverside Menidia beryllina; and an amphipod, Ampelisca abdita. Initial tests indicated that only the shrimp was sensitive to the unknown toxicant. The first phase of the TIE indicated that the toxicity to the shrimp could be eliminated by either the addition of EDTA or manipulation of the cation exchange column. Elevated concentrations of Cd were detected by inductively coupled plasma analysis, and metal toxicity was confirmed when the cation exchange column treatment successfully isolated the toxic metal. Analysis of affected fish tissue indicated Cd levels ranging from less than 0.3 ng/g in the muscle to 200 μg/g in the liver. This study demonstrates a unique application of TIE methods to diagnose toxicity problems in aquari...

The identification of toxicants affecting aquatic benthic systems is critical to sound assessment and management of our nation's waterways. Identification of toxicants can be useful in designing effective sediment remediation plans and reasonable options for sediment disposal. Knowledge of which contaminants affect benthic systems allows managers to link pollution to specific dischargers and prevent further release of toxicant(s). In addition, identification of major causes of toxicity in sediments may guide programs such as those developing environmental sediment guidelines and registering pesticides, while knowledge of the causes of toxicity which drive ecological changes such as shifts in benthic community structure would be useful in performing ecological risk assessments. To this end, the US Environmental Protection Agency has developed tools (toxicity identification and evaluation (TIE) methods) that allow investigators to characterize and identify chemicals causing acute toxicity in sediments and dredged materials. To date, most sediment TIEs have been performed on interstitial waters. Preliminary evidence from the use of interstitial water TIEs reveals certain patterns in causes of sediment toxicity. First, among all sediments tested, there is no one predominant cause of toxicity; metals, organics, and ammonia play approximately equal roles in causing toxicity. Second, within a single sediment there are multiple causes of toxicity detected; not just one chemical class is active. Third, the role of ammonia is very prominent in these interstitial waters. Finally, if sediments are divided into marine or freshwater, TIEs perforMed on interstitial waters from freshwater sediments indicate a variety of toxicants in fairly equal proportions, while TIEs performed on interstitial waters from marine sediments have identified only ammonia and organics as toxicants, with metals playing a minor role. Preliminary evidence from whole sediment TIEs indicates that organic compounds play a major role in the toxicity of marine sediments, with almost no evidence for either metal or ammonia toxicity. However, interpretation of these results may be skewed because only a small number of interstitial water (n = 13) and whole sediment (n = 5) TIEs have been completed. These trends may change as more data are collected.

The toxicity, bioaccumulation, and biotransformation of citrate and polyvinylpyrrolidone (PVP) coated silver nanoparticles (NPs) (AgNP-citrate and AgNP-PVP) in marine organisms via marine sediment exposure was investigated. Results from 7-d sediment toxicity tests indicate that AgNP-citrate and AgNP-PVP did not exhibit toxicity to the amphipod (Ampelisca abdita) and mysid (Americamysis bahia) at ≤75 mg/kg dry wt. A 28-d bioaccumulation study showed that Ag was significantly accumulated in the marine polychaete Nereis virens (N. virens) in the AgNP-citrate, AgNP-PVP and a conventional salt (AgNO3) treatments. Synchrotron X-ray absorption spectroscopy (XAS) results showed the distribution of Ag species in marine sediments amended with AgNP-citrate, AgNP-PVP, and AgNO3 was AgCl (50–65%) > Ag2S (32–42%) > Ag metal (Ag0) (3–11%). In N virens, AgCl (25–59%) and Ag2S (10–31%) generally decreased and, Ag metal (32–44%) increased, relative to the sediments. The patterns of speciation in the worm were different depending upon the coating of the AgNP and both types of AgNPs were different than the AgNO3 salt. These results show that the AgNP surface capping agents influenced Ag uptake, biotransformation, and/or excretion. To our knowledge, this is the first demonstration of the bioaccumulation and speciation of AgNPs in a marine organism (N. virens).

Little is known about environmental biodegradability or biotransformations of single-walled carbon nanotubes (SWNT). Because of their strong association with aquatic organic matter, detailed knowledge of the ultimate fate and persistence of SWNT requires investigation of possible biotransformations (i.e., biodegradation) in environmental media. In the present study, [(14)C]SWNT were utilized to track biodegradation over 6 mo by pure liquid culture of the fungus Trametes versicolor and mixed bacterial isolates from field-collected sediment or aerated wastewater treatment plant sludge. The mixed cultures were chosen as more environmentally relevant media where SWNT will likely be deposited under both aerobic and anaerobic conditions. Activity of [(14)C] was assessed in solid, aqueous, and (14)CO2 gaseous phases to determine amounts of intact SWNT, partially soluble SWNT degradation products, and mineralized SWNT, respectively, during the 6 mo of the experiment. Mass balances based on radiocarbon activity were approximately 100% over 6 mo, and no significant degradation of SWNT was observed. Approximately 99% of the [(14)C] activity remained in the solid phase, 0.8% in the aqueous phase, and less than 0.1% was mineralized to (14)CO2, regardless of culture type. These results suggest that SWNT are not readily biodegraded by pure fungal cultures or environmental microbial communities, and are likely persistent in environmental media.