Predictive Analysis Using Chemical-Gene Interaction Networks Consistent with Observed Endocrine Activity and Mutagenicity of U.S. Streams.

In a recent U.S. Geological Survey/U.S. Environmental Protection Agency study assessing more than 700 organic compounds in 38 streams, in vitro assays indicated generally low estrogen, androgen, and glucocorticoid receptor activities, with 13 surface waters with 17ß-estradiol-equivalent (E2Eq) activities greater than a 1-ng/L estimated effects-based trigger value for estrogenic effects in male fish. Among the 36 samples assayed for mutagenicity in the Salmonella bioassay (reported here), 25% had low mutagenic activity and 75% were not mutagenic. Endocrine and mutagenic activities of the water samples were well correlated with each other and with the total number and cumulative concentrations of detected chemical contaminants. To test the predictive utility of knowledge-base-leveraging approaches, site-specific predicted chemical-gene (pCGA) and predicted analogous pathway-linked (pPLA) association networks identified in the Comparative Toxicogenomics Database were compared with observed endocrine/mutagenic bioactivities. We evaluated pCGA/pPLA patterns among sites by cluster analysis and principal component analysis and grouped the pPLA into broad mode-of-action classes. Measured E2eq and mutagenic activities correlated well with predicted pathways. The pPLA analysis also revealed correlations with signaling, metabolic, and regulatory groups, suggesting that other effects pathways may be associated with chemical contaminants in these waters and indicating the need for broader bioassay coverage to assess potential adverse impacts.

Expanded Target-Chemical Analysis Reveals Extensive Mixed-Organic-Contaminant Exposure in U.S. Streams.

Surface water from 38 streams nationwide was assessed using 14 target-organic methods (719 compounds). Designed-bioactive anthropogenic contaminants (biocides, pharmaceuticals) comprised 57% of 406 organics detected at least once. The 10 most-frequently detected anthropogenic-organics included eight pesticides (desulfinylfipronil, AMPA, chlorpyrifos, dieldrin, metolachlor, atrazine, CIAT, glyphosate) and two pharmaceuticals (caffeine, metformin) with detection frequencies ranging 66-84% of all sites. Detected contaminant concentrations varied from less than 1 ng L-1 to greater than 10 µg L-1, with 77 and 278 having median detected concentrations greater than 100 ng L-1 and 10 ng L-1, respectively. Cumulative detections and concentrations ranged 4-161 compounds (median 70) and 8.5-102 847 ng L-1, respectively, and correlated significantly with wastewater discharge, watershed development, and toxic release inventory metrics. Log10 concentrations of widely monitored HHCB, triclosan, and carbamazepine explained 71-82% of the variability in the total number of compounds detected (linear regression; p-values: < 0.001-0.012), providing a statistical inference tool for unmonitored contaminants. Due to multiple modes of action, high bioactivity, biorecalcitrance, and direct environment application (pesticides), designed-bioactive organics (median 41 per site at µg L-1 cumulative concentrations) in developed watersheds present aquatic health concerns, given their acknowledged potential for sublethal effects to sensitive species and lifecycle stages at low ng L-1.

Regional variability in bed-sediment concentrations of wastewater compounds, hormones and PAHs for portions of coastal New York and New Jersey impacted by hurricane Sandy.

Bed sediment samples from 79 coastal New York and New Jersey, USA sites were analyzed for 75 compounds including wastewater associated contaminants, PAHs, and other organic compounds to assess the post-Hurricane Sandy distribution of organic contaminants among six regions. These results provide the first assessment of wastewater compounds, hormones, and PAHs in bed sediment for this region. Concentrations of most wastewater contaminants and PAHs were highest in the most developed region (Upper Harbor/Newark Bay, UHNB) and reflected the wastewater inputs to this area. Although the lack of pre-Hurricane Sandy data for most of these compounds make it impossible to assess the effect of the storm on wastewater contaminant concentrations, PAH concentrations in the UHNB region reflect pre-Hurricane Sandy conditions in this region. Lower hormone concentrations than predicted by the total organic carbon relation occurred in UHNB samples, suggesting that hormones are being degraded in the UHNB region.

Environmental implications of the use of sulfidic back-bay sediments for dune reconstruction - Lessons learned post Hurricane Sandy.

Some barrier-island dunes damaged or destroyed by Hurricane Sandy's storm surges in October 2012 have been reconstructed using sediments dredged from back bays. These sand-, clay-, and iron sulfide-rich sediments were used to make berm-like cores for the reconstructed dunes, which were then covered by beach sand. In November 2013, we sampled and analyzed partially weathered materials collected from the cores of reconstructed dunes. There are generally low levels of metal toxicants in the reconstructed dune materials. However oxidation of reactive iron sulfides by percolating rainwater produces acid-sulfate pore waters, which evaporate during dry periods to produce efflorescent gypsum and sodium jarosite salts. The results suggest use of sulfidic sediments in dune reconstruction has both drawbacks (e.g., potential to generate acid runoff from dune cores following rainfall, enhanced corrosion of steel bulwarks) and possible benefits (e.g., efflorescent salts may enhance structural integrity).

Sediment chemistry and toxicity in Barnegat Bay, New Jersey: Pre- and post-Hurricane Sandy, 2012-13.

Hurricane Sandy made landfall in Barnegat Bay, October, 29, 2012, damaging shorelines and infrastructure. Estuarine sediment chemistry and toxicity were investigated before and after to evaluate potential environmental health impacts and to establish post-event baseline sediment-quality conditions. Trace element concentrations increased throughout Barnegat Bay up to two orders of magnitude, especially north of Barnegat Inlet, consistent with northward redistribution of silt. Loss of organic compounds, clay, and organic carbon is consistent with sediment winnowing and transport through the inlets and sediment transport modeling results. The number of sites exceeding sediment quality guidance levels for trace elements tripled post-Sandy. Sediment toxicity post-Sandy was mostly unaffected relative to pre-Sandy conditions, but at the site with the greatest relative increase for trace elements, survival rate of the test amphipod decreased (indicating degradation). This study would not have been possible without comprehensive baseline data enabling the evaluation of storm-derived changes in sediment quality.

Young of the year bluefish (Pomatomus saltatrix) as a bioindicator of estuarine health: Establishing a new baseline for persistent organic pollutants after Hurricane Sandy for selected estuaries in New Jersey and New York.

Atlantic coastal bays of the US are essential habitat for young of year bluefish (Pomatomus saltatrix). Their residence in these estuaries during critical life stages, high lipid content, and piscivory make bluefish an ideal bioindicator species for evaluating estuarine health. Individual whole fish from four estuaries impacted by Hurricane Sandy were collected in August 2013, analyzed for a suite of persistent organic pollutants (POPs) including polychlorinated biphenyls, polybrominated diphenyl ethers and organochlorine pesticides and evaluated using health metrics. Concentrations in whole bluefish differed by estuary; however, concentrations for many POPs decreased or were similar to those observed prior to the hurricane. Prevalence of the ectoparasitic gill isopod (Lironeca ovalis) varied by estuary and no relationships between contaminants and lesions were observed. Bluefish should be considered for monitoring programs and, if sampled frequently, could be an effective bioindicator of incremental and episodic changes in contaminants within aquatic food webs.

Screening tool to evaluate the vulnerability of down-gradient receptors to groundwater contaminants from uncapped landfills.

A screening tool for quantifying levels of concern for contaminants detected in monitoring wells on or near landfills to down-gradient receptors (streams, wetlands and residential lots) was developed and evaluated. The tool uses Quick Domenico Multi-scenario (QDM), a spreadsheet implementation of Domenico-based solute transport, to estimate concentrations of contaminants reaching receptors under steady-state conditions from a constant-strength source. Unlike most other available Domenico-based model applications, QDM calculates the time for down-gradient contaminant concentrations to approach steady state and appropriate dispersivity values, and allows for up to fifty simulations on a single spreadsheet. Sensitivity of QDM solutions to critical model parameters was quantified. The screening tool uses QDM results to categorize landfills as having high, moderate and low levels of concern, based on contaminant concentrations reaching receptors relative to regulatory concentrations. The application of this tool was demonstrated by assessing levels of concern (as defined by the New Jersey Pinelands Commission) for thirty closed, uncapped landfills in the New Jersey Pinelands National Reserve, using historic water-quality data from monitoring wells on and near landfills and hydraulic parameters from regional flow models. Twelve of these landfills are categorized as having high levels of concern, indicating a need for further assessment. This tool is not a replacement for conventional numerically-based transport model or other available Domenico-based applications, but is suitable for quickly assessing the level of concern posed by a landfill or other contaminant point source before expensive and lengthy monitoring or remediation measures are taken. In addition to quantifying the level of concern using historic groundwater-monitoring data, the tool allows for archiving model scenarios and adding refinements as new data become available.

ASSESSING THE POTENTIAL EFFECTS OF FUNGICIDES ON NONTARGET GUT FUNGI (TRICHOMYCETES) AND THEIR ASSOCIATED LARVAL BLACK FLY HOSTS.

Fungicides are moderately hydrophobic and have been detected in water and sediment, particularly in agricultural watersheds, but typically are not included in routine water quality monitoring efforts. This is despite their widespread use and frequent application to combat fungal pathogens. Whereas the efficacy of these compounds on fungal pathogens is well documented, little is known about their effects on nontarget fungi. This pilot study, a field survey in southwestern Idaho from April to December 2010 on four streams with varying pesticide inputs (two agricultural and two reference sites), was conducted to assess nontarget impact of fungicides on gut fungi, or trichomycetes. Tissues of larval black flies (Diptera: Simuliidae), hosts of gut fungi, were analyzed for pesticide accumulation. Fungicides were detected in hosts from streams within agricultural watersheds but were not detected in hosts from reference streams. Gut fungi from agricultural sites exhibited decreased percent infestation, density within the gut, and sporulation, and black fly tissues had elevated pesticide concentrations. Differences observed between the sites demonstrate a potential effect on this symbiotic system. Future research is needed to parse out the details of the complex biotic and abiotic relationships; however, these preliminary results indicate that impacts to nontarget organisms could have far-reaching consequences within aquatic ecosystems.

Occurrence and persistence of fungicides in bed sediments and suspended solids from three targeted use areas in the United States.

To document the environmental occurrence and persistence of fungicides, a robust and sensitive analytical method was used to measure 34 fungicides and an additional 57 current-use pesticides in bed sediments and suspended solids collected from areas of intense fungicide use within three geographic areas across the United States. Sampling sites were selected near or within agricultural research farms using prophylactic fungicides at rates and types typical of their geographic location. At least two fungicides were detected in 55% of the bed and 83% of the suspended solid samples and were detected in conjunction with herbicides and insecticides. Six fungicides were detected in all samples including pyraclostrobin (75%), boscalid (53%), chlorothalonil (41%) and zoxamide (22%). Pyraclostrobin, a strobilurin fungicide, used frequently in the United States on a variety of crops, was detected more frequently than p,p'-DDE, the primary degradate of p,p'-DDT, which is typically one of the most frequently occurring pesticides in sediments collected within highly agricultural areas. Maximum fungicide concentrations in bed sediments and suspended solids were 198 and 56.7 µg/kg dry weight, respectively. There is limited information on the occurrence, fate, and persistence of many fungicides in sediment and the environmental impacts are largely unknown. The results of this study indicate the importance of documenting the persistence of fungicides in the environment and the need for a better understanding of off-site transport mechanisms, particularly in areas where crops are grown that require frequent treatments to prevent fungal diseases.

Occurrence of boscalid and other selected fungicides in surface water and groundwater in three targeted use areas in the United States.

To provide an assessment of the occurrence of fungicides in water resources, the US Geological Survey used a newly developed analytical method to measure 33 fungicides and an additional 57 current-use pesticides in water samples from streams, ponds, and shallow groundwater in areas of intense fungicide use within three geographic areas across the United States. Sampling sites were selected near or within farms using prophylactic fungicides at rates and types typical of their geographic location. At least one fungicide was detected in 75% of the surface waters and 58% of the groundwater wells sampled. Twelve fungicides were detected including boscalid (72%), azoxystrobin (51%), pyraclostrobin (40%), chlorothalonil (38%) and pyrimethanil (28%). Boscalid, a carboxamide fungicide registered for use in the US in 2003, was detected more frequently than atrazine and metolachlor, two herbicides that are typically the most frequently occurring pesticides in many large-scale water quality studies. Fungicide concentrations ranged from less than the method detection limit to approximately 2000 ngL(-1). Currently, limited toxicological data for non-target species exists and the environmental impacts are largely unknown. The results of this study indicate the importance of including fungicides in pesticide monitoring programs, particularly in areas where crops are grown that require frequent treatments to prevent fungal diseases.