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James L. Gray

Publications and source records attributed to James L. Gray.

At least 37 records · Page 2Linked to original sources

Pilot-scale expanded assessment of inorganic and organic tapwater exposures and predicted effects in Puerto Rico, USA

A pilot-scale expanded target assessment of mixtures of inorganic and organic contaminants in point-of-consumption drinking water (tapwater, TW) was conducted in Puerto Rico (PR) to continue to inform TW exposures and corresponding estimations of cumulative human-health risks across the US. In August 2018, a spatial synoptic pilot assessment of than 524 organic, 37 inorganic, and select microbiological contaminant indicators was conducted in 14 locations (7 home; 7 commercial) across PR. A follow-up 3-day temporal assessment of TW variability was conducted in December 2018 at two of the synoptic locations (1 home, 1 commercial) and included daily pre- and post-flush samples. Concentrations of regulated and unregulated TW contaminants were used to calculate cumulative in vitro bioactivity ratios and Hazard Indices (HI) based on existing human-health benchmarks. Synoptic results confirmed that human exposures to inorganic and organic contaminant mixtures, which are rarely monitored together in drinking water at the point of consumption, occurred across PR and consisted of elevated concentrations of inorganic contaminants (e.g., lead, copper), disinfection byproducts (DBP), and to a lesser extent per/polyfluoroalkyl substances (PFAS) and phthalates. Exceedances of human-health benchmarks in every synoptic TW sample support further investigation of the potential cumulative risk to vulnerable populations in PR and emphasize the importance of continued broad characterization of drinking-water exposures at the tap with analytical capabilities that better represent the complexity of both inorganic and organic contaminant mixtures known to occur in ambient source waters. Such health-based monitoring data are essential to support public engagement in source water sustainability and treatment and to inform consumer point-of-use treatment decision making in PR and throughout the US.

Puerto Rico↗

Mixed organic and inorganic tapwater exposures and potential effects in greater Chicago area, USA

Safe drinking water at the point of use (tapwater, TW) is a public-health priority. TW exposures and potential human-health concerns of 540 organics and 35 inorganics were assessed in 45 Chicago area United States (US) homes in 2017. No US Environmental Protection Agency (EPA) enforceable Maximum Contaminant Level(s) (MCL) were exceeded in any residential or water treatment plant (WTP) pre-distribution TW sample. Ninety percent (90%) of organic analytes were not detected in treated TW, emphasizing the high quality of the Lake Michigan drinking-water source and the efficacy of the drinking-water treatment and monitoring. Sixteen (16) organics were detected in >25% of TW samples, with about 50 detected at least once. Low-level TW exposures to unregulated disinfection byproducts (DBP) of emerging concern, per/polyfluoroalkyl substances (PFAS), and three pesticides were ubiquitous. Common exceedances of non-enforceable EPA MCL Goal(s) (MCLG) of zero for arsenic [As], lead [Pb], uranium [U]), bromodichloromethane, and tribromomethane suggest potential human health concerns and emphasize the continuing need for improved understanding of cumulative effects of low-concentration mixtures on vulnerable sub-populations. Because DBP dominated TW organics, residential TW concentrations are potentially predictable with expanded pre-distribution DBP monitoring. However, several TW chemicals, notably Pb and several infrequently detected organic compounds, were not readily explained by pre distribution samples, illustrating the need for continued broad inorganic/organic TW characterization to support consumer assessment of acceptable risk and point-of-use treatment options.

Illinois↗

Landfill leachate contributes per-/poly-fluoroalkyl substances (PFAS) and pharmaceuticals to municipal wastewater

Widespread disposal of landfill leachate to municipal sewer infrastructure in the United States calls for an improved understanding of the relative organic-chemical contributions to the wastewater treatment plant (WWTP) waste stream and associated surface-water discharge to receptors in the environment. Landfill leachate, WWTP influent, and WWTP effluent samples were collected from three landfill-WWTP systems and compared with analogous influent and effluent samples from two WWTPs that did not receive leachate. Samples were analyzed for 73 per-/poly-fluoroalkyl substances (PFAS), 109 pharmaceuticals, and 21 hormones and related compounds. PFAS were detected more frequently in leachate (92%) than in influent (55%). Total PFAS concentrations in leachate (93,100 ng/L) were more than ten times higher than in influent (6,950 ng/L), and effluent samples (3,730 ng/L). Concentrations of bisphenol A; the nonprescription pharmaceuticals cotinine, lidocaine, nicotine; and the prescription pharmaceuticals amphetamine, carisoprodol, pentoxifylline, and thiabendazole were an order of magnitude higher in landfill leachate than WWTP influent. Leachate load contributions for PFAS (0.78 to 31 g/d), bisphenol A (0.97 to 8.3 g/d), and nonprescription (2.0 to 3.1 g/d) and prescription (0.48 to 2.5 g/d) pharmaceuticals to WWTP influent were generally low (<10 g/d) for most compounds because of high influent-to-leachate volumetric ratios (0.983). No clear differences in concentrations were apparent between effluents from WWTPs receiving landfill leachate and those that did not receive landfill leachate.

Environmental Science: Water Research & Technology↗

Reconnaissance of mixed organic and inorganic chemicals in private and public supply tapwaters at selected residential and workplace sites in the United States

Safe drinking water at the point-of-use (tapwater, TW) is a United States public health priority. Multiple lines of evidence were used to evaluate potential human health concerns of 482 organics and 19 inorganics in TW from 13 (7 public supply, 6 private well self-supply) home and 12 (public supply) workplace locations in 11 states. Only uranium (61.9 μg L –1 , private well) exceeded a National Primary Drinking Water Regulation maximum contaminant level (MCL: 30 μg L –1 ). Lead was detected in 23 samples (MCL goal: zero). Seventy-five organics were detected at least once, with median detections of 5 and 17 compounds in self-supply and public supply samples, respectively (corresponding maxima: 12 and 29). Disinfection byproducts predominated in public supply samples, comprising 21% of all detected and 6 of the 10 most frequently detected. Chemicals designed to be bioactive (26 pesticides, 10 pharmaceuticals) comprised 48% of detected organics. Site-specific cumulative exposure–activity ratios (∑ EAR ) were calculated for the 36 detected organics with ToxCast data. Because these detections are fractional indicators of a largely uncharacterized contaminant space, ∑ EAR in excess of 0.001 and 0.01 in 74 and 26% of public supply samples, respectively, provide an argument for prioritized assessment of cumulative effects to vulnerable populations from trace-level TW exposures.

Environmental Science & Technology↗

Methods used for the collection and analysis of chemical and biological data for the Tapwater Exposure Study, United States, 2016–17

In 2016, the U.S. Geological Survey (USGS) Environmental Health Mission Area, initiated the Tapwater Exposure Study as part of an infrastructure project to assess human exposure to potential threats from complex mixtures of contaminants. In the pilot phase (2016), samples were collected from 11 States throughout the United States, and in the second phase (2017), the study focused on the Greater Chicago area, including North and South Chicago, Illinois, and East Chicago, Indiana. Residential tapwater samples were collected at private residences during both phases, and during the first phase, samples were collected from Federal office buildings and from one office 19-liter water-bottle source. During the second phase, raw intake and treated (pre-distributional) water samples also were collected from four drinking-water treatment facilities in the Greater Chicago area. Samples were sent to laboratories at the USGS, U.S. Environmental Protection Agency, National Institute of Environmental Health Sciences, and Colorado School of Mines Center for Environmental Risk Assessment, for potential drinking-water pathogens, chemical, and bioassay analyses. These analyses included more than 400 chemicals such as trace elements, steroid hormones, pharmaceuticals, volatile organic compounds, pesticides, per- and polyfluorinated alkyl substances, cyanotoxins, and other organic compounds. The in vitro bioassay analyses included estrogen, androgen, and glucocorticoid receptor activity.

Open-File Report↗

Pharmaceutical manufacturing facility discharges can substantially increase the pharmaceutical load to U.S. wastewaters

Discharges from pharmaceutical manufacturing facilities (PMFs) previously have been identified as important sources of pharmaceuticals to the environment. Yet few studies are available to establish the influence of PMFs on the pharmaceutical source contribution to wastewater treatment plants (WWTPs) and waterways at the national scale. Consequently, a national network of 13 WWTPs receiving PMF discharges, six WWTPs with no PMF input, and one WWTP that transitioned through a PMF closure were selected from across the United States to assess the influence of PMF inputs on pharmaceutical loading to WWTPs. Effluent samples were analyzed for 120 pharmaceuticals and pharmaceutical degradates. Of these, 33 pharmaceuticals had concentrations substantially higher in PMF-influenced effluent (maximum 555,000 ng/L) compared to effluent from control sites (maximum 175 ng/L). Concentrations in WWTP receiving PMF input are variable, as discharges from PMFs are episodic, indicating that production activities can vary substantially over relatively short (several months) periods and have the potential to rapidly transition to other pharmaceutical products. Results show that PMFs are an important, national-scale source of pharmaceuticals to the environment.

Science of the Total Environment↗

Rainfall-runoff of anthropogenic waste indicators from agricultural fields applied with municipal biosolids

The presence of anthropogenic contaminants such as antimicrobials, flame-retardants, and plasticizers in runoff from agricultural fields applied with municipal biosolids may pose a potential threat to the environment. This study assesses the potential for rainfall-induced runoff of 69 anthropogenic waste indicators (AWIs), widely found in household and industrial products, from biosolids amended field plots. The agricultural field containing the test plots was treated with biosolids for the first time immediately prior to this study. AWIs present in soil and biosolids were isolated by continuous liquid-liquid extraction and analyzed by full-scan gas chromatography/mass spectrometry. Results for 18 AWIs were not evaluated due to their presence in field blank QC samples, and another 34 did not have sufficient detection frequency in samples to analyze trends in data. A total of 17 AWIs, including 4-nonylphenol, triclosan, and tris(2-butoxyethyl)phosphate, were present in runoff with acceptable data quality and frequency for subsequent interpretation. Runoff samples were collected 5 days prior to and 1, 9, and 35 days after biosolids application. Of the 17 AWIs considered, 14 were not detected in pre-application samples, or their concentrations were much smaller than in the sample collected one day after application. A range of trends was observed for individual AWI concentrations (typically from 0.1 to 10 μg/L) over the course of the study, depending on the combination of partitioning and degradation mechanisms affecting each compound most strongly. Overall, these results indicate that rainfall can mobilize anthropogenic contaminants from biosolids-amended agricultural fields, directly to surface waters and redistribute them to terrestrial sites away from the point of application via runoff. For 14 of 17 compounds examined, the potential for runoff remobilization during rainstorms persists even after three 100-year rainstorm-equivalent simulations and the passage of a month.

Science of the Total Environment↗

Landfill leachate as a mirror of today's disposable society: Pharmaceuticals and other contaminants of emerging concern in final leachate from landfills in the conterminous United States

Final leachates (leachate after storage or treatment processes) from 22 landfills in 12 states were analyzed for 190 pharmaceuticals and other contaminants of emerging concern (CECs), which were detected in every sample, with the number of CECs ranging from 1 to 58 (median&thinsp;=&thinsp;22). In total, 101 different CECs were detected in leachate samples, including 43 prescription pharmaceuticals, 22 industrial chemicals, 15 household chemicals, 12 nonprescription pharmaceuticals, 5 steroid hormones, and 4 animal/plant sterols. The most frequently detected CECs were lidocaine (91%, local anesthetic), cotinine (86%, nicotine degradate), carisoprodol (82%, muscle relaxant), bisphenol A (77%, component of plastics and thermal paper), carbamazepine (77%, anticonvulsant), and N,N-diethyltoluamide (68%, insect repellent). Concentrations of CECs spanned 7 orders of magnitude, ranging from 2.0&thinsp;ng/L (estrone) to 17&thinsp;200&thinsp;000&thinsp;ng/L (bisphenol A). Concentrations of household and industrial chemicals were the greatest (&sim;1000-1&thinsp;000&thinsp;000&thinsp;ng/L), followed by plant/animal sterols (&sim;1000-100&thinsp;000&thinsp;ng/L), nonprescription pharmaceuticals (&sim;100-10&thinsp;000&thinsp;ng/L), prescription pharmaceuticals (&sim;10-10&thinsp;000&thinsp;ng/L), and steroid hormones (&sim;10-100&thinsp;ng/L). The CEC concentrations in leachate from active landfills were significantly greater than those in leachate from closed, unlined landfills (p&thinsp;=&thinsp;0.05). The CEC concentrations were significantly greater (p&thinsp;<&thinsp;0.01) in untreated leachate compared with treated leachate. The CEC concentrations were significantly greater in leachate disposed to wastewater treatment plants from modern lined landfills than in leachate released to groundwater from closed, unlined landfills (p&thinsp;=&thinsp;0.04). The CEC concentrations were significantly greater (p&thinsp;=&thinsp;0.06) in the fresh leachate (leachate before storage or treatment) reported in a previous study compared with the final leachate sampled for the present study.

Arkansas, Florida, Iowa, Kentucky, Maine, Minnesot↗

Concentrations of hormones, pharmaceuticals and other micropollutants in groundwater affected by septic systems in New England and New York

Septic-system discharges can be an important source of micropollutants (including pharmaceuticals and endocrine active compounds) to adjacent groundwater and surface water systems. Groundwater samples were collected from well networks tapping glacial till in New England (NE) and sandy surficial aquifer New York (NY) during one sampling round in 2011. The NE network assesses the effect of a single large septic system that receives discharge from an extended health care facility for the elderly. The NY network assesses the effect of many small septic systems used seasonally on a densely populated portion of Fire Island. The data collected from these two networks indicate that hydrogeologic and demographic factors affect micropollutant concentrations in these systems. The highest micropollutant concentrations from the NE network were present in samples collected from below the leach beds and in a well downgradient of the leach beds. Total concentrations for personal care/domestic use compounds, pharmaceutical compounds and plasticizer compounds generally ranged from 1 to over 20 &mu;g/L in the NE network samples. High tris(2-butoxyethyl phosphate) plasticizer concentrations in wells beneath and downgradient of the leach beds (> 20 &mu;g/L) may reflect the presence of this compound in cleaning agents at the extended health-care facility. The highest micropollutant concentrations for the NY network were present in the shoreline wells and reflect groundwater that is most affected by septic system discharges. One of the shoreline wells had personal care/domestic use, pharmaceutical, and plasticizer concentrations ranging from 0.4 to 5.7 &mu;g/L. Estradiol equivalency quotient concentrations were also highest in a shoreline well sample (3.1 ng/L). Most micropollutant concentrations increase with increasing specific conductance and total nitrogen concentrations for shoreline well samples. These findings suggest that septic systems serving institutional settings and densely populated areas in coastal settings may be locally important sources of micropollutants to adjacent aquifer and marine systems.

New York↗

Pharmaceuticals and other contaminants of emerging concern in landfill leachate of the United States

Landfills are commonly the final respository for a heterogeneous mixture of waste from residential, commercial, and industrial sources. The use of landfills as a means of waste disposal will likely increase as the global population increases and nations develop. Thus, landfills receiving such waste have the potential to produce leachate containing numerous organic chemicals including contaminants of emerging concern (CECs) such as pharmaceuticals, personal care products, and hormones. This leachate is often discharged to pathways that lead directly (e.g. groundwater, streams) or indirectly (e.g. wastewater treament plants) to the environment. Limited research, however, has been conducted regarding the characterisation of landfill leachate for CECs. To provide the first national-scale assessment of CECs in landfill leachate across the United States, fresh leachate samples (i.e. prior to onsite treatment) from 19 landfills in 16 states were collected in 2011 and analysed for 202 CECs [1]. The targeted CECs were selected for analysis because they were expected to be persistent in the environment; are used, excreted, or disposed of in substantial quantities; may have human or environmental health effects; or are potential indicators of environmentally relevant classes of chemicals or source materials.

Norman Network Bulletin↗

Presence of the Corexit component dioctyl sodium sulfosuccinate in Gulf of Mexico waters after the 2010 Deepwater Horizon oil spill

Between April 22 and July 15, 2010, approximately 4.9 million barrels of oil were released into the Gulf of Mexico from the Deepwater Horizon oil well. Approximately 16% of the oil was chemically dispersed, at the surface and at 1500 m depth, using Corexit 9527 and Corexit 9500, which contain dioctyl sodium sulfosuccinate (DOSS) as a major surfactant component. This was the largest documented release of oil in history at substantial depth, and the first time large quantities of dispersant (0.77 million gallons of approximately 1.9 million gallons total) were applied to a subsurface oil plume. During two cruises in late May and early June, water samples were collected at the surface and at depth for DOSS analysis. Real-time fluorimetry data was used to infer the presence of oil components to select appropriate sampling depths. Samples were stored frozen and in the dark for approximately 6 months prior to analysis by liquid chromatography/tandem mass spectrometry with isotope-dilution quantification. The blank-limited method detection limit (0.25 μg L −1 ) was substantially less than the U.S. Environmental Protection Agency’s (USEPA) aquatic life benchmark of 40 μg L −1 . Concentrations of DOSS exceeding 200 μg L −1 were observed in one surface sample near the well site; in subsurface samples DOSS did not exceed 40 μg L −1 . Although DOSS was present at high concentration in the immediate vicinity of the well where it was being continuously applied, a combination of biodegradation, photolysis, and dilution likely reduced persistence at concentrations exceeding the USEPA aquatic life benchmark beyond this immediate area.

Gulf Of Mexico↗

Contaminants of emerging concern in fresh leachate from landfills in the conterminous United States

To better understand the composition of contaminants of emerging concern (CECs) in landfill leachate, fresh leachate from 19 landfills was sampled across the United States during 2011. The sampled network included 12 municipal and 7 private landfills with varying landfill waste compositions, geographic and climatic settings, ages of waste, waste loads, and leachate production. A total of 129 out of 202 CECs were detected during this study, including 62 prescription pharmaceuticals, 23 industrial chemicals, 18 nonprescription pharmaceuticals, 16 household chemicals, 6 steroid hormones, and 4 plant/animal sterols. CECs were detected in every leachate sample, with the total number of detected CECs in samples ranging from 6 to 82 (median = 31). Bisphenol A (BPA), cotinine, and N , N -diethyltoluamide (DEET) were the most frequently detected CECs, being found in 95% of the leachate samples, followed by lidocaine (89%) and camphor (84%). Other frequently detected CECs included benzophenone, naphthalene, and amphetamine, each detected in 79% of the leachate samples. CEC concentrations spanned six orders of magnitude, ranging from ng L &minus;1 to mg L &minus;1 . Industrial and household chemicals were measured in the greatest concentrations, composing more than 82% of the total measured CEC concentrations. Maximum concentrations for three household and industrial chemicals, para -cresol (7 020 000 ng L &minus;1 ), BPA (6 380 000 ng L &minus;1 ), and phenol (1 550 000 ng L &minus;1 ), were the largest measured, with these CECs composing 70% of the total measured CEC concentrations. Nonprescription pharmaceuticals represented 12%, plant/animal sterols 4%, prescription pharmaceuticals 1%, and steroid hormones <1% of the total measured CEC concentrations. Leachate from landfills in areas receiving greater amounts of precipitation had greater frequencies of CEC detections and concentrations in leachate than landfills receiving less precipitation.

Environmental Science: Processes and Impacts↗

Spatiotemporal variations in estrogenicity, hormones, and endocrine-disrupting compounds in influents and effluents of selected wastewater-treatment plants and receiving streams in New York, 2008-09

Endocrine-disrupting compounds (EDCs) in wastewater effluents have been linked to changes in sex ratios, intersex (in males), behavioral modifications, and developmental abnormalities in aquatic organisms. Yet efforts to identify and regulate specific EDCs in complex mixtures are problematic because little is known about the estrogen activity (estrogenicity) levels of many common and emerging contaminants. The potential effects of EDCs on the water quality and health of biota in streams of the New York City water supply is especially worrisome because more than 150 wastewater-treatment plants (WWTPs) are permitted to discharge effluents into surface waters and groundwaters of watersheds that provide potable water to more than 9 million people. In 2008, the U.S. Geological Survey (USGS), the New York State Department of Environmental Conservation (NYSDEC), New York State Department of Health (NYSDOH), and New York City Department of Environmental Protection (NYCDEP) began a pilot study to increase the understanding of estrogenicity and EDCs in effluents and receiving streams mainly in southeastern New York. The primary goals of this study were to document and assess the spatial and temporal variability of estrogenicity levels; the effectiveness of various treatment-plant types to remove estrogenicity; the concentrations of hormones, EDCs, and pharmaceuticals, personal care products (PPCPs); and the relations between estrogenicity and concentrations of hormones, EDCs, and PPCPs. The levels of estrogenicity and selected hormones, non-hormone EDCs, and PPCPs were characterized in samples collected seasonally in effluents from 7 WWTPs, once or twice in effluents from 34 WWTPs, and once in influents to 6 WWTPs. Estrogenicity was quantified, as estradiol equivalents, using both the biological e-screen assay and a chemical model. Results generally show that (1) estrogenicity levels in effluents varied spatially and seasonally, (2) a wide range of known and unknown EDCs were present in both WWTP effluents and receiving streams, (3) some effluents may be important sources of estrogenicity in weakly diluted streams, (4) measured levels of biological estrogenicity were often higher than estimated levels of chemical estrogenicity, and (5) the type of treatment had a large effect on the removal efficacy, and consequently, the estrogenicity levels observed in treated effluents.

New York↗

An isotope-dilution standard GC/MS/MS method for steroid hormones in water

An isotope-dilution quantification method was developed for 20 natural and synthetic steroid hormones and additional compounds in filtered and unfiltered water. Deuterium- or carbon-13-labeled isotope-dilution standards (IDSs) are added to the water sample, which is passed through an octadecylsilyl solid-phase extraction (SPE) disk. Following extract cleanup using Florisil SPE, method compounds are converted to trimethylsilyl derivatives and analyzed by gas chromatography with tandem mass spectrometry. Validation matrices included reagent water, wastewater-affected surface water, and primary (no biological treatment) and secondary wastewater effluent. Overall method recovery for all analytes in these matrices averaged 100%; with overall relative standard deviation of 28%. Mean recoveries of the 20 individual analytes for spiked reagent-water samples prepared along with field samples analyzed in 2009–2010 ranged from 84–104%, with relative standard deviations of 6–36%. Detection levels estimated using ASTM International’s D6091–07 procedure range from 0.4 to 4 ng/L for 17 analytes. Higher censoring levels of 100 ng/L for bisphenol A and 200 ng/L for cholesterol and 3-beta-coprostanol are used to prevent bias and false positives associated with the presence of these analytes in blanks. Absolute method recoveries of the IDSs provide sample-specific performance information and guide data reporting. Careful selection of labeled compounds for use as IDSs is important because both inexact IDS-analyte matches and deuterium label loss affect an IDS’s ability to emulate analyte performance. Six IDS compounds initially tested and applied in this method exhibited deuterium loss and are not used in the final method.

Book chapter↗

Persistence and potential effects of complex organic contaminant mixtures in wastewater-impacted streams

Natural and synthetic organic contaminants in municipal wastewater treatment plant (WWTP) effluents can cause ecosystem impacts, raising concerns about their persistence in receiving streams. In this study, Lagrangian sampling, in which the same approximate parcel of water is tracked as it moves downstream, was conducted at Boulder Creek, Colorado and Fourmile Creek, Iowa to determine in-stream transport and attenuation of organic contaminants discharged from two secondary WWTPs. Similar stream reaches were evaluated, and samples were collected at multiple sites during summer and spring hydrologic conditions. Travel times to the most downstream (7.4 km) site in Boulder Creek were 6.2 h during the summer and 9.3 h during the spring, and to the Fourmile Creek 8.4 km downstream site times were 18 and 8.8 h, respectively. Discharge was measured at each site, and integrated composite samples were collected and analyzed for >200 organic contaminants including metal complexing agents, nonionic surfactant degradates, personal care products, pharmaceuticals, steroidal hormones, and pesticides. The highest concentration (>100 μg L –1 ) compounds detected in both WWTP effluents were ethylenediaminetetraacetic acid and 4-nonylphenolethoxycarboxylate oligomers, both of which persisted for at least 7 km downstream from the WWTPs. Concentrations of pharmaceuticals were lower (<1 μg L –1 ), and several compounds, including carbamazepine and sulfamethoxazole, were detected throughout the study reaches. After accounting for in-stream dilution, a complex mixture of contaminants showed little attenuation and was persistent in the receiving streams at concentrations with potential ecosystem implications.

Colorado, Iowa↗

Chemical contaminants in water and sediment near fish nesting sites in the Potomac River basin: determining potential exposures to smallmouth bass (Micropterus dolomieu)

The Potomac River basin is an area where a high prevalence of abnormalities such as testicular oocytes (TO), skin lesions, and mortality has been observed in smallmouth bass (SMB, Micropterus dolomieu). Previous research documented a variety of chemicals in regional streams, implicating chemical exposure as one plausible explanation for these biological effects. Six stream sites in the Potomac basin (and one out-of-basin reference site) were sampled to provide an assessment of chemicals in these streams. Potential early life-stage exposure to chemicals detected was assessed by collecting samples in and around SMB nesting areas. Target chemicals included those known to be associated with important agricultural and municipal wastewater sources in the Potomac basin. The prevalence and severity of TO in SMB were also measured to determine potential relations between chemistry and biological effects. A total of 39 chemicals were detected at least once in the discrete-water samples, with atrazine, caffeine, deethylatrazine, simazine, and iso-chlorotetracycline being most frequently detected. Of the most frequently detected chemicals, only caffeine was detected in water from the reference site. No biogenic hormones/sterols were detected in the discrete-water samples. In contrast, 100 chemicals (including six biogenic hormones/sterols) were found in a least one passive-water sample, with 25 being detected at all such samples. In addition, 46 chemicals (including seven biogenic hormones/sterols) were found in the bed-sediment samples, with caffeine, cholesterol, indole, para-cresol, and sitosterol detected in all such samples. The number of herbicides detected in discrete-water samples per site had a significant positive relation to TO rank (a nonparametric indicator of TO), with significant positive relations between TO rank and atrazine concentrations in discrete-water samples and to total hormone/sterol concentration in bed-sediment samples. Such significant correlations do not necessarily imply causation, as these chemical compositions and concentrations likely do not adequately reflect total SMB exposure history, particularly during critical life stages.

Potomac River Basin↗

Bioassay of estrogenicity and chemical analyses of estrogens in streams across the United States associated with livestock operations

Animal manures, used as a nitrogen source for crop production, are often associated with negative impacts on nutrient levels in surface water. The concentrations of estrogens in streams from these manures also are of concern due to potential endocrine disruption in aquatic species. Streams associated with livestock operations were sampled by discrete samples (n = 38) or by time-integrated polar organic chemical integrative samplers (POCIS,n = 19). Samples were analyzed for estrogens by gas chromatography-tandem mass spectrometry (GC-MSM 2 ) and estrogenic activity was assessed by three bioassays: Yeast Estrogen Screen (YES), T47D-KBluc Assay, MCF-7 Estrogenicity Screen (E-Screen). Samples were collected from 19 streams within small (∼1-30 km 2 ) watersheds in 12 U.S. states representing a range of hydrogeologic conditions, dominated by: dairy (3), grazing beef (3), feedlot cattle (1); swine (5); poultry (3); and 4 areas where no livestock were raised or manure was applied. Water samples were consistently below the United Kingdom proposed Lowest Observable Effect Concentration for 17b-estradiol in fish (10 ng/L) in all watersheds, regardless of land use. Estrogenic activity was often higher in samples during runoff conditions following a period of manure application. Estrone was the most commonly detected estrogen (13 of 38 water samples, mean 1.9, maximum 8.3 ng/L). Because of the T47D-KBluc assay’s sensitivity towards estrone (1.4 times 17β-estradiol) it was the most sensitive method for detecting estrogens, followed by the E-Screen, GC-MS 2 , and YES. POCIS resulted in more frequent detections of estrogens than discrete water samples across all sites, even when applying the less-sensitive YES bioassay to the POCIS extracts.

Water Research↗

Effects of surface applications of biosolids on groundwater quality and trace-element concentrations in crops near Deer Trail, Colorado, 2004-2010

The U.S. Geological Survey (USGS), in cooperation with Metro Wastewater Reclamation District (Metro District), studied biosolids composition and the effects of biosolids applications on groundwater quality and trace-element concentrations in crops of the Metro District properties near Deer Trail, Colorado, during 2004 through 2010. Priority parameters for each monitoring component included the nine trace elements regulated by Colorado for biosolids (arsenic, cadmium, copper, lead, mercury, molybdenum, nickel, selenium, and zinc); other constituents also were analyzed. All concentrations for the priority parameters in monthly biosolids samples were less than Colorado regulatory limits, and the concentrations were relatively consistent. Biosolids likely were the largest source of nitrogen and phosphorus on the Metro District properties. Plutonium isotopes were not detected in the biosolids, but many organic wastewater compounds (organic wastewater compounds: wastewater indicators, pharmaceuticals, and hormones) were detected in substantial concentrations relative to minimum reporting levels and various surface-water concentrations. Bismuth, copper, mercury, nitrogen, phosphorus, silver, biogenic sterols, detergent degradates, disinfectants, fire retardants, fragrances, pharmaceuticals, and plasticizers would be the most likely biosolids signature to indicate the presence of Metro District biosolids in soil or streambed sediment from the study area. Antimony, cadmium, cobalt, copper, molybdenum, nickel, nitrogen, phosphorus, selenium, tungsten, vanadium, zinc, detergent degradates, disinfectants, fire retardants, fragrances, pharmaceuticals or their degradates, and plasticizers would be the most likely biosolids signature for groundwater and surface water in the study area. More biosolids-signature components detected and larger concentration differences from untreated materials, baseline, and blank samples indicate more evidence of biosolids presence or effects. Although the inorganic constituent concentrations were relatively large in samples from one monitoring well, the concentrations of organic wastewater compounds in groundwater samples were not correspondingly large. Concentrations of organic wastewater compounds in the groundwater samples from all five monitoring wells were less than the minimum reporting levels with only a few detections. Some of the organic wastewater compounds detected could have anthropogenic sources that are not biosolids. Concentrations of priority parameters in groundwater varied spatially and temporally but generally were less than Colorado regulatory limits. Concentrations of dissolved nitrate, arsenic, and selenium, in addition to chloride, sulfate, total dissolved solids, boron, iron, manganese, and uranium, in samples from some wells exceeded the Colorado standards. Concentrations of dissolved nitrate (three wells), molybdenum (one well), selenium (two wells), and uranium (one well) in shallow groundwater had significant (alpha = 0.05) upward trends in some parts of the study area. The biosolids-signature results indicate that the aquifers intercepted by the five routinely sampled wells likely have received some recharge through treated (biosolids-applied) fields or biosolids-affected ponds. Adverse effects from this biosolids-related recharge range from few (if any) at one well to large and significantly (alpha = 0.05) increasing nitrate concentrations at another well. A statistical evaluation of five paired wheat-grain samples from treated (biosolids-applied) fields and untreated (control) fields did not indicate any evidence that biosolids applications significantly (alpha = 0.05 or 0.10) increased concentration of any of these constituents in wheat grain. The wheat-grain concentrations from this study were similar to those from other studies for fields in North America where no biosolids were applied. The data for the limited crop samples indicate that biosolids applications are not increasing the concentrations of arsenic, cadmium, copper, lead, mercury, molybdenum, nickel, selenium, sulfur, and zinc in mature wheat grain from the study area.

Colorado↗