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Arsenic transformation and mobilization from minerals by the arsenite oxidizing strain WAO

Analysis of arsenic concentrations in New Jersey well water from the Newark Basin showed up to 15% of the wells exceed 10 ??g L-1, with a maximum of 215 ??g L-1. In some geologic settings in the basin, this mobile arsenic could be from the weathering of pyrite (FeS2) found in black shale that contains up to 4% arsenic by weight. We hypothesized that under oxic conditions at circumneutral pH, the microbially mediated oxidation of sulfide in the pyrite lattice would lead to the release of pyrite-bound arsenic. Moreover, the oxidation of aqueous As(III) to As(V) by aerobic microorganisms could further enhance arsenic mobilization from the solid phase. Enrichment cultures under aerobic, As(III)-oxidizing conditions were established under circumneutral pH with weathered black shale from the Newark Basin as the inoculum source. Strain WAO, an autotrophic inorganic-sulfur and As(III)-oxidizer, was isolated and phylogenetically and physiologically characterized. Arsenic mobilization studies from arsenopyrite (FeAsS) mineral, conducted with strain WAO at circumneutral pH, showed microbially enhanced mobilization of arsenic and complete oxidation of released arsenic and sulfur to stoichiometric amounts of arsenate and sulfate. In addition, WAO preferentially colonized pyrite on the surface of arsenic-bearing, black shale thick sections. These findings support the hypothesis that microorganisms can directly mobilize and transform arsenic bound in mineral form at circumneutral pH and suggest that the microbial mobilization of arsenic into groundwater may be important in other arsenic-impacted aquifers. ?? 2008 American Chemical Society.

Environmental Science & Technology↗

N-15 NMR study of the immobilization of 2,4- and 2,6-dinitrotoluene in aerobic compost

Large-scale aerobic windrow composting has been used to bioremediate washout lagoon soils contaminated with the explosives TNT (2,4,6-trinitrotoluene) and RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) at several sites within the United States. We previously used 15 N NMR to investigate the reduction and binding of T 15 NT in aerobic bench -scale reactors simulating the conditions of windrow composting. These studies have been extended to 2,4-dinitrotoluene (2,4DNT) and 2,6-dinitrotoluene (2,6DNT), which, as impurities in TNT, are usually present wherever soils have been contaminated with TNT. Liquid-state 15 N NMR analyses of laboratory reactions between 4-methyl-3-nitroaniline- 15 N , the major monoamine reduction product of 2,4DNT, and the Elliot soil humic acid, both in the presence and absence of horseradish peroxidase, indicated that the amine underwent covalent binding with quinone and other carbonyl groups in the soil humic acid to form both heterocyclic and non-heterocyclic condensation products. Liquid-state 15 N NMR analyses of the methanol extracts of 20 day aerobic bench-scale composts of 2,4-di- 15 N -nitrotoluene and 2,6-di- 15 N -nitrotoluene revealed the presence of nitrite and monoamine, but not diamine, reduction products, indicating the occurrence of both dioxygenase enzyme and reductive degradation pathways. Solid-state CP/MAS 15 N NMR analyses of the whole composts, however, suggested that reduction to monoamines followed by covalent binding of the amines to organic matter was the predominant pathway.

Environmental Science & Technology↗

Reproductive disruption in fish downstream from an estrogenic wastewater effluent

To assess the impact of an estrogenic wastewater treatment plant (WWTP) effluent on fish reproduction, white suckers ( Catostomus commersoni ) were collected from immediately upstream and downstream (effluent site) of the city of Boulder, CO, WWTP outfall. Gonadal intersex, altered sex ratios, reduced gonad size, disrupted ovarian and testicular histopathology, and vitellogenin induction consistent with exposure to estrogenic wastewater contaminants were identified in white suckers downstream from the WWTP outfall and not at the upstream site. The sex ratio was female-biased at the effluent site in both the fall of 2003 and the spring of 2004; the frequency of males at the effluent site (17–21%) was half that of the upstream site (36–46%). Intersex white suckers comprised 18–22% of the population at the effluent site. Intersex fish were not found at the upstream site. Chemical analyses determined that the WWTP effluent contained a complex mixture of endocrine-active chemicals, including 17β-estradiol (E 2 ) 17α-ethynylestradiol, alkylphenols, and bisphenol A resulting in an estimated total estrogen equivalence of up to 31 ng E 2 L −1 . These results indicate that the reproductive potential of native fishes may be compromised in wastewater-dominated streams.

Colorado↗

Contaminated salmon and the public's trust

Scientific uncertainties often make it difficult for environmental policy makers to determine how to communicate risks to the public. A constructive, holistic, multisectoral dialogue about an issue can improve understanding of uncertainties from different perspectives and clarify options for risk communication. Many environmental issues could benefit from explicit promotion of such a dialogue. When issues are complex, unconstructive advocacy, narrow focus, and exclusion of selected parties from decision making can erode public trust in science and lead to cynicism about the policies of government and the private sector.

Environmental Science & Technology↗

Pesticides in U.S. streams and groundwater

A 10­-year study by the U.S. Geological Survey’s (USGS’s) National Water-­Quality Assessment (NAWQA) Program provides a national-­scale view of pesticide occurrence in streams and groundwater. The 1992-2001 study builds upon a preliminary analysis from NAWQA’s first phase of studies during 1992-1996 (1, 2). Pesticide data available from various studies prior to 1992 did not allow national assessment because of limited and variable geographic coverage (usually focusing on individual states or regions), sparse and inconsistent inclusion of pesticides in use, and variable sampling designs (3-5). The expanded geographic coverage and improved data following 10 years of study (Figure 1) confirm and reinforce previously reported findings and enable more detailed analyses of each topic. This article summarizes selected findings from a comprehensive report (6), with a focus on the nature of pesticide occurrence and potential significance to human health and stream ecosystems. Information on study design and methods as well as additional analysis of geographic patterns and trends in relation to use and management practices are available in the full report (6).

Environmental Science & Technology↗

In vitro studies evaluating leaching of mercury from mine waste calcine using simulated human body fluids

In vitro bioaccessibility (IVBA) studies were carried out on samples of mercury (Hg) mine-waste calcine (roasted Hg ore) by leaching with simulated human body fluids. The objective was to estimate potential human exposure to Hg due to inhalation of airborne calcine particulates and hand-to-mouth ingestion of Hg-bearing calcines. Mine waste calcines collected from Hg mines at Almadén, Spain, and Terlingua, Texas, contain Hg sulfide, elemental Hg, and soluble Hg compounds, which constitute primary ore or compounds formed during Hg retorting. Elevated leachate Hg concentrations were found during calcine leaching using a simulated gastric fluid (as much as 6200 μg of Hg leached/g sample). Elevated Hg concentrations were also found in calcine leachates using a simulated lung fluid (as much as 9200 μg of Hg leached/g), serum-based fluid (as much as 1600 μg of Hg leached/g), and water of pH 5 (as much as 880 μg of Hg leached/g). The leaching capacity of Hg is controlled by calcine mineralogy; thus, calcines containing soluble Hg compounds contain higher leachate Hg concentrations. Results indicate that ingestion or inhalation of Hg mine-waste calcine may lead to increased Hg concentrations in the human body, especially through the ingestion pathway.

Environmental Science & Technology↗

Uses and biases of volunteer water quality data

State water quality monitoring has been augmented by volunteer monitoring programs throughout the United States. Although a significant effort has been put forth by volunteers, questions remain as to whether volunteer data are accurate and can be used by regulators. In this study, typical volunteer water quality measurements from laboratory and environmental samples in Iowa were analyzed for error and bias. Volunteer measurements of nitrate+nitrite were significantly lower (about 2-fold) than concentrations determined via standard methods in both laboratory-prepared and environmental samples. Total reactive phosphorus concentrations analyzed by volunteers were similar to measurements determined via standard methods in laboratory-prepared samples and environmental samples, but were statistically lower than the actual concentration in four of the five laboratory-prepared samples. Volunteer water quality measurements were successful in identifying and classifying most of the waters which violate United States Environmental Protection Agency recommended water quality criteria for total nitrogen (66%) and for total phosphorus (52%) with the accuracy improving when accounting for error and biases in the volunteer data. An understanding of the error and bias in volunteer water quality measurements can allow regulators to incorporate volunteer water quality data into total maximum daily load planning or state water quality reporting. ?? 2010 American Chemical Society.

Environmental Science & Technology↗

Variability in pesticide deposition and source contributions to snowpack in western U.S. National Parks

Fifty-six seasonal snowpack samples were collected at remote alpine, subarctic, and arctic sites in eight Western U.S. national parks during three consecutive years (2003−2005). Four current-use pesticides (CUPs) (dacthal (DCPA), chlorpyrifos, endosulfans, and γ-hexachlorocyclohexane (HCH)) and four historic-use pesticides (HUPs) (dieldrin, α-HCH, chlordanes, and hexachlorobenzene (HCB)) were commonly measured at all sites, during all years. The mean coefficient of variation for pesticide concentrations was 15% for site replicate samples, 41% for intrapark replicate samples, and 59% for interannual replicate samples. The relative pesticide concentration profiles were consistent from year to year but unique for individual parks, indicating a regional source effect. HUP concentrations were well-correlated with regional cropland intensity when the effect of temperature on snow-air partitioning was considered. The mass of individual CUPs used in regions located one-day upwind of the parks was calculated using air mass back trajectories, and this was used to explain the distribution of CUPs among the parks. The percent of the snowpack pesticide concentration due to regional transport was high (>75%) for the majority of pesticides in all parks. These results suggest that the majority of pesticide contamination in U.S. national parks is due to regional pesticide use in North America.

Environmental Science & Technology↗

Pharmaceutical formulation facilities as sources of opioids and other pharmaceuticals to wastewater treatment plant effluents

Facilities involved in the manufacture of pharmaceutical products are an under-investigated source of pharmaceuticals to the environment. Between 2004 and 2009, 35 to 38 effluent samples were collected from each of three wastewater treatment plants (WWTPs) in New York and analyzed for seven pharmaceuticals including opioids and muscle relaxants. Two WWTPs (NY2 and NY3) receive substantial flows (>20% of plant flow) from pharmaceutical formulation facilities (PFF) and one (NY1) receives no PFF flow. Samples of effluents from 23 WWTPs across the United States were analyzed once for these pharmaceuticals as part of a national survey. Maximum pharmaceutical effluent concentrations for the national survey and NY1 effluent samples were generally <1 microg/L. Four pharmaceuticals (methadone, oxycodone, butalbital, and metaxalone) in samples of NY3 effluent had median concentrations ranging from 3.4 to >400 microg/L. Maximum concentrations of oxycodone (1700 microg/L) and metaxalone (3800 microg/L) in samples from NY3 effluent exceeded 1000 microg/L. Three pharmaceuticals (butalbital, carisoprodol, and oxycodone) in samples of NY2 effluent had median concentrations ranging from 2 to 11 microg/L. These findings suggest that current manufacturing practices at these PFFs can result in pharmaceuticals concentrations from 10 to 1000 times higher than those typically found in WWTP effluents.

Environmental Science & Technology↗

Nitrate in groundwater of the United States, 1991-2003

An assessment of nitrate concentrations in groundwater in the United States indicates that concentrations are highest in shallow, oxic groundwater beneath areas with high N inputs. During 1991-2003, 5101 wells were sampled in 51 study areas throughout the U.S. as part of the U.S. Geological Survey National Water-Quality Assessment (NAWQA) program. The well networks reflect the existing used resource represented by domestic wells in major aquifers (major aquifer studies), and recently recharged groundwater beneath dominant land-surface activities (land-use studies). Nitrate concentrations were highest in shallow groundwater beneath agricultural land use in areas with well-drained soils and oxic geochemical conditions. Nitrate concentrations were lowest in deep groundwater where groundwater is reduced, or where groundwater is older and hence concentrations reflect historically low N application rates. Classification and regression tree analysis was used to identify the relative importance of N inputs, biogeochemical processes, and physical aquifer properties in explaining nitrate concentrations in groundwater. Factors ranked by reduction in sum of squares indicate that dissolved iron concentrations explained most of the variation in groundwater nitrate concentration, followed by manganese, calcium, farm N fertilizer inputs, percent well-drained soils, and dissolved oxygen. Overall, nitrate concentrations in groundwater are most significantly affected by redox conditions, followed by nonpoint-source N inputs. Other water-quality indicators and physical variables had a secondary influence on nitrate concentrations.

Environmental Science & Technology↗

Assessment of sewer source contamination of drinking water wells using tracers and human enteric viruses

This study investigated the source, transport, and occurrence of human enteric viruses in municipal well water, focusing on sanitary sewer sources. A total of 33 wells from 14 communities were sampled once for wastewater tracers and viruses. Wastewater tracers were detected in four of these wells, and five wells were virus- positive by qRT-PCR. These results, along with exclusion of wells with surface water sources, were used to select three wells for additional investigation. Viruses and wastewater tracers were found in the groundwater at all sites. Some wastewater tracers, such as ionic detergents, flame retardants, and cholesterol, were considered unambiguous evidence of wastewater. Sampling at any given time may not show concurrent virus and tracer presence; however, given sufficient sampling over time, a relation between wastewater tracers and virus occurrence was identified. Presence of infectious viruses at the wellhead demonstrates that high-capacity pumping induced sufficiently short travel times for the transport of infectious viruses. Therefore, drinking-water wells are vulnerable to contaminants that travel along fast groundwater flowpaths even if they contribute a small amount of virus-laden water to the well. These results suggest that vulnerability assessments require characterization of "low yield-fast transport" in addition to traditional "high yield-slow transport", pathways. ?? 2010 American Chemical Society.

Environmental Science & Technology↗

Coastal loading and transport of Escherichia coli at an embayed beach in Lake Michigan

A Chicago beach in southwest Lake Michigan was revisited to determine the influence of nearshore hydrodynamic effects on the variability of Escherichia coli (E. coli) concentration in both knee-deep and offshore waters. Explanatory variables that could be used for identifying potential bacteria loading mechanisms, such as bed shear stress due to a combined wave-current boundary layer and wave runup on the beach surface, were derived from an existing wave and current database. The derived hydrodynamic variables, along with the actual observed E. coli concentrations in the submerged and foreshore sands, were expected to reveal bacteria loading through nearshore sediment resuspension and swash on the beach surface, respectively. Based on the observation that onshore waves tend to result in a more active hydrodynamic system at this embayed beach, multiple linear regression analysis of onshore-wave cases further indicated the significance of sediment resuspension and the interaction of swash with gull-droppings in explaining the variability of E. coli concentration in the knee-deep water. For cases with longshore currents, numerical simulations using the Princeton Ocean Model revealed current circulation patterns inside the embayment, which can effectively entrain bacteria from the swash zone into the central area of the embayed beach water and eventually release them out of the embayment. The embayed circulation patterns are consistent with the statistical results that identified that 1) the submerged sediment was an additional net source of E. coli to the offshore water and 2) variability of E. coli concentration in the knee-deep water contributed adversely to that in the offshore water for longshore-current cases. The embayed beach setting and the statistical and numerical methods used in the present study have wide applicability for analyzing recreational water quality at similar marine and freshwater sites. ?? 2010 American Chemical Society.

Environmental Science & Technology↗

Use and environmental occurrence of pharmaceuticals in freestall dairy farms with manured forage fields

Environmental releases of antibiotics from concentrated animal feeding operations (CAFOs) are of increasing regulatory concern. This study investigates the use and occurrence of antibiotics in dairy CAFOs and their potential transport into first-encountered groundwater. On two dairies we conducted four seasonal sampling campaigns, each across 13 animal production and waste management systems and associated environmental pathways: application to animals, excretion to surfaces, manure collection systems, soils, and shallow groundwater. Concentrations of antibiotics were determined using on line solid phase extraction (OLSPE) and liquid chromatography-tandem mass spectrometry (LC/MS/MS) with electrospray ionization (ESI) for water samples, and accelerated solvent extraction (ASE) LC/MS/MS with ESI for solid samples. A variety of antibiotics were applied at both farms leading to antibiotics excretion of several hundred grams per farm per day. Sulfonamides, tetracyclines, and their epimers/isomers, and lincomycin were most frequently detected. Yet, despite decades of use, antibiotic occurrence appeared constrained to within farm boundaries. The most frequent antibiotic detections were associated with lagoons, hospital pens, and calf hutches. When detected below ground, tetracyclines were mainly found in soils, whereas sulfonamides were found in shallow groundwater reflecting key differences in their physicochemical properties. In manure lagoons, 10 compounds were detected including tetracyclines and trimethoprim. Of these 10, sulfadimethoxine, sulfamethazine, and lincomycin were found in shallow groundwater directly downgradient from the lagoons. Antibiotics were sporadically detected in field surface samples on fields with manure applications, but not in underlying sandy soils. Sulfadimethoxine and sulfamethazine were detected in shallow groundwater near field flood irrigation gates, but at highly attenuated levels.

Environmental Science & Technology↗

Cyanotoxin mixtures and taste-and-odor compounds in cyanobacterial blooms from the midwestern united states

The mixtures of toxins and taste-and-odor compounds present during cyanobacterial blooms are not well characterized and of particular concern when evaluating potential human health risks. Cyanobacterial blooms were sampled in twenty-three Midwestern United States lakes and analyzed for community composition, thirteen cyanotoxins by liquid chromatography/mass spectrometry and immunoassay, and two taste-and-odor compounds by gas chromatography/mass spectrometry. Aphanizomenon, Cylindrospermopsis and/or Microcystis were dominant in most (96%) blooms, but community composition was not strongly correlated with toxin and taste-and-odor occurrence. Microcystins occurred in all blooms. Total microcystin concentrations measured by liquid chromatography/mass spectrometry and immunoassay were linearly related (rs = 0.76, p < 0.01) and LC/MS/MS concentrations were lower than or similar to ELISA in most (85%) samples. Geosmin (87%), 2-methylisoborneol (39%), anatoxin-a (30%), saxitoxins (17%), cylindrospermopsins (9%), and nodularin-R (9%) also were present in these blooms. Multiple classes of cyanotoxins occurred in 48% of blooms and 95% had multiple microcystin variants. Toxins and taste-and-odor compounds frequently co-occurred (91% of blooms), indicating odor may serve as a warning that cyanotoxins likely are present. However, toxins occurred more frequently than taste-and-odor compounds, so odor alone does not provide sufficient warning to ensure human-health protection.

Environmental Science & Technology↗

Assessment of PDMS-water partition coefficients: implications for passive environmental sampling of hydrophobic organic compounds

Solid-phase microextraction (SPME) has shown potential as an in situ passive-sampling technique in aquatic environments. The reliability of this method depends upon accurate determination of the partition coefficient between the fiber coating and water (K f ). For some hydrophobic organic compounds (HOCs), K f values spanning 4 orders of magnitude have been reported for polydimethylsiloxane (PDMS) and water. However, 24% of the published data examined in this review did not pass the criterion for negligible depletion, resulting in questionable K f values. The range in reported K f is reduced to just over 2 orders of magnitude for some polychlorinated biphenyls (PCBs) when these questionable values are removed. Other factors that could account for the range in reported K f , such as fiber-coating thickness and fiber manufacturer, were evaluated and found to be insignificant. In addition to accurate measurement of K f , an understanding of the impact of environmental variables, such as temperature and ionic strength, on partitioning is essential for application of laboratory-measured K f values to field samples. To date, few studies have measured K f for HOCs at conditions other than at 20 degrees or 25 degrees C in distilled water. The available data indicate measurable variations in K f at different temperatures and different ionic strengths. Therefore, if the appropriate environmental variables are not taken into account, significant error will be introduced into calculated aqueous concentrations using this passive sampling technique. A multiparameter linear solvation energy relationship (LSER) was developed to estimate log K f in distilled water at 25 degrees C based on published physicochemical parameters. This method provided a good correlation (R2 = 0.94) between measured and predicted log K f values for several compound classes. Thus, an LSER approach may offer a reliable means of predicting log K f for HOCs whose experimental log K f values are presently unavailable. Future research should focus on understanding the impact of environmental variables on K f . Obtaining the data needed for an LSER approach to estimate K f for all environmentally relevant HOCs would be beneficial to the application of SPME as a passive-sampling technique.

Environmental Science & Technology↗

A fresh look at road salt: Aquatic toxicity and water-quality impacts on local, regional, and national scales

A new perspective on the severity of aquatic toxicity impact of road salt was gained by a focused research effort directed at winter runoff periods. Dramatic impacts were observed on local, regional, and national scales. Locally, samples from 7 of 13 Milwaukee, Wisconsin area streams exhibited toxicity in Ceriodaphnia dubia and Pimephales promelas bioassays during road-salt runoff. Another Milwaukee stream was sampled from 1996 to 2008 with 72% of 37 samples exhibiting toxicity in chronic bioassays and 43% in acute bioassays. The maximum chloride concentration was 7730 mg/L. Regionally, in southeast Wisconsin, continuous specific conductance was monitored as a chloride surrogate in 11 watersheds with urban land use from 6.0 to 100%. Elevated specific conductance was observed between November and April at all sites, with continuing effects between May and October at sites with the highest specific conductance. Specific conductance was measured as high as 30 800 ??S/cm (Cl = 11 200 mg/L). Chloride concentrations exceeded U.S. Environmental Protection Agency (USEPA) acute (860 mg/L) and chronic (230 mg/L) water-quality criteria at 55 and 100% of monitored sites, respectively. Nationally, U.S. Geological Survey historical data were examined for 13 northern and 4 southern metropolitan areas. Chloride concentrations exceeded USEPA water-quality criteria at 55% (chronic) and 25% (acute) of the 168 monitoring locations in northern metropolitan areas from November to April. Only 16% (chronic) and 1% (acute) of sites exceeded criteria from May to October. At southern sites, very few samples exceeded chronic water-quality criteria, and no samples exceeded acute criteria. ?? 2010 American Chemical Society.

Environmental Science & Technology↗

The plight of the bees

The loss of biodiversity is a trend that is garnering much concern. As organisms have evolved mutualistic and synergistic relationships, the loss of one or a few species can have a much wider environmental impact. Since much pollination is facilitated by bees, the reported colony collapse disorder has many worried of widespread agricultural fallout and thus deleterious impact on human foodstocks. In this Feature, Spivak et al. review what is known of the present state of bee populations and provide information on how to mitigate and reverse the trend.

Environmental Science & Technology↗

A role for analytical chemistry in advancing our understanding of the occurrence, fate, and effects of Corexit Oil Dispersants

On April 24, 2010, the sinking of the Deepwater Horizon oil rig resulted in the release of oil into the Gulf of Mexico. As of July 19, 2010, the federal government's Deepwater Horizon Incident Joint Information Center estimates the cumulative range of oil released is 3,067,000 to 5,258,000 barrels, with a relief well to be completed in early August. By comparison, the Exxon Valdez oil spill released a total of 260,000 barrels of crude oil into the environment. As of June 9, BP has used over 1 million gallons of Corexit oil dispersants to solubilize oil and help prevent the development of a surface oil slick. Oil dispersants are mixtures containing solvents and surfactants that can exhibit toxicity toward aquatic life and may enhance the toxicity of components of weathered crude oil. Detailed knowledge of the composition of both Corexit formulations and other dispersants applied in the Gulf will facilitate comprehensive monitoring programs for determining the occurrence, fate, and biological effects of the dispersant chemicals. The lack of information on the potential impacts of oil dispersants has caught industry, federal, and state officials off guard. Until compositions of Corexit 9500 and 9527 were released by the U.S. Environmental Protection Agency online, the only information available consisted of Material Safety Data Sheets (MSDS), patent documentation, and a National Research Council report on oil dispersants. Several trade and common names are used for the components of the Corexits. For example, Tween 80 and Tween 85 are oligomeric mixtures.

Environmental Science & Technology↗