Coral Reef Arks: An In Situ Mesocosm and Toolkit for Assembling Reef Communities.

Coral reefs thrive and provide maximal ecosystem services when they support a multi-level trophic structure and grow in favorable water quality conditions that include high light levels, rapid water flow, and low nutrient levels. Poor water quality and other anthropogenic stressors have caused coral mortality in recent decades, leading to trophic downgrading and the loss of biological complexity on many reefs. Solutions to reverse the causes of trophic downgrading remain elusive, in part because efforts to restore reefs are often attempted in the same diminished conditions that caused coral mortality in the first place. Coral Arks, positively buoyant, midwater structures, are designed to provide improved water quality conditions and supportive cryptic biodiversity for translocated and naturally recruited corals to assemble healthy reef mesocosms for use as long-term research platforms. Autonomous Reef Monitoring Structures (ARMS), passive settlement devices, are used to translocate the cryptic reef biodiversity to the Coral Arks, thereby providing a "boost" to natural recruitment and contributing ecological support to the coral health. We modeled and experimentally tested two designs of Arks to evaluate the drag characteristics of the structures and assess their long-term stability in the midwater based on their response to hydrodynamic forces. We then installed two designs of Arks structures at two Caribbean reef sites and measured several water quality metrics associated with the Arks environment over time. At deployment and 6 months after, the Coral Arks displayed enhanced metrics of reef function, including higher flow, light, and dissolved oxygen, higher survival of translocated corals, and reduced sedimentation and microbialization relative to nearby seafloor sites at the same depth. This method provides researchers with an adaptable, long-term platform for building reef communities where local water quality conditions can be adjusted by altering deployment parameters such as the depth and site.

Characterization of Metal Pulsed Exposure to Aquatic Organisms with Post-Exposure Monitoring: Implications for Stormwater Exposure Assessment.

Freshwater organisms are often exposed to contaminants such as heavy metals from stormwater discharges, which are dependent on rainfall duration and intensity. Therefore, standardized (48- or 96-h) continuous exposure methods developed for whole effluent toxicity (WET) testing might not always accurately convey the effects of stormwater and runoff contaminants. The present study characterized the acute toxicity of copper (Cu), zinc (Zn), and cadmium (Cd) to freshwater amphipods (Hyalella azteca) and cadmium (Cd) to water fleas (Ceriodaphnia dubia) using a modified exposure design that integrated relevant pulsed durations and included post-exposure monitoring. Less than 24-h-old C. dubia and 7 to 8-day-old H. azteca were exposed to water spiked with Cu, Zn, or Cd using 6-, 12-, 26-, or 96-h durations under standard laboratory conditions and monitored for cumulative mortality and reproduction (C. dubia only). Lethal effect (LC10s, LC25s, LC50s) and reproductive effect (EC25s, EC50s) were determined based on either mortality or reproduction of organisms at the end of each pulse (6, 12, or 26 h) and at the end of their respective tests (96 h). For all metals exposed to each organism, acute toxicity was found to be highest for the (96 h) continuous exposures. For pulsed exposures, mortality continued to increase following transfer to clean water for post-exposure monitoring. These results indicate a latent effect of Cu, Zn, and Cd to H. azteca and Cd to C. dubia. The present study concluded that using the continuous (48- or 96-h) WET exposure method overestimates the effects of stormwater and runoff contaminants. However, pulsed exposures without post-exposure monitoring also underestimate the toxicity of contaminants. The proposed pulsed exposure design provides a compromise that is more realistic than current WET methods to assess impacts from episodic events and accounts for potential latent effects that may be overlooked without monitoring post-exposure. Environ Toxicol Chem 2022;41:2488-2499. © 2022 SETAC.

Long-Term Monitoring of an In Situ Activated Carbon Treatment to Reduce Polychlorinated Biphenyl Availability in an Active Harbor.

Activated carbon-based amendments have been demonstrated as a means of sequestering sediment-associated organic compounds such as polychlorinated biphenyls (PCBs). In a 2012 effort, an activated carbon amendment was placed at a 0.5-acre amendment area adjacent to and underneath Pier 7 at the Puget Sound Naval Shipyard and Intermediate Maintenance Facility, Bremerton, Washington, USA to reduce PCB availability. Multiple postplacement monitoring events over a 3-year period showed an 80%-90% reduction in PCBs, stability of activated carbon, and no significant negative impacts to the benthic community. To further evaluate the long-term performance, a follow-on to the approximately 7-year (82-month) postplacement monitoring event was conducted in 2019. The results of in situ porewater and bioaccumulation evaluations were consistent with previous observations, indicating overall PCB availability reductions of approximately 80%-90% from preamendment conditions. Multiple measurement approaches for quantifying activated carbon and amendment presence indicated that the amendment was present and stable in the amendment area and that the activated carbon content was similar to levels observed previously. As in the previous investigation, benthic invertebrate community metrics indicated that the amendment did not significantly impair benthic health. An application of carbon petrography to quantify activated carbon content in surface sediments was also explored. The results were found to correspond within a factor of 1.3 (on average) with those of data for the black carbon content via a black carbon chemical oxidation method, an approach that quantifies all forms of black carbon (including activated carbon). The results suggest that at sites with low soot-derived black carbon content in sediment (relative to the targeted activated carbon dose), the black carbon chemical oxidation method would be a reasonable method for measurement of activated carbon dosage in sediment at sites amended with activated carbon. Environ Toxicol Chem 2022;41:1568-1574. © 2022 SETAC.

Environmental Characterization of Underwater Munitions Constituents at a Former Military Training Range.

As a result of military activities, unexploded ordnance and discarded military munitions are present in underwater environments, which has resulted in the release of munitions constituents including the high explosives 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), along with their primary degradation products, to the water column and adjacent sediments. The present study focused on the characterization of underwater exposure and concentrations of energetics such as TNT and RDX at the former Vieques Naval Training Range at Bahia Salina del Sur (Vieques, Puerto Rico, USA), a bay with documented high incidence of munitions. In situ passive sampling using polar organic chemical integrative samplers (POCIS) was used for the detection and quantification of constituents in water at target locations approximately 15 to 30 cm from 15 individual potentially leaking munitions, and also at 15 unbiased locations approximately evenly spaced across the Bay. For comparison with POCIS-derived concentrations, grab samples were taken at the POCIS target locations. The POCIS-derived and averaged grab samples agreed within a factor of 3. When detected, munitions constituent concentrations (primarily TNT and RDX) were observed at ultratrace concentrations (as low as 4 ng/L for RDX), except 30 cm from one General Purpose bomb where the TNT concentration was 5.3 µg/L, indicating that low-level contamination exists at Bahia Salina del Sur on a very localized scale despite the relatively high density of munitions, similar to previously reported results for other munitions sites around the world. Sediment and porewater sampled at 4 stations where munitions constituents were detected in the water column had concentrations below detection (approximately 5 µg/kg and 5 ng/L, respectively), suggesting that the sediment was not a sink for these constituents at those locations. Environ Toxicol Chem 2022;41:275-286. © 2021 SETAC. This article has been contributed to by US Government employees and their work is in the public domain in the USA.

Pulsed exposure toxicity testing: Baseline evaluations and considerations using copper and zinc with two marine species.

Methods to assess environmental impacts from episodic discharges on receiving water bodies need a more environmentally relevant and scientifically defensible toxicity test design. Many permittees are regularly required to conduct 96-h toxicity tests on discharges associated with events that are generally less than 24 h in duration. Current standardized methods do not adequately reflect these episodic discharge conditions at either the point of compliance nor as it mixes with the receiving environment. In order to evaluate more representative biological effects, an alternative toxicity approach is described incorporating pulsed exposures of effluents and subsequent transfer of test organisms to clean water for the remainder of the test. This pulsed exposure protocol incorporates a slight modification to USEPA Whole Effluent Toxicity (WET) chronic and acute methods for two marine species, purple sea urchin embryos, Strongylocentrotus purpuratus, and juvenile mysid shrimp Americamysis bahia. Tests were performed with toxicants using standard static (96 h) and pulsed (6, 12, and 26 h) exposures. Following pulsed exposures, organisms were transferred to uncontaminated seawater for the remainder of the 96-h test period. Results for these species and endpoints indicated that the sensitivity of these species to copper and zinc were up to two orders of magnitude greater using standard continuous exposures compared to shorter pulsed exposures. Additional considerations assessed included timing of the onset of a pulse and latent effects following an exposure. This modified approach requires minimal modification to current standard methods and increases the realism to more accurately assess toxic effects resulting from episodic discharges.

Aquatic toxicity evaluations of PFOS and PFOA for five standard marine endpoints.

Per- and poly-fluoroalkyl substances (PFAS) are emerging contaminants that are coming under increasing scrutiny. Currently, there is a paucity of effects data for marine aquatic life, limiting the assessment of ecological risks and compliance with water quality policies. In the present study, the toxicity of perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) to four standard marine laboratory toxicity testing species, encompassing five endpoints, were evaluated: 1) 96-h embryo-larval normal development for the purple sea urchin (Strongylocentrotus purpuratus); 2) 48-h embryo-larval normal development and normal survival for the Mediterranean mussel (Mytilus galloprovincialis); 3) 96-h survival of opossum shrimp (Americamysis bahia); and 4) 24-h light output for the bioluminescent dinoflagellate Pyrocystis lunula. All species were tested using standard United States Environmental Protection Agency (USEPA) and/or American Society for Testing and Materials (ASTM) International protocols. For PFOS and PFOA, the order of species sensitivity, starting with the most sensitive, was M. galloprovincialis, S. purpuratus, P. lunula, and A. bahia. The range of median lethal or median effect concentrations for PFOS (1.1-5.1 mg L-1) and PFOA (10-24 mg L-1) are comparable to the relatively few toxicity effect values available for marine species. In addition to providing effects data for PFOA and PFOS, this study indicates these species and endpoints are sensitive to PFAS such that their use will be appropriate for deriving toxicity data with other PFAS in marine ecosystems.

Assessing Biota Accumulation Due to Contamination of Sediments by Storm Water Heavy Metals.

Evaluating sediment recontamination due to storm water discharges is important when evaluating the long-term effectiveness of sediment remediation efforts at reducing biological impacts. The bioaccumulation of the heavy metals zinc, nickel, copper, cadmium, mercury, and lead and the metalloid arsenic in a clam (Macoma nasuta) was studied in surficial sediments before and after storm water inputs from Paleta Creek, California, USA, during wet seasons in 2015 to 2016 and 2016 to 2017. The bioaccumulation was compared with bulk sediment concentrations and porewater concentrations measured by diffusion gradient in thin film devices. Significant reductions in biota accumulation and porewater concentrations were observed in samples collected after storm seasons compared with before storm seasons despite bulk sediment concentrations remaining the same or increasing. This was apparently the result of the deposition of storm water contaminants in low bioavailable forms. The bioaccumulation of all the measured contaminants showed a positive significant correlation with porewater concentrations (p < 0.1, α = 0.1) and weak or no correlations with bulk sediment concentration. In conclusion, observed bulk sediment recontamination due to storm water should not be assumed to lead directly to greater biota accumulation without bioavailability assessment. Environ Toxicol Chem 2020;39:2475-2484. © 2020 SETAC.

Assessing sediment recontamination from metals in stormwater.

Recontamination of sediments by stormwater is a major concern when evaluating the potential effectiveness of sediment remediation. Stormwater and sediment sampling were conducted in a mixed-use watershed at Paleta Creek in San Diego, CA to evaluate methods for assessing sediment recontamination by metals. Size-segregated stormwater contaminant loads with simultaneous receiving water and sediment measurements were used to identify dominant sources and contaminants with respect to their impact on sediment recontamination. Most of the stormwater contaminant loads of Cd, Cu, Pb, and Zn were associated with residential and highway sources from the upstream portions of the watershed and As, Ni and Hg were more significantly influenced by the downstream area of the watershed. Cd was strongly associated with large particles (>63 µm) and observed to settle in near shore areas with some attenuation due to mixing and dilution. Cu, in contrast, was associated more with the filtered fraction (<0.45 µm) and clay fraction (0.45-5 µm), resulting in less near shore sediment recontamination. Depositing sediment and other metals, particularly Cu and Hg, exhibited greater accumulation in settling traps than could be attributed to stormwater loads indicating the importance of other sources or resuspension of bay sediments on surficial sediment concentrations. Pb, Zn, Ni, and As showed influences of both stormwater and other sources. The study showed that measurement of size-segregated stormwater contaminant mass and concentrations combined with simultaneous measurements of deposition in sediment traps could differentiate between recontamination by stormwater and that of other sources.

A Novel In Situ Toxicity Identification Evaluation (iTIE) System for Determining which Chemicals Drive Impairments at Contaminated Sites.

Human-dominated waterways contain thousands of chemicals. Determining which chemical is the most important stressor is important, yet very challenging. The Toxicity Identification Evaluation (TIE) procedure from the US Environmental Protection Agency uses a series of chemical and physical manipulations to fractionate compounds within a matrix and systematically identify potential toxicants through laboratory bioassay testing. Although this may provide useful information, it lacks ecological realism because it is subject to laboratory-related artifacts and is resource intensive. The in situ Toxicity Identification Evaluation (iTIE) technology was developed to improve this approach and has undergone a number of modifications over the past several years. The novel prototype 3 consists of an array of iTIE ambient water fractionation units. Each unit is connected to a peristaltic pumping system with an organism exposure chamber that receives water from a resin chamber to chemically fractionate test site water. Test organisms included freshwater and marine standard toxicity test species. Postfractionation waters are collected for subsequent chemical analyses. Currently, the resins allow for separation of ammonia, metals, and nonpolar organics; the subsequent toxicity responses are compared between treatments and unfractionated, ambient exposures. The iTIE system was deployed to a depth of 3 m and evaluated in streams and marine harbors. Chemical analyses of water and iTIE chemical sorptive resins confirmed chemical groups causing lethal to sublethal responses. The system proved to be as sensitive or more so than the traditional phase 1 TIE test and required almost half of the resources to complete. This iTIE prototype provides a robust technology that improves stressor-causality linkages and thereby supports strong evidence for ecological risk weight-of-evidence assessments. Environ Toxicol Chem 2020;39:1746-1754. © 2020 SETAC.

Estimates of environmental loading from copper alloy materials.

Metal release rates were measured from four different copper alloy-based materials used by the aquaculture industry: copper sheet machined into a diamond mesh, copper alloy mesh (CAM), silicon bronze welded wire mesh, and copper sheeting, and compared with conventional nylon aquaculture net treated with a cuprous oxide antifouling (AF) coating. Release rates were measured in situ in San Diego Bay using a Navy-developed Dome enclosure system at nine different time points over one year. As expected, copper was the predominant metal released, followed by zinc and nickel, which were fractional components of the materials tested. Release rates followed a temporal trend similar to those observed with copper AF coatings applied to vessel hulls: an initial spike in copper release was followed by a decline to an asymptotic low. Leachate toxicity was consistent with prior studies and was directly related to the metal concentrations, indicating the alloys tested had no additional toxicity above pure metals.

Toward Validation of Toxicological Interpretation of Diffusive Gradients in Thin Films in Marine Waters Impacted by Copper.

Determination of the median effective concentration (EC50) of Cu on Mytilus galloprovincialis larvae by diffusive gradient in thin films (DGT) has been shown to effectively reduce the need to consider dissolved organic carbon (DOC) concentration and quality. A standard toxicity test protocol was used to validate previously modeled protective effects, afforded to highly sensitive marine larvae by ligand competition, in 5 diverse site waters. The results demonstrate significant narrowing of M. galloprovincialis toxicological endpoints, where EC50s ranged from 3.74 to 6.67 µg/L as CDGT Cu versus 8.76 to 26.8 µg/L as dissolved Cu (CuDISS ) over a DOC range of 0.74 to 3.11 mg/L; Strongylocentrotus purpuratus EC50s were 10.5 to 19.3 µg/L as CDGT Cu versus 22.7 to 67.1 µg/L as CuDISS over the same DOC range. The quality of DOC was characterized by fluorescence excitation and emission matrices. The results indicate that the heterogeneity of competing Cu binding ligands, in common marine waters, minimizes the need for class determinations toward explaining the degree of protection. Using conservative assumptions, an M. galloprovincialis CDGT Cu EC50 of 3.7 µg/L and corresponding criterion maximum concentration CDGT Cu of 1.8 µg/L, for universal application by regulatory compliance-monitoring programs, are proposed as a superior approach toward both integration of dynamic water quality over effective exposure periods and quantification of biologically relevant trace Cu speciation. Environ Toxicol Chem 2020;39:873-881. © 2020 SETAC.

Seasonal Toxicity Observed with Amphipods (Eohaustorius estuarius) at Paleta Creek, San Diego Bay, USA.

To assess potential impacts on receiving systems, associated with storm water contaminants, laboratory 10-d amphipod (Eohaustorius estuarius) survival toxicity tests were performed using intact sediment cores collected from Paleta Creek (San Diego Bay, CA, USA) on 5 occasions between 2015 and 2017. The approach included deposition-associated sediment particles collected from sediment traps placed at each of 4 locations during the 2015 to 2016 wet seasons. The bioassays demonstrated wet season toxicity, especially closest to the creek mouth, and greater mortality associated with particles deposited in the wet season compared with dry season samples. Grain size analysis of sediment trap material indicated coarser sediment at the mouth of the creek and finer sediment in the outer depositional areas. Contaminant concentrations of metals (Cd, Cu, Hg, Ni, Pb, and Zn) and organic compounds (polycyclic aromatic hydrocarbons [PAHs], polychlorinated biphenyls [PCBs], and pesticides) were quantified to assess possible causes of toxicity. Contaminant concentrations were determined in the top 5 cm of sediment and porewater (using passive samplers). Whereas metals, PAHs, and PCBs were rarely detected at sufficient concentrations to elicit a response, pyrethroid pesticides were highly correlated with amphipod toxicity. Summing individual pyrethroid constituents using a toxic unit approach suggested that toxicity to E. estuarius could be associated with pyrethroids. This unique test design allowed delineation of spatial and temporal differences in toxicity, suggesting that storm water discharge from Paleta Creek may be the source of seasonal toxicity. Environ Toxicol Chem 2019;39:229-239. © 2019 SETAC.

Release of Munitions Constituents in Aquatic Environments Under Realistic Scenarios and Validation of Polar Organic Chemical Integrative Samplers for Monitoring.

Munitions constituents (MC) may be released into aquatic environments as a result of underwater military munitions (UWMM) corrosion and breach. The present study investigated the release of 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) from Composition B fragments under 2 realistic exposure scenarios in a large flume with flow set at 15 cm/s: the first represented the release of MC from fully exposed Composition B, and the second represented release through a small hole, simulating a breached munition. Release of MC through a small hole was approximately 10 times lower than from exposed Composition B, demonstrating the strong influence of exposure to flow on release. The rate of release of MC into the flume was similar to that previously reported in a related field experiment, but a similar mass loss resulted in MC concentration in the field >300 times lower, likely by the dilution effect of hydrodynamic transport. The present study corroborates previous findings of release of MC at UWMM sites resulting in concentrations below the toxicity threshold to most species. In the flume water, MC was quantified using frequent grab sampling and polar organic chemical integrative samplers (POCIS). For TNT, POCIS-estimated time-weighted average concentrations were up to 40% higher than those derived from grab samples, whereas for RDX differences were 6% or less, demonstrating that POCIS provide reliable temporal integration of changing environmental concentrations for common MC. Environ Toxicol Chem 2019;38:2383-2391. 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.

Effects of Dissolved Organic Carbon on Copper Toxicity to Embryos of Mytilus galloprovincialis as Measured by Diffusive Gradient in Thin Films.

Diffusive gradient in thin films (DGT) potentially better quantifies bioavailable copper (Cu) in seawater. Laboratory exposure of DGTs and Mytilus galloprovincialis embryos at varying concentrations of dissolved organic carbon and Cu were performed to resolve the degree to which mimicry of toxicity buffering occurs in passive sampler quantification. The results provide preliminary median effect concentrations (EC50s) ranging from 4.8 to 11.5 µg/L as CDGT Cu over the span of 0.896 to 8.36 mg/L DOC. Environ Toxicol Chem 2019;00:1-6. 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.

Field validation of POCIS for monitoring at underwater munitions sites.

The present study evaluated polar organic chemical integrative samplers (POCIS) for quantification of conventional munitions constituents, including trinitrotoluene (TNT), aminodinitrotoluenes, diaminonitrotoluenes, dinitrotoluene, and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in a field setting. The POCIS were deployed at varying distances from the commonly used explosive formulation composition B (39.5% TNT, 59.5% RDX, 1% wax) in an embayment of Santa Rosa Sound (Pensacola, FL, USA). Time-weighted averaged water concentrations from a 13-d deployment ranged from 9 to 103 ng/L for TNT and RDX, respectively, approximately 0.3 to 2 m from the source. Concentrations decreased with increasing distance from the source to below quantitation limits (5-7 ng/L) at stations greater than 2 m away. Moderate biofouling of POCIS membranes after 13 d led to a subsequent effort to quantify potential effects of biofouling on the sampling rate for munitions constituents. After biofouling was allowed to occur for periods of 0, 7, 14, or 28 d at the field site, POCIS were transferred to aquaria spiked with munitions constituents. No significant differences in uptake of TNT or RDX were observed across a gradient of biofouling presence, although the mass of fouling organisms on the membranes was statistically greater for the 28-d field exposure. The present study verified the high sensitivity and integrative nature of POCIS for relevant munitions constituents potentially present in aquatic environments, indicating that application at underwater military munitions sites may be useful for ecological risk assessment. Environ Toxicol Chem 2018;37:2257-2267. 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.

Performance of an in situ activated carbon treatment to reduce PCB availability in an active harbor.

In situ amendment of surface sediment with activated carbon is a promising technique for reducing the availability of hydrophobic organic compounds in surface sediment. The present study evaluated the performance of a logistically challenging activated carbon placement in a high-energy hydrodynamic environment adjacent to and beneath a pier in an active military harbor. Measurements conducted preamendment and 10, 21, and 33 months (mo) postamendment using in situ exposures of benthic invertebrates and passive samplers indicated that the targeted 4% (by weight) addition of activated carbon (particle diameter ≤74 µm) in the uppermost 10 cm of surface sediment reduced polychlorinated biphenyl availability by an average (± standard deviation) of 81 ± 11% in the first 10 mo after amendment. The final monitoring event (33 mo after amendment) indicated an approximate 90 ± 6% reduction in availability, reflecting a slight increase in performance and showing the stability of the amendment. Benthic invertebrate census and sediment profile imagery did not indicate significant differences in benthic community ecological metrics among the preamendment and 3 postamendment monitoring events, supporting existing scientific literature that this approximate activated carbon dosage level does not significantly impair native benthic invertebrate communities. Recommendations for optimizing typical site-specific assessments of activated carbon performance are also discussed and include quantifying reductions in availability and confirming placement of activated carbon. Environ Toxicol Chem 2018;37:1767-1777. 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.

Investigation of polar organic chemical integrative sampler (POCIS) flow rate dependence for munition constituents in underwater environments.

Munition constituents (MC) are present in aquatic environments throughout the world. Potential for fluctuating release with low residence times may cause concentrations of MC to vary widely over time at contaminated sites. Recently, polar organic chemical integrative samplers (POCIS) have been demonstrated to be valuable tools for the environmental exposure assessment of MC in water. Flow rate is known to influence sampling by POCIS. Because POCIS sampling rates (Rs) for MC have only been determined under quasi-static conditions, the present study evaluated the uptake of 2,4,6-trinitrotoluene (TNT), RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), and 2,4- and 2,6-dinitrotoluenes (DNT), by POCIS in a controlled water flume at 7, 15, and 30 cm/s in 10-day experiments using samplers both within and without a protective cage. Sampling rate increased with flow rate for all MC investigated, but flow rate had the strongest impact on TNT and the weakest impact on RDX. For uncaged POCIS, mean Rs for 30 cm/s was significantly higher than that for 7 cm by 2.7, 1.9, 1.9, and 1.3 folds for TNT, 2,4-DNT, 2,6-DNT, and RDX, respectively. For all MC except RDX, mean Rs for caged POCIS at 7 cm/s were significantly lower than for uncaged samplers and similar to those measured at quasi-static condition, but except for 2,6-DNT, no caging effect was measured at the highest flow rate, indicating that the impact of caging on Rs is flow rate-dependent. When flow rates are known, flow rate-specific Rs should be used for generating POCIS-derived time-averaged concentrations of MC at contaminated sites.

Accumulation and depuration of trinitrotoluene and related extractable and nonextractable (bound) residues in marine fish and mussels.

To determine if trinitrotoluene (TNT) forms nonextractable residues in mussels (Mytilus galloprovincialis) and fish (Cyprinodon variegatus) and to measure the relative degree of accumulation as compared to extractable TNT and its major metabolites, organisms were exposed to water fortified with (14)C-TNT. After 24 h, nonextractable residues made up 75% (mussel) and 83% (fish) while TNT accounted for 2% of total radioactivity. Depuration half-lives for extractable TNT, aminodinitrotoluenes (ADNTs) and diaminonitrotoluenes (DANTs) were fast initially (<0.5 h), but slower for nonextractable residues. Nonextractable residues from organisms were identified as ADNTs and DANTs using 0.1 M HCL for solubilization followed by liquid chromatography-tandem mass spectrometry. Recovered metabolites only accounted for a small fraction of the bound residue quantified using a radiotracer likely because of low extraction or hydrolysis efficiency or alternative pathways of incorporation of radiolabel into tissue.

Application of POCIS for exposure assessment of munitions constituents during constant and fluctuating exposure.

The present study examined the potential use of polar organic chemical integrative samplers (POCIS) for exposure assessment of munitions constituents, including 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and their breakdown products (aminodinitrotoluenes [ADNTs], diaminonitrotoluenes [DANTs], and hexahydro-1,3,5-trinitroso-1,3,5-triazine [TNX]). Loss of munitions constituents from the sorbent phase after uptake was observed for the "pesticide" POCIS configuration but not for the "pharmaceutical" configuration. Therefore, the latter was selected for further investigation. Under constant exposure conditions, TNT, ADNTs, DANT, RDX, and atrazine (a common environmental contaminant) accumulated at a linear rate for at least 14 d, with sampling rates between 34 mL/d and 215 mL/d. When POCIS were exposed to fluctuating concentrations, analyte accumulation values were similar to values found during constant exposure, indicating that the sampler was indeed integrative. In contrast, caffeine (a common polar contaminant) and TNX did not accumulate at a linear rate and had a reduction in accumulation of greater than 50% on the POCIS during fluctuating exposures, demonstrating that POCIS did not sample those chemicals in an integrative manner. Moreover, in a flow-through microcosm containing the explosive formulation Composition B, TNT and RDX were readily measured using POCIS, despite relatively high turnover rates and thus reduced water concentrations. Mean water concentrations estimated from POCIS were ± 37% of mean water concentrations measured by traditional grab sample collection. Thus, POCIS were found to have high utility for quantifying exposure to most munitions constituents evaluated (TNT, ADNTs, and RDX) and atrazine.

Copper bioavailability and toxicity to Mytilus galloprovincialis in Shelter Island Yacht Basin, San Diego, CA.

The bioavailability and toxicity of copper (Cu) in Shelter Island Yacht Basin (SIYB), San Diego, CA, USA, was assessed with simultaneous toxicological, chemical, and modeling approaches. Toxicological measurements included laboratory toxicity testing with Mytilus galloprovincialis (Mediterranean mussel) embryos added to both site water (ambient) and site water spiked with multiple Cu concentrations. Chemical assessment of ambient samples included total and dissolved Cu concentrations, and Cu complexation capacity measurements. Modeling was based on chemical speciation and predictions of bioavailability and toxicity using a marine Biotic Ligand Model (BLM). Cumulatively, these methods assessed the natural buffering capacity of Cu in SIYB during singular wet and dry season sampling events. Overall, the three approaches suggested negligible bioavailability, and isolated observed or predicted toxicity, despite an observed gradient of increasing Cu concentration, both horizontally and vertically within the water body, exceeding current water quality criteria for saltwater.