Comparison of detection limits estimated using single- and multi-concentration spike-based and blank-based procedures.

Spike- and blank-based procedures were applied to estimate the detection limits (DLs) for example analytes from inorganic and organic methods for water samples to compare with the U.S. Environmental Protection Agency's (EPA) Method Detection Limit (MDL) procedures (revisions 1.11 and 2.0). The multi-concentration spike-based procedures ASTM Within-laboratory Critical Level (DQCALC) and EPA's Lowest Concentration Minimum Reporting Level were compared in one application, with DQCALC further applied to many methods. The blank-based DLs, MDLb99 (99th percentile) or MDLbY (= mean blank concentration + s × t), estimated using large numbers (>100) of blank samples often provide DLs that better approach or achieve the desired ≤1% false positive risk level compared to spike-based DLs. For primarily organic methods that do not provide many uncensored blank results, spike-based DQCALC or MDL rev. 2.0 are needed to simulate the blank distribution and estimate the DL. DQCALC is especially useful for estimating DLs for multi-analyte methods having very different analyte response characteristics. Time series plots of DLs estimated using different procedures reveal that DLs are dependent on the applied procedure, should not be expected to be static over time, and seem best viewed as falling over a range versus being a single value. Use of both blank- and spike-based DL procedures help inform this DL range. Data reporting conventions that censor data at a threshold and report "less than" that threshold concentration as the reporting level have unknown and potentially high false negative risk. The U.S. Geological Survey National Water Quality Laboratory's Laboratory Reporting Level (LRL) convention (applied primarily to organic methods) attempts to simultaneously minimize both the false positive and false negative risk when 

Urban Stormwater: An Overlooked Pathway of Extensive Mixed Contaminants to Surface and Groundwaters in the United States.

Increasing global reliance on stormwater control measures to reduce discharge to surface water, increase groundwater recharge, and minimize contaminant delivery to receiving waterbodies necessitates improved understanding of stormwater-contaminant profiles. A multiagency study of organic and inorganic chemicals in urban stormwater from 50 runoff events at 21 sites across the United States demonstrated that stormwater transports substantial mixtures of polycyclic aromatic hydrocarbons, bioactive contaminants (pesticides and pharmaceuticals), and other organic chemicals known or suspected to pose environmental health concern. Numerous organic-chemical detections per site (median number of chemicals detected = 73), individual concentrations exceeding 10 000 ng/L, and cumulative concentrations up to 263 000 ng/L suggested concern for potential environmental effects during runoff events. Organic concentrations, loads, and yields were positively correlated with impervious surfaces and highly developed urban catchments. Episodic storm-event organic concentrations and loads were comparable to and often exceeded those of daily wastewater plant discharges. Inorganic chemical concentrations were generally dilute in concentration and did not exceed chronic aquatic life criteria. Methylmercury was measured in 90% of samples with concentrations that ranged from 0.05 to 1.0 ng/L.

Hormones and Pharmaceuticals in Groundwater Used As a Source of Drinking Water Across the United States.

This is the first large-scale, systematic assessment of hormone and pharmaceutical occurrence in groundwater used for drinking across the United States. Samples from 1091 sites in Principal Aquifers representing 60% of the volume pumped for drinking-water supply had final data for 21 hormones and 103 pharmaceuticals. At least one compound was detected at 5.9% of 844 sites representing the resource used for public supply across the entirety of 15 Principal Aquifers, and at 11.3% of 247 sites representing the resource used for domestic supply over subareas of nine Principal Aquifers. Of 34 compounds detected, one plastics component (bisphenol A), three pharmaceuticals (carbamazepine, sulfamethoxazole, and meprobamate), and the caffeine degradate 1,7-dimethylxanthine were detected in more than 0.5% of samples. Hydrocortisone had a concentration greater than a human-health benchmark at 1 site. Compounds with high solubility and low Koc were most likely to be detected. Detections were most common in shallow wells with a component of recent recharge, particularly in crystalline-rock and mixed land-use settings. Results indicate vulnerability of groundwater used for drinking water in the U.S. to contamination by these compounds is generally limited, and exposure to these compounds at detected concentrations is unlikely to have adverse effects on human health.

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.

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.

Enabling Science Support for Better Decision-Making when Responding to Chemical Spills.

Chemical spills and accidents contaminate the environment and disrupt societies and economies around the globe. In the United States there were approximately 172,000 chemical spills that affected US waterbodies from 2004 to 2014. More than 8000 of these spills involved non-petroleum-related chemicals. Traditional emergency responses or incident command structures (ICSs) that respond to chemical spills require coordinated efforts by predominantly government personnel from multiple disciplines, including disaster management, public health, and environmental protection. However, the requirements of emergency response teams for science support might not be met within the traditional ICS. We describe the US ICS as an example of emergency-response approaches to chemical spills and provide examples in which external scientific support from research personnel benefitted the ICS emergency response, focusing primarily on nonpetroleum chemical spills. We then propose immediate, near-term, and long-term activities to support the response to chemical spills, focusing on nonpetroleum chemical spills. Further, we call for science support for spill prevention and near-term spill-incident response and identify longer-term research needs. The development of a formal mechanism for external science support of ICS from governmental and nongovernmental scientists would benefit rapid responders, advance incident- and crisis-response science, and aid society in coping with and recovering from chemical spills.

The impact of onsite wastewater disposal systems on groundwater in areas inundated by Hurricane Sandy in New York and New Jersey.

Coastal onsite wastewater disposal systems (OWDS) were inundated by Hurricane Sandy's storm tide. This study compares the shallow groundwater quality (nutrients, pharmaceuticals, and hormones) downgradient of OWDS before and after Hurricane Sandy, where available, and establishes a baseline for wastewater influence on groundwater in coastal communities inundated by Hurricane Sandy. Nutrients and contaminants of emerging concern (CECs) were detected in shallow groundwater downgradient of OWDS in two settings along the New Jersey and New York coastlines: 1) a single, centralized OWDS in a park; and 2) multiple OWDS (cesspools) in low-density residential and mixed-use/medium density residential areas. The most frequently detected pharmaceuticals were lidocaine (40%), carbamazepine (36%), and fexofenadine, bupropion, desvenlafaxine, meprobamate, and tramadol (24-32%). Increases in the number and total concentration of pharmaceuticals after Hurricane Sandy may reflect other factors (seasonality, usage) besides inundation, and demonstrate the importance of analyzing for a wide variety of CECs in regional studies.

Pre/post-closure assessment of groundwater pharmaceutical fate in a wastewater-facility-impacted stream reach.

Pharmaceutical contamination of contiguous groundwater is a substantial concern in wastewater-impacted streams, due to ubiquity in effluent, high aqueous mobility, designed bioactivity, and to effluent-driven hydraulic gradients. Wastewater treatment facility (WWTF) closures are rare environmental remediation events; offering unique insights into contaminant persistence, long-term wastewater impacts, and ecosystem recovery processes. The USGS conducted a combined pre/post-closure groundwater assessment adjacent to an effluent-impacted reach of Fourmile Creek, Ankeny, Iowa, USA. Higher surface-water concentrations, consistent surface-water to groundwater concentration gradients, and sustained groundwater detections tens of meters from the stream bank demonstrated the importance of WWTF effluent as the source of groundwater pharmaceuticals as well as the persistence of these contaminants under effluent-driven, pre-closure conditions. The number of analytes (110 total) detected in surface water decreased from 69 prior to closure down to 8 in the first post-closure sampling event approximately 30 d later, with a corresponding 2 order of magnitude decrease in the cumulative concentration of detected analytes. Post-closure cumulative concentrations of detected analytes were approximately 5 times higher in proximal groundwater than in surface water. About 40% of the 21 contaminants detected in a downstream groundwater transect immediately before WWTF closure exhibited rapid attenuation with estimated half-lives on the order of a few days; however, a comparable number exhibited no consistent attenuation during the year-long post-closure assessment. The results demonstrate the potential for effluent-impacted shallow groundwater systems to accumulate pharmaceutical contaminants and serve as long-term residual sources, further increasing the risk of adverse ecological effects in groundwater and the near-stream ecosystem.

Contamination with bacterial zoonotic pathogen genes in U.S. streams influenced by varying types of animal agriculture.

Animal waste, stream water, and streambed sediment from 19 small (<32km(2)) watersheds in 12U.S. states having either no major animal agriculture (control, n=4), or predominantly beef (n=4), dairy (n=3), swine (n=5), or poultry (n=3) were tested for: 1) cholesterol, coprostanol, estrone, and fecal indicator bacteria (FIB) concentrations, and 2) shiga-toxin producing and enterotoxigenic Escherichia coli, Salmonella, Campylobacter, and pathogenic and vancomycin-resistant enterococci by polymerase chain reaction (PCR) on enrichments, and/or direct quantitative PCR. Pathogen genes were most frequently detected in dairy wastes, followed by beef, swine and poultry wastes in that order; there was only one detection of an animal-source-specific pathogen gene (stx1) in any water or sediment sample in any control watershed. Post-rainfall pathogen gene numbers in stream water were significantly correlated with FIB, cholesterol and coprostanol concentrations, and were most highly correlated in dairy watershed samples collected from 3 different states. Although collected across multiple states and ecoregions, animal-waste gene profiles were distinctive via discriminant analysis. Stream water gene profiles could also be discriminated by the watershed animal type. Although pathogen genes were not abundant in stream water or streambed samples, PCR on enrichments indicated that many genes were from viable organisms, including several (shiga-toxin producing or enterotoxigenic E. coli, Salmonella, vancomycin-resistant enterococci) that could potentially affect either human or animal health. Pathogen gene numbers and types in stream water samples were influenced most by animal type, by local factors such as whether animals had stream access, and by the amount of local rainfall, and not by studied watershed soil or physical characteristics. Our results indicated that stream water in small agricultural U.S. watersheds was susceptible to pathogen gene inputs under typical agricultural practices and environmental conditions. Pathogen gene profiles may offer the potential to address both source of, and risks associated with, fecal pollution.

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.

Genes Indicative of Zoonotic and Swine Pathogens Are Persistent in Stream Water and Sediment following a Swine Manure Spill.

Manure spills into streams are relatively frequent, but no studies have characterized stream contamination with zoonotic and veterinary pathogens, or fecal chemicals, following a spill. We tested stream water and sediment over 25 days and downstream for 7.6 km for the following: fecal indicator bacteria (FIB), the fecal indicator chemicals cholesterol and coprostanol, 20 genes for zoonotic and swine-specific bacterial pathogens by presence/absence PCR for viable cells, one swine-specific Escherichia coli toxin gene (STII gene) by quantitative PCR (qPCR), and nine human and animal viruses by qPCR or reverse transcription-qPCR. Twelve days postspill, and 4.2 km downstream, water concentrations of FIB, cholesterol, and coprostanol were 1 to 2 orders of magnitude greater than those detected before, or above, the spill, and genes indicating viable zoonotic or swine-infectious Escherichia coli were detected in water or sediment. STII gene levels increased from undetectable before or above the spill to 10(5) copies/100 ml of water 12 days postspill. Thirteen of 14 water (8/9 sediment) samples had viable STII-carrying cells postspill. Eighteen days postspill, porcine adenovirus and teschovirus were detected 5.6 km downstream. FIB concentrations (per gram [wet weight]) in sediment were greater than in water, and sediment was a continuous reservoir of genes and chemicals postspill. Constituent concentrations were much lower, and detections less frequent, in a runoff event (200 days postspill) following manure application, although the swine-associated STII and stx2e genes were detected. Manure spills are an underappreciated pathway for livestock-derived contaminants to enter streams, with persistent environmental outcomes and the potential for human and veterinary health consequences.

Determination of (4-methylcyclohexyl)methanol isomers by heated purge-and-trap GC/MS in water samples from the 2014 Elk River, West Virginia, chemical spill.

A heated purge-and-trap gas chromatography/mass spectrometry method was used to determine the cis- and trans-isomers of (4-methylcyclohexyl)methanol (4-MCHM), the reported major component of the Crude MCHM/Dowanol™ PPh glycol ether material spilled into the Elk River upriver from Charleston, West Virginia, on January 9, 2014. The trans-isomer eluted first and method detection limits were 0.16-µg L(-1)trans-, 0.28-µg L(-1)cis-, and 0.4-µg L(-1) Total (total response of isomers) 4-MCHM. Estimated concentrations in the spill source material were 491-g L(-1)trans- and 277-g L(-1)cis-4-MCHM, the sum constituting 84% of the source material assuming its density equaled 4-MCHM. Elk River samples collected⩽3.2 km downriver from the spill on January 15 had low (⩽2.9 µg L(-1) Total) 4-MCHM concentrations, whereas the isomers were not detected in samples collected 2 d earlier at the same sites. Similar 4-MCHM concentrations (range 4.2-5.5 µg L(-1) Total) occurred for samples of the Ohio River at Louisville, Kentucky, on January 17, ∼630 km downriver from the spill. Total 4-MCHM concentrations in Charleston, WV, office tap water decreased from 129 µg L(-1) on January 27 to 2.2 µg L(-1) on February 3, but remained detectable in tap samples through final collection on February 25 indicating some persistence of 4-MCHM within the water distribution system. One isomer of methyl 4-methylcyclohexanecarboxylate was detected in all Ohio River and tap water samples, and both isomers were detected in the source material spilled.

Riverbank filtration potential of pharmaceuticals in a wastewater-impacted stream.

Pharmaceutical contamination of shallow groundwater is a substantial concern in effluent-dominated streams, due to high aqueous mobility, designed bioactivity, and effluent-driven hydraulic gradients. In October and December 2012, effluent contributed approximately 99% and 71%, respectively, to downstream flow in Fourmile Creek, Iowa, USA. Strong hydrologic connectivity was observed between surface-water and shallow-groundwater. Carbamazepine, sulfamethoxazole, and immunologically-related compounds were detected in groundwater at greater than 0.02 µg L(-1) at distances up to 6 m from the stream bank. Direct aqueous-injection HPLC-MS/MS revealed 43% and 55% of 110 total pharmaceutical analytes in surface-water samples in October and December, respectively, with 16% and 6%, respectively, detected in groundwater approximately 20 m from the stream bank. The results demonstrate the importance of effluent discharge as a driver of local hydrologic conditions in an effluent-impacted stream and thus as a fundamental control on surface-water to groundwater transport of effluent-derived pharmaceutical contaminants.

Integrated assessment of runoff from livestock farming operations: Analytical chemistry, in vitro bioassays, and in vivo fish exposures.

Animal waste from livestock farming operations can contain varying levels of natural and synthetic androgens and/or estrogens, which can contaminate surrounding waterways. In the present study, surface stream water was collected from 6 basins containing livestock farming operations. Aqueous concentrations of 12 hormones were determined via chemical analyses. Relative androgenic and estrogenic activity was measured using in vitro cell assays (MDA-kb2 and T47D-Kbluc assays, respectively). In parallel, 48-h static-renewal in vivo exposures were conducted to examine potential endocrine-disrupting effects in fathead minnows. Mature fish were exposed to surface water dilutions (0%, 25%, 50%, and 100%) and 10-ng/L of 17α-ethynylestradiol or 50-ng/L of 17ß-trenbolone as positive controls. Hepatic expression of vitellogenin and estrogen receptor α mRNA, gonadal ex vivo testosterone and 17ß-estradiol production, and plasma vitellogenin concentrations were examined. Potentially estrogenic and androgenic steroids were detected at low nanogram per liter concentrations. In vitro estrogenic activity was detected in all samples, whereas androgenic activity was detected in only 1 sample. In vivo exposures to the surface water had no significant dose-dependent effect on any of the biological endpoints, with the exception of increased male testosterone production in 1 exposure. The present study, which combines analytical chemistry measurements, in vitro bioassays, and in vivo fish exposures, highlights the integrated value and future use of a combination of techniques to obtain a comprehensive characterization of an environmental chemical mixture.

Pesticides in Mississippi air and rain: a comparison between 1995 and 2007.

A variety of current-use pesticides were determined in weekly composite air and rain samples collected during the 1995 and 2007 growing seasons in the Mississippi Delta (MS, USA) agricultural region. Similar sampling and analytical methods allowed for direct comparison of results. Decreased overall pesticide use in 2007 relative to 1995 generally resulted in decreased detection frequencies in air and rain; observed concentration ranges were similar between years, however, even though the 1995 sampling site was 500 m from active fields whereas the 2007 sampling site was within 3 m of a field. Mean concentrations of detections were sometimes greater in 2007 than in 1995, but the median values were often lower. Seven compounds in 1995 and 5 in 2007 were detected in ≥50% of both air and rain samples. Atrazine, metolachlor, and propanil were detected in ≥50% of the air and rain samples in both years. Glyphosate and its degradation product, aminomethyl-phosphonic acid (AMPA), were detected in ≥75% of air and rain samples in 2007 but were not measured in 1995. The 1995 seasonal wet depositional flux was dominated by methyl parathion (88%) and was >4.5 times the 2007 flux. Total herbicide flux in 2007 was slightly greater than in 1995 and was dominated by glyphosate. Malathion, methyl parathion, and degradation products made up most of the 2007 nonherbicide flux.

Concentrations of polycyclic aromatic hydrocarbons (PAHs) and azaarenes in runoff from coal-tar- and asphalt-sealcoated pavement.

Coal-tar-based sealcoat, used extensively on parking lots and driveways in North America, is a potent source of PAHs. We investigated how concentrations and assemblages of PAHs and azaarenes in runoff from pavement newly sealed with coal-tar-based (CT) or asphalt-based (AS) sealcoat changed over time. Samples of simulated runoff were collected from pavement 5 h to 111 d following application of AS or CT sealcoat. Concentrations of the sum of 16 PAHs (median concentrations of 328 and 35 µg/L for CT and AS runoff, respectively) in runoff varied relatively little, but rapid decreases in concentrations of azaarenes and low molecular weight PAHs were offset by increases in high molecular weight PAHs. The results demonstrate that runoff from CT-sealcoated pavement, in particular, continues to contain elevated concentrations of PAHs long after a 24-h curing time, with implications for the fate, transport, and ecotoxicological effects of contaminants in runoff from CT-sealcoated pavement.

Sampling trace organic compounds in water: a comparison of a continuous active sampler to continuous passive and discrete sampling methods.

A continuous active sampling method was compared to continuous passive and discrete sampling methods for the sampling of trace organic compounds (TOCs) in water. Results from each method are compared and contrasted in order to provide information for future investigators to use while selecting appropriate sampling methods for their research. The continuous low-level aquatic monitoring (CLAM) sampler (C.I.Agent® Storm-Water Solutions) is a submersible, low flow-rate sampler, that continuously draws water through solid-phase extraction media. CLAM samplers were deployed at two wastewater-dominated stream field sites in conjunction with the deployment of polar organic chemical integrative samplers (POCIS) and the collection of discrete (grab) water samples. All samples were analyzed for a suite of 69 TOCs. The CLAM and POCIS samples represent time-integrated samples that accumulate the TOCs present in the water over the deployment period (19-23 h for CLAM and 29 days for POCIS); the discrete samples represent only the TOCs present in the water at the time and place of sampling. Non-metric multi-dimensional scaling and cluster analysis were used to examine patterns in both TOC detections and relative concentrations between the three sampling methods. A greater number of TOCs were detected in the CLAM samples than in corresponding discrete and POCIS samples, but TOC concentrations in the CLAM samples were significantly lower than in the discrete and (or) POCIS samples. Thirteen TOCs of varying polarity were detected by all of the three methods. TOC detections and concentrations obtained by the three sampling methods, however, are dependent on multiple factors. This study found that stream discharge, constituent loading, and compound type all affected TOC concentrations detected by each method. In addition, TOC detections and concentrations were affected by the reporting limits, bias, recovery, and performance of each method.

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.

Chiral pesticides: identification, description, and environmental implications.

Of the 1,693 pesticides considered in this review, 1,594 are organic chemicals, 47 are inorganic chemicals, 53 are of biological origin (largely non chemical; insect,fungus, bacteria, virus, etc.), and 2 have an undetermined structure. Considering that the EPA's Office of Pesticide Programs found 1,252 pesticide active ingredients(EPA Pesticides Customer Service 2011), we consider this dataset to be comprehensive; however, no direct comparison of the compound lists was undertaken. Of all pesticides reviewed, 482 (28%) are chiral; 30% are chiral when considering only the organic chemical pesticides. A graph of this distribution is shown in Fig. 7a. Each pesticide is classified with up to three pesticidal utilities (e.g., fungicide, plant growth regulator, rodenticide, etc.), taken first from the Pesticide Manual as a primary source, and the Compendium of Common Pesticide Names website as a secondary source. Of the chiral pesticides, 195 (34%) are insecticides (including attractants, pheromones, and repellents), 150 (27%) are herbicides (including plant growth regulators and herbicide safeners), 104 (18%) are fungicides, and 55 (10%)are acaricides. The distribution of chiral pesticides by utility is shown in Fig. 7b,including categories of pesticides that make up 3%t or less of the usage categories.Figure 7c shows a similar distribution of non chiral pesticide usage categories. Of the chiral pesticides, 270 (56%) have one chiral feature, 105 (22%) have two chiral features, 30 (6.2%) have three chiral features, and 29 (6.0%) have ten or more chiral features.Chiral chemicals pose many difficulties in stereospecific synthesis, characterization, and analysis. When these compounds are purposely put into the environment,even more interesting complications arise in tracking, monitoring, and predicting their fate and risks. More than 475 pesticides are chiral, as are other chiral contaminants such as pharmaceuticals, polychlorinated biphenyls, brominated flame retardants, synthetic musks, and their degradates (Kallenborn and Hiihnerfuss 2001;Heeb et al. 2007; Hihnerfuss and Shah 2009). The stereoisomers of pesticides can have widely different efficacy, toxicity to nontarget organisms, and metabolic rates in biota. For these reasons, it is important to first be aware of likely fate and effect differences, to incorporate molecular asymmetry insights into research projects, and to study the individual stereoisomers of the applied pesticide material.With the advent of enantioselective chromatography techniques, the chirality of pesticides has been increasingly studied. While the ChirBase (Advanced ChemistryDevelopment 1997-2010) database does not include all published chiral analytical separations, it does contain more than 3,500 records for 146 of the 482 chiral pesticides (30%). The majority of the records are found in the liquid chromatography database (2,677 or 76%), followed by the gas chromatography database (652 or 18%),and the capillary electrophoresis database (203 or 6%). The finding that only 30% of the chiral pesticides covered in this review have entries in ChirBase highlights the need for expanded efforts to develop additional enantioselective chromatographic methods. Other techniques (e.g., nuclear magnetic resonance and other spectroscopy)are available for investigation of chiral compounds, but often are not utilized because of cost, complexity, or simply not recognizing that a pesticide is chiral.In this review, we have listed and have briefly described the general nature of chiral fungicides, herbicides, insecticides, and other miscellaneous classes. A data-set generated for this review contains 1,693 pesticides, the number of enantioselective separation records in ChirBase, pesticide usage class, SMILES structure string and counts of stereogenic centers. This dataset is publically available for download at the following website: http://www.epa.gov/heasd/products/products.html. With the information herein coupled to the publically accessible dataset, we can begin to develop the tools to handle molecular asymmetry as it applies to agrochemicals.Additional structure-based resources would allow further analysis of key parameters (e.g., exposure, toxicity, environmental fate, degradation, and risks) for individual stereoisomers of chiral compounds.

Volatilization of polycyclic aromatic hydrocarbons from coal-tar-sealed pavement.

Coal-tar-based pavement sealants, a major source of PAHs to urban water bodies, are a potential source of volatile PAHs to the atmosphere. An initial assessment of volatilization of PAHs from coal-tar-sealed pavement is presented here in which we measured summertime gas-phase PAH concentrations 0.03 m and 1.28 m above the pavement surface of seven sealed (six with coal-tar-based sealant and one with asphalt-based sealant) and three unsealed (two asphalt and one concrete) parking lots in central Texas. PAHs also were measured in parking lot dust. The geometric mean concentration of the sum of eight frequently detected PAHs (ΣPAH(8)) in the 0.03-m samples above sealed lots (1320 ng m(-3)) during the hottest part of the day was 20 times greater than that above unsealed lots (66.5 ng m(-3)). The geometric mean concentration in the 1.28-m samples above sealed lots (138 ng m(-3)) was five times greater than above unsealed lots (26.0 ng m(-3)). Estimated PAH flux from the sealed lots was 60 times greater than that from unsealed lots (geometric means of 88 and 1.4 µg m(-2) h(-1), respectively). Although the data set presented here is small, the much higher estimated fluxes from sealed pavement than from unsealed pavement indicate that coal-tar-based sealants are emitting PAHs to urban air at high rates compared to other paved surfaces.