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Results for “Environmental Science & Technology Water”

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USGS1996

Physiological considerations in applying laboratory-determined buoyant densities to predictions of bacterial and protozoan transport in groundwater: Results of in-situ and laboratory tests

Buoyant densities were determined for groundwater bacteria and microflagellates (protozoa) from a sandy aquifer (Cape Cod, MA) using two methods: (1) density-gradient centrifugation (DGC) and (2) Stoke's law approximations using sedimentation rates observed during natural-gradient injection and recovery tests. The dwarf (average cell size, 0.3 μm), unattached bacteria inhabiting a pristine zone just beneath the water table and a majority (∼80%) of the morphologically diverse community of free-living bacteria inhabiting a 5-km-long plume of organically-contaminated groundwater had DGC-determined buoyant densities <1.019 g/cm 3 before culturing. In the aquifer, sinking rates for the uncultured 2-μm size class of contaminant plume bacteria were comparable to that of the bromide tracer (1.9 × 10 - 3 M), also suggesting a low buoyant density. Culturing groundwater bacteria resulted in larger (0.8−1.3 μm), less neutrally-buoyant (1.043−1.081 g/cm 3 ) cells with potential sedimentation rates up to 64-fold higher than those predicted for the uncultured populations. Although sedimentation generally could be neglected in predicting subsurface transport for the community of free-living groundwater bacteria, it appeared to be important for the cultured isolates, at least until they readapt to aquifer conditions. Culturing-induced alterations in size of the contaminant-plume microflagellates (2−3 μm) were ameliorated by using a lower nutrient, acidic (pH 5) porous growth medium. Buoyant densities of the cultured microflagellates were low, i.e., 1.024−1.034 g/cm 3 (using the DGC assay) and 1.017−1.039 g/cm 3 (estimated from in-situ sedimentation rates), sug gesting good potential for subsurface transport under favorable conditions.

Environmental Science & Technology↗

USGS2013

In-stream attenuation of neuro-active pharmaceuticals and their metabolites

In-stream attenuation was determined for 14 neuro-active pharmaceuticals and associated metabolites. Lagrangian sampling, which follows a parcel of water as it moves downstream, was used to link hydrological and chemical transformation processes. Wastewater loading of neuro-active compounds varied considerably over a span of several hours, and thus a sampling regime was used to verify that the Lagrangian parcel was being sampled and a mechanism was developed to correct measured concentrations if it was not. In-stream attenuation over the 5.4-km evaluated reach could be modeled as pseudo-first-order decay for 11 of the 14 evaluated neuro-active pharmaceutical compounds, illustrating the capacity of streams to reduce conveyance of neuro-active compounds downstream. Fluoxetine and N -desmethyl citalopram were the most rapidly attenuated compounds ( t 1/2 = 3.6 ± 0.3 h, 4.0 ± 0.2 h, respectively). Lamotrigine, 10,11,-dihydro-10,11,-dihydroxy-carbamazepine, and carbamazepine were the most persistent ( t 1/2 = 12 ± 2.0 h, 12 ± 2.6 h, 21 ± 4.5 h, respectively). Parent compounds (e.g., buproprion, carbamazepine, lamotrigine) generally were more persistent relative to their metabolites. Several compounds (citalopram, venlafaxine, O -desmethyl-venlafaxine) were not attenuated. It was postulated that the primary mechanism of removal for these compounds was interaction with bed sediments and stream biofilms, based on measured concentrations in stream biofilms and a column experiment using stream sediments.

Environmental Science & Technology↗

USGS2021

A review of algal toxin exposures on reserved federal lands and among trust species in the United States

Associated health effects from algal toxin exposure are a growing concern for human and animal health. Algal toxin poisonings may occur from contact with or consumption of water supplies or from ingestion of contaminated animals. The U.S. Federal Government owns or holds in trust about 259 million hectares of land, in addition to the Trust species obligations. We completed the first comprehensive review of potential toxin-producing algal blooms in surface waters on Federal lands and Trust species exposed to algal toxins. Events were sorted into three tiers based on potentially toxic algae abundance or toxin concentration and related effects on animal morbidity and mortality. At least 11.1% of Federal lands are known to have been affected by algal events, but exposure is likely underreported. The occurrence of potential toxin producers and their toxins (Tier 1) have been documented 337 times, health advisory threshold exceedances (Tier 2) were reported 943 times, and 86 events involved animal sickness or death linked to cyanobacteria or marine toxins (Tier 3). Trust species exposed to cyano- or algal toxins included marine mammals, migratory birds, threatened and endangered species, and species of concern. We report numerous data gaps ranging from potential effects on human health from consuming intoxicated animals to the infrequency of measuring and reporting certain toxins. Improvements to field and laboratory methods, more consistent evaluation of toxin exposure, decreased latency on data analysis, delivery and interpretation will be necessary to improve response and management strategies for protecting human and animal health where issues persist.

Critical Reviews in Environmental Science and Tech↗

USGS2020

Reduction in drinking water arsenic exposure and health risk through arsenic treatment among private well households in Maine and New Jersey, USA

Over 2 million people in the United States (U.S.) drink water from private wells that contain arsenic (As) exceeding the U.S. Environmental Protection Agency (USEPA) Maximum Contaminant Level (MCL) of 10 micrograms per liter (μg/L). While there are a number of commercially available treatment technologies for removing As from drinking water, it is up to the private well households to decide whether to treat for As or not. However, how well existing treatment technologies perform in real world situations, and to what extent they reduce health risks, are not well understood. This study evaluates the effectiveness of household As treatment systems in southern-central Maine (ME, n=156) and northern New Jersey (NJ, n=94) and ascertains how untreated well water chemistry and other factors influence As removal. Untreated and treated water samples, as well as a treatment questionnaire, were collected. Most ME households in this study had point-of-use reverse-osmosis systems (POU RO), while in NJ, dual-tank point-of-entry (POE) whole house systems were popular. Arsenic treatment systems reduced well water arsenic concentrations ([As]) by up to two orders of magnitude, i.e. from a median of 71.7 to 0.8 μg/L and from a mean of 105 to 14.3 μg/L in ME, and from a median of 8.6 to 0.2 μg/L and a mean of 15.8 to 2.1 μg/L in NJ. More than half (53%) of the systems in ME reduced water [As] to below 1 µg/L, compared to 69% in NJ. The treatment system failure rates were 19% in ME (> USEPA MCL 10 µg/L) and 16% in NJ (> NJ standard 5 μg/L). In both states, the higher the untreated well water [As] and the As(III)/As ratio, the higher the rate of treatment failure. POE systems failed less than POU systems, as did the treatment systems installed and maintained by vendors than those by homeowners. The 7-fold reduction of [As] in the treated water reduced skin cancer risk alone from 3,765 to 514 in 1 million in ME, and from 568 to 75 in 1 million in NJ.

Maine, New Jersey↗

USGS2018

Human-associated indicator bacteria and human-specific viruses in surface water: a spatial assessment with implications on fate and transport

Hydrologic, seasonal, and spatial variability of sewage contamination was studied at six locations within a watershed upstream from water reclamation facility (WRF) effluent to define relative loadings of sewage from different portions of the watershed. Fecal pollution from human sources was spatially quantified by measuring two human-associated indicator bacteria (HIB) and eight human-specific viruses (HSV) at six stream locations in the Menomonee River watershed in Milwaukee, Wisconsin from April 2009 to March 2011. A custom, automated water sampler, which included HSV filtration, was deployed at each location providing unattended, flow-weighted, large-volume (30-913 L) sampling. In addition, wastewater influent samples were composited over discrete seven-day periods from the two Milwaukee WRFs. Of the eight HSV only three were detected, present in up to 38% of the 228 stream samples, while at least one HSV was detected in all WRF influent samples. HIB occurred more often with significantly higher concentrations than the HSV in stream and WRF influent samples (p<0.05). HSV yield calculations showed a loss from upstream to the most downstream sub-watershed of the Menomonee River, and in contrast, a positive HIB yield from this same sub-watershed emphasizes the complexity in fate and transport properties between HSV and HIB. This study demonstrates the utility of analyzing multiple HSV and HIB to provide a weight of evidence approach for assessment of fecal contamination at the watershed level, provides an assessment of relative loadings for prioritizing areas within a watershed, and demonstrates how loadings of HSV and HIB can be inconsistent, inferring potential differences in fate and transport between the two indicators of human fecal presence.

Wisconsin↗

USGS1995

Linear solvation energy relationship of the limiting partition coefficient of organic solutes between water and activated carbon

A linear solvation energy relationship has been found for 353 values of the limiting adsorption coefficients of diverse chemicals: log K = −0.37 + 0.0341 V i − 1.07β + D + 0.65 P with R = 0.951, s = 0.51, n = 353, and F = 818.0, where V i is the intrinsic molar volume; β is a measure of the hydrogen bond acceptor strength of the solute; D is an index parameter for the research group which includes the effects of the different types of carbon used, the temperature, and the length of time allowed for the adsorption equilibrium to be established; and P is an index parameter for the flatness of the molecule. P is defined to be unity if there is an aromatic system in the molecule or if there is a double bond or series of conjugated double bonds with no more that one non-hydrogen atom beyond the double bond and zero otherwise. A slightly better fit is obtained if the two-thirds power of V i is used as a measure of the surface area in place of the volume term: log K = −1.75 + 0.227 V 2/3 − 1.10β + D + 0.60 P with R = 0.954, s = 0.49, n = 353, and F = 895.39. This is the first quantitative measure of the effect of the shape of the molecule on its tendency to be adsorbed on activated carbon.

Environmental Science & Technology↗

USGS2005

Transport of chemical and microbial compounds from known wastewater discharges: Potential for use as indicators of human fecal contamination

The quality of drinking and recreational water is currently (2005) determined using indicator bacteria. However, the culture tests used to analyze for these bacteria require a long time to complete and do not discriminate between human and animal fecal material sources. One complementary approach is to use chemicals found in human wastewater, which would have the advantages of (1) potentially shorter analysis times than the bacterial culture tests and (2) being selected for human-source specificity. At 10 locations, water samples were collected upstream and at two successive points downstream from a wastewaster treatment plant (WWTP); a treated effluent sample was also collected at each WWTP. This sampling plan was used to determine the persistence of a chemically diverse suite of emerging contaminants in streams. Samples were also collected at two reference locations assumed to have minimal human impacts. Of the 110 chemical analytes investigated in this project, 78 were detected at least once. The number of compounds in a given sample ranged from 3 at a reference location to 50 in a WWTP effluent sample. The total analyte load at each location varied from 0.018 μg/L at the reference location to 97.7 μg/L in a separate WWTP effluent sample. Although most of the compound concentrations were in the range of 0.01−1.0 μg/L, in some samples, individual concentrations were in the range of 5−38 μg/L. The concentrations of the majority of the chemicals present in the samples generally followed the expected trend:  they were either nonexistent or at trace levels in the upstream samples, had their maximum concentrations in the WWTP effluent samples, and then declined in the two downstream samples. This research suggests that selected chemicals are useful as tracers of human wastewater discharge.

Environmental Science & Technology↗

USGS2010

Relationship and variation of qPCR and culturable enterococci estimates in ambient surface waters are predictable

The quantitative polymerase chain reaction (qPCR) method provides rapid estimates of fecal indicator bacteria densities that have been indicated to be useful in the assessment of water quality. Primarily because this method provides faster results than standard culture-based methods, the U.S. Environmental Protection Agency is currently considering its use as a basis for revised ambient water quality criteria. In anticipation of this possibility, we sought to examine the relationship between qPCR-based and culture-based estimates of enterococci in surface waters. Using data from several research groups, we compared enterococci estimates by the two methods in water samples collected from 37 sites across the United States. A consistent linear pattern in the relationship between cell equivalents (CCE), based on the qPCR method, and colony-forming units (CFU), based on the traditional culturable method, was significant (P < 0.05) at most sites. A linearly decreasing variance of CCE with increasing CFU levels was significant (P < 0.05) or evident for all sites. Both marine and freshwater sites under continuous influence of point-source contamination tended to reveal a relatively constant proportion of CCE to CFU. The consistency in the mean and variance patterns of CCE versus CFU indicates that the relationship of results based on these two methods is more predictable at high CFU levels (e.g., log 10 CFU > 2.0/100 mL) while uncertainty increases at lower CFU values. It was further noted that the relative error in replicated qPCR estimates was generally higher than that in replicated culture counts even at relatively high target levels, suggesting a greater need for replicated analyses in the qPCR method to reduce relative error. Further studies evaluating the relationship between culture and qPCR should take into account analytical uncertainty as well as potential differences in results of these methods that may arise from sample variability, different sources of pollution, and environmental factors.

Environmental Science & Technology↗

USGS2017

Trends in methyl tert-butyl ether concentrations in private wells in southeast New Hampshire: 2005 to 2015

In southeast New Hampshire, where reformulated gasoline was used from the 1990s to 2007, methyl tert- butyl ether (MtBE) concentrations ≥0.2 μg/L were found in water from 26.7% of 195 domestic wells sampled in 2005. Ten years later in 2015, and eight years after MtBE was banned, 10.3% continue to have MtBE. Most wells (140 of 195) had no MtBE detections (concentrations <0.2 μg/L) in 2005 and 2015. Of the remaining wells, MtBE concentrations increased in 4 wells, decreased in 47 wells, and did not change in 4 wells. On average, MtBE concentrations decreased 65% among 47 wells whereas MtBE concentrations increased 17% among 4 wells between 2005 and 2015. The percent change in detection frequency from 2005 to 2015 (the decontamination rate) was lowest (45.5%) in high-population-density areas and in wells completed in the Berwick Formation geologic units. The decontamination rate was the highest (78.6%) where population densities were low and wells were completed in bedrock composed of granite, metamorphic, and mafic rocks. Wells in the Berwick Formation are characteristically deeper and have lower yields than wells in other rock types and have shallower overburden cover, which may allow for more rapid transport of MtBE from land-surface releases. Low-yielding, deep bedrock wells may require large contributing areas to achieve adequate well yield, and thus have a greater chance of intercepting MtBE, in addition to diluting contaminants at a slower rate and thus requiring more time to decontaminate.

New Hampshire↗

USGS1999

The urban environmental gradient: Anthropogenic influences on the spatial and temporal distributions of lead and zinc in sediments

U rban settings are a focal point for environmental contamination due to emissions from industrial and municipal activities and the widespread use of motor vehicles. As part of the National Water-Quality Assessment Program of the U.S. Geological Survey, streambed-sediment and dated reservoir-sediment samples were collected from the Chattahoochee River Basin and analyzed for total lead (Pb) and zinc (Zn) concentrations. The sampling transect extends from northern Georgia, through Atlanta, to the Gulf of Mexico and reflects a steep gradient in population density from nearly 1000 people/km 2 in the Atlanta Metropolitan Area to fewer than 50 people/km 2 in rural areas of southern Georgia and northern Florida. Correlations among population density, traffic density, and total and anthropogenic Pb and Zn concentrations indicate that population density is strongly related to traffic density and is a predictor of Pb and Zn concentrations in the environment derived from anthropogenic activities. Differences in the distributions of total Pb and Zn concentrations along the urban−suburban−rural gradient from Atlanta to the Florida Panhandle are related to temporal and spatial processes. That is, with the removal of leaded gasoline starting in the late 1970s, peak Pb concentrations have decreased to the present. Conversely, increased vehicular usage has kept Zn concentrations elevated in runoff from population centers, which is reflected in the continued enrichment of Zn in aquatic sediments. Sediments from rural areas also contain elevated concentrations of Zn, possibly in response to substantial power plant emissions for the region, as well as vehicular traffic.

Georgia, Florida↗

USGS2021

Isolating the AFFF signature in coastal watersheds using oxidizable PFAS precursors and unexplained organofluorine

Water supplies for millions of U.S. individuals exceed maximum contaminant levels for per- and polyfluoroalkyl substances (PFAS). Contemporary and legacy use of aqueous film forming foams (AFFF) is a major contamination source. However, diverse PFAS sources are present within watersheds, making it difficult to isolate their predominant origins. Here we examine PFAS source signatures among six adjacent coastal watersheds on Cape Cod, MA, U.S.A. using multivariate clustering techniques. A distinct signature of AFFF contamination enriched in precursors with six perfluorinated carbons (C6) was identified in watersheds with an AFFF source, while others were enriched in C4 precursors. Principal component analysis of PFAS composition in impacted watersheds showed a decline in precursor composition relative to AFFF stocks and a corresponding increase in terminal perfluoroalkyl sulfonates with < C6 but not those with ≥ C6. Prior work shows that in AFFF stocks, all extractable organofluorine (EOF) can be explained by targeted PFAS and precursors inferred using Bayesian inference on the total oxidizable precursor assay. Using the same techniques for the first time in impacted watersheds, we find that only 24%–63% of the EOF can be explained by targeted PFAS and oxidizable precursors. Our work thus indicates the presence of large non-AFFF organofluorine sources in these coastal watersheds.

Massachusetts↗

USGS2018

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↗

USGS2017

Methane and benzene in drinking-water wells overlying the Eagle Ford, Fayetteville, and Haynesville Shale hydrocarbon production areas

Water wells ( n = 116) overlying the Eagle Ford, Fayetteville, and Haynesville Shale hydrocarbon production areas were sampled for chemical, isotopic, and groundwater-age tracers to investigate the occurrence and sources of selected hydrocarbons in groundwater. Methane isotopes and hydrocarbon gas compositions indicate most of the methane in the wells was biogenic and produced by the CO 2 reduction pathway, not from thermogenic shale gas. Two samples contained methane from the fermentation pathway that could be associated with hydrocarbon degradation based on their co-occurrence with hydrocarbons such as ethylbenzene and butane. Benzene was detected at low concentrations (<0.15 μg/L), but relatively high frequencies (2.4–13.3% of samples), in the study areas. Eight of nine samples containing benzene had groundwater ages >2500 years, indicating the benzene was from subsurface sources such as natural hydrocarbon migration or leaking hydrocarbon wells. One sample contained benzene that could be from a surface release associated with hydrocarbon production activities based on its age (10 ± 2.4 years) and proximity to hydrocarbon wells. Groundwater travel times inferred from the age-data indicate decades or longer may be needed to fully assess the effects of potential subsurface and surface releases of hydrocarbons on the wells.

Environmental Science & Technology↗

USGS2011

Trophic magnification of PCBs and its relationship to the octanol-water partition coefficient

We investigated polychlorinated biphenyl (PCB) bioaccumulation relative to octanol-water partition coefficient (KOW) and organism trophic position (TP) at the Lake Hartwell Superfund site (South Carolina). We measured PCBs (127 congeners) and stable isotopes (??15N) in sediment, organic matter, phytoplankton, zooplankton, macroinvertebrates, and fish. TP, as calculated from ??15N, was significantly, positively related to PCB concentrations, and food web trophic magnification factors (TMFs) ranged from 1.5-6.6 among congeners. TMFs of individual congeners increased strongly with log KOW, as did the predictive power (r2) of individual TP-PCB regression models used to calculate TMFs. We developed log KOW-TMF models for eight food webs with vastly different environments (freshwater, marine, arctic, temperate) and species composition (cold- vs warmblooded consumers). The effect of KOW on congener TMFs varied strongly across food webs (model slopes 0.0-15.0) because the range of TMFs among studies was also highly variable. We standardized TMFs within studies to mean = 0, standard deviation (SD) = 1 to normalize for scale differences and found a remarkably consistent KOW effect on TMFs (no difference in model slopes among food webs). Our findings underscore the importance of hydrophobicity (as characterized by KOW) in regulating bioaccumulation of recalcitrant compounds in aquatic systems, and demonstrate that relationships between chemical KOW and bioaccumulation from field studies are more generalized than previously recognized. ?? This article not subject to U.S. Copyright. Published 2011 by the American Chemical Society.

Environmental Science & Technology↗

USGS2013

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↗

USGS2007

Incidence of the enterococcal surface protein ( esp ) gene in human and animal fecal sources

The occurrence of the enterococcal surface protein ( esp ) gene in the opportunistic pathogens Enterococcus faecalis and E. faecium is well-documented in clinical research. Recently, the esp gene has been proposed as a marker of human pollution in environmental waters; however, information on its relative incidence in various human and animal fecal sources is limited. We have determined the occurrence of the esp gene in enterococci from human ( n = 64) and animal ( n = 233) fecal samples by polymerase chain reaction using two primer sets: one presumably specific for E. faecium ( esp fm ) and the other for both E. faecalis and E. faecium ( esp fs/fm ). We believe that this research is the first to explore the use of esp fs/fm for the detection of human waste in natural environmental settings. The incidence in human sources was 93.1% esp fm and 100% esp fs/fm in raw sewage influent; 30% for both esp fm and esp fs/fm in septic waste; and 0% esp fm and 80% esp fs/fm in active pit toilets. The overall occurrence of the gene in animal feces was 7.7% ( esp fs/fm ) and 4.7% ( esp fm ); animal types with positive results included dogs (9/43, all esp fm ), gulls (10/34, esp fs/fm ; 2/34, esp fm ), mice (3/22, all esp fs/fm ), and songbirds (5/55, all esp fs/fm ). The esp gene was not detected in cat (0/34), deer (0/4), goose (0/18), or raccoon (0/23) feces. The inconsistent occurrence, especially in septic and pit toilet sewage, suggests a low statistical power of discrimination between animal and human sources, which means a large number of replicates should be collected. Both esp fm and esp fs/fm were common in raw sewage, but neither one efficiently differentiated between animal and other human sources.

Environmental Science & Technology↗

USGS2010

Natural chlorate in the environment: Application of a new IC-ESI/MS/MS method with a Cl18O3- internal standard

A new ion chromatography electrospray tandem mass spectrometry (IC-ESI/MS/MS) method has been developed for quantification and confirmation of chlorate (ClO 3 − ) in environmental samples. The method involves the electro-chemical generation of isotopically labeled chlorate internal standard (Cl 18 O 3 − ) using 18 O water (H 2 18 O). The standard was added to all samples prior to analysis thereby minimizing the matrix effects that are associated with common ions without the need for expensive sample pretreatments. The method detection limit (MDL) for ClO 3 − was 2 ng L −1 for a 1 mL volume sample injection. The proposed method was successfully applied to analyze ClO 3 − in difficult environmental samples including soil and plant leachates. The IC-ESI/MS/MS method described here was also compared to established EPA method 317.0 for ClO 3 − analysis. Samples collected from a variety of environments previously shown to contain natural perchlorate (ClO 4 − ) occurrence were analyzed using the proposed method and ClO 3 − was found to co-occur with ClO 4 − at concentrations ranging from <2 ng L −1 in precipitation from Texas and Puerto Rico to >500 mg kg −1 in caliche salt deposits from the Atacama Desert in Chile. Relatively low concentrations of ClO 3 − in some natural groundwater samples (<0.1 μg L −1 ) analyzed in this work may indicate lower stability when compared to ClO 4 − in the subsurface. The high concentrations of ClO 3 − in caliches and soils (3−6 orders of magnitude greater) as compared to precipitation samples indicate that ClO 3 − , like ClO 4 − , may be atmospherically produced and deposited, then concentrated in dry soils, and is possibly a minor component in the biogeochemical cycle of chlorine.

Environmental Science & Technology↗

USGS2011

Tracking nonpoint source nitrogen pollution in human-impacted watersheds

Nonpoint source nitrogen (N) pollution is a leading contributor to U.S. water quality impairments. We combined watershed N mass balances and stable isotopes to investigate fate and transport of nonpoint N in forest, agricultural, and urbanized watersheds at the Baltimore Long-Term Ecological Research site. Annual N retention was 55%, 68%, and 82% for agricultural, suburban, and forest watersheds, respectively. Analysis of δ 15 N-NO 3 – , and δ 18 O-NO 3 – indicated wastewater was an important nitrate source in urbanized streams during baseflow. Negative correlations between δ 15 N-NO 3 – and δ 18 O-NO 3 – in urban watersheds indicated mixing between atmospheric deposition and wastewater, and N source contributions changed with storm magnitude (atmospheric sources contributed &sim;50% at peak storm N loads). Positive correlations between δ 15 N-NO 3 – and δ 18 O-NO 3 – in watersheds suggested denitrification was removing septic system and agriculturally derived N, but N from belowground leaking sewers was less susceptible to denitrification. N transformations were also observed in a storm drain (no natural drainage network) potentially due to organic carbon inputs. Overall, nonpoint sources such as atmospheric deposition, wastewater, and fertilizer showed different susceptibility to watershed N export. There were large changes in nitrate sources as a function of runoff, and anticipating source changes in response to climate and storms will be critical for managing nonpoint N pollution.

Environmental Science & Technology↗