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Occurrence and geochemistry of lead-210 and polonium-210 radionuclides in public-drinking-water supplies from principal aquifers of the United States

On the basis of lifetime cancer risks, lead-210 ( 210 Pb) and polonium-210 ( 210 Po) ≥ 1.0 and 0.7 pCi/L (picocuries per liter), respectively, in drinking-water supplies may pose human-health concerns. 210 Pb and 210 Po were detected at concentrations greater than these thresholds at 3.7 and 1.5%, respectively, of filtered untreated groundwater samples from 1263 public-supply wells in 19 principal aquifers across the United States. Nationally, 72% of samples with radon-222 ( 222 Rn) concentrations > 4000 pCi/L had 210 Pb ≥ 1.0 pCi/L. 210 Pb is mobilized by alpha recoil associated with the decay of 222 Rn and short-lived progeny. 210 Pb concentrations ≥ 1.0 pCi/L occurred most frequently where acidic groundwaters inhibited 210 Pb readsorption (felsic-crystalline rocks) and where reducing alkaline conditions favored dissolution of iron–manganese- (Fe–Mn-) oxyhydroxides (which adsorb 210 Pb) and formation of lead–carbonate complexes (enhancing lead (Pb) mobility). 210 Po concentrations ≥ 0.7 pCi/L occurred almost exclusively in confined Coastal Plain aquifers where old (low percent-modern carbon-14) groundwaters were reducing, with high pH (>7.5) and high sodium/chloride (Na/Cl) ratios resulting from cation exchange. In high-pH environments, aqueous polonium (Po) is poorly sorbed, occurring as dihydrogen polonate (H 2 PoO 3 (aq)) or, under strongly reducing conditions, as a hydrogen-polonide anion (HPo – ). Fe–Mn- and sulfate-reduction and cation-exchange processes may mobilize polonium from mineral surfaces. Po 2+ occurrence in low-to-neutral-pH waters is attenuated by adsorption.

Environmental Science Technology

Fate of 4-nonylphenol and 17β-estradiol in the Redwood River of Minnesota

The majority of previous research investigating the fate of endocrine-disrupting compounds has focused on single processes generally in controlled laboratory experiments, and limited studies have directly evaluated their fate and transport in rivers. This study evaluated the fate and transport of 4-nonylphenol, 17β-estradiol, and estrone in a 10-km reach of the Redwood River in southwestern Minnesota. The same parcel of water was sampled as it moved downstream, integrating chemical transformation and hydrologic processes. The conservative tracer bromide was used to track the parcel of water being sampled, and the change in mass of the target compounds relative to bromide was determined at two locations downstream from a wastewater treatment plant effluent outfall. In-stream attenuation coefficients ( k stream ) were calculated by assuming first-order kinetics (negative values correspond to attenuation, whereas positive values indicate production). Attenuation of 17β-estradiol ( k stream = −3.2 ± 1.0 day –1 ) was attributed primarily due to sorption and biodegradation by the stream biofilm and bed sediments. Estrone ( k stream = 0.6 ± 0.8 day –1 ) and 4-nonylphenol ( k stream = 1.4 ± 1.9 day –1 ) were produced in the evaluated 10-km reach, likely due to biochemical transformation from parent compounds (17β-estradiol, 4-nonylphenolpolyethoxylates, and 4-nonyphenolpolyethoxycarboxylates). Despite attenuation, these compounds were transported kilometers downstream, and thus additive concentrations from multiple sources and transformation of parent compounds into degradates having estrogenic activity can explain their environmental persistence and widespread observations of biological disruption in surface waters.

Minnesota

Uranium(VI) interactions with mackinawite in the presence and absence of bicarbonate and oxygen

Mackinawite, Fe(II)S, samples loaded with uranium (10 -5 , 10 -4 , and 10 -3 mol U/g FeS) at pH 5, 7, and 9, were characterized using X-ray absorption spectroscopy and X-ray diffraction to determine the effects of pH, bicarbonate, and oxidation on uptake. Under anoxic conditions, a 5 g/L suspension of mackinawite lowered 5 × 10 -5 M uranium(VI) to below 30 ppb (1.26 × 10 -7 M) U. Between 82 and 88% of the uranium removed from solution by mackinawite was U(IV) and was nearly completely reduced to U(IV) when 0.012 M bicarbonate was added. Near-neighbor coordination consisting of uranium–oxygen and uranium-uranium distances indicates the formation of uraninite in the presence and absence of bicarbonate, suggesting reductive precipitation as the dominant removal mechanism. Following equilibration in air, mackinawite was oxidized to mainly goethite and sulfur and about 76% of U(IV) was reoxidized to U(VI) with coordination of uranium to axial and equatorial oxygen, similar to uranyl. Additionally, uranium-iron distances, typical of coprecipitation of uranium with iron oxides, and uranium-sulfur distances indicating bidentate coordination of U(VI) to sulfate were evident. The affinity of mackinawite and its oxidation products for U(VI) provides impetus for further study of mackinawite as a potential reactive medium for remediation of uranium-contaminated water.

Environmental Science & Technology

Occurrence of alachlor and its sulfonated metabolite in rivers and reservoirs of the midwestern United States: The importance of sulfonation in the transport of chloroacetanilide herbicides

Alachlor and its metabolite, 2-[(2',6'-diethylphenyl)- (methoxymethyl)amino]-2-oxoethanesulfonate (ESA), were identified in 76 reservoirs in the midwestern United States using immunoassay, liquid chromatography, and gas chromatography/mass spectrometry. The median concentration of ESA (0.48 ??g/L) exceeded the median concentration of alachlor (<0.05 ??g/L), with highest values in the upper Midwest. ESA also was detected in the Mississippi River from the mouth to the headwaters at concentrations of 0.2-1.5 ??g/L, exceeding the concentration of alachlor. In a field runoff study, alachlor rapidly formed ESA. It is hypothesized that a glutathione conjugate forms, which later oxidizes in soil to ESA. The removal of the chlorine atom lessens the toxicity of the parent compound and increases runoff potential. It is hypothesized further that sulfonic acid metabolites of other chloroacetanilides, including acetochlor, butachlor, metolachlor, and propachlor, also occur in surface water.

Midwest

Occurrence and behavior of the herbicide Prometon in the hydrologic system

Prometon, a triazine herbicide, is used for total vegetation control on industrial sites, on noncrop areas on farms, in and under asphalt, and to a small extent by homeowners. Prometon has often been detected in surface water and groundwater in studies reported in the literature, but its presence is seldom discussed, partly because of its infrequent inclusion on lists of herbicides used in either agricultural or urban areas. In recent large-scale studies by the U.S. Geological Survey, prometon has been the most commonly detected herbicide in surface water and groundwater in urban areas and the third and fourth most commonly detected herbicide in groundwater and surface water, respectively, in agricultural areas. It also has been detected in rain. The frequent detection of prometon in the environment is discussed in relation to its use practices and predicted environmental behavior. Prometon is compared to atrazine, a structurally similar agricultural triazine herbicide that is one of the most studied and most commonly detected herbicides found in the hydrologic environment. The environmental data presented here demonstrate the wide-scale occurrence of prometon in all components of the hydrologic system, particularly in the surface water and groundwater of urban areas.Prometon, a triazine herbicide, is used for total vegetation control on industrial sites, on noncrop areas on farms, in and under asphalt, and to a small extent by homeowners. Prometon has often been detected in surface water and groundwater in studies reported in the literature, but its presence is seldom discussed, partly because of its infrequent inclusion on lists of herbicides used in either agricultural or urban areas. In recent large-scale studies by the U.S. Geological Survey, prometon has been the most commonly detected herbicide in surface water and groundwater in urban areas and the third and fourth most commonly detected herbicide in groundwater and surface water, respectively, in agricultural areas. It also has been detected in rain. The frequent detection of prometon in the environment is discussed in relation to its use practices and predicted environmental behavior. Prometon is compared to atrazine, a structurally similar agricultural triazine herbicide that is one of the most studied and most commonly detected herbicides found in the hydrologic environment. The environmental data presented here demonstrate the wide-scale occurrence of prometon in all components of the hydrologic system, particularly in the surface water and groundwater of urban areas.

Environmental Science & Technology

Intersection of wildfire and legacy mining poses risk to water quality

Mining and wildfires are both landscape disturbances that pose elevated and substantial hazards to water supplies and ecosystems due to increased erosion and transport of sediment, metals, and debris to downstream waters. The risk to water supplies may be amplified when these disturbances occur in the same watershed. This work describes mechanisms by which the intersection of mining and wildfire may lead to elevated metal concentrations in downstream waters: (1) conveyance of metal-rich ash and soil to surface waters, (2) increased dissolution and transport of dissolved metals due to direct contact of precipitation with mine waste, (3) increased erosion and transport of metal-rich sediment from mining waste, (4) remobilization of previously deposited metal-contaminated floodplain sediment by higher postfire flood flows, and (5) increased metal transport from underground mine workings. Predicted increases in wildfire size, frequency, and burn severity, together with the ongoing need for metal resources, indicate that improved mapping, monitoring, modeling, and mitigation techniques are needed to manage the geochemical hazard of the intersection of wildfire and mining and implications for water availability.

Environmental Science and Technology

Fifteen years of WRTDS for advancing water-quality science: A critical review of methodological developments and global applications

Contamination by nutrients, major ions, and metals poses a major threat to global water sustainability. Understanding how these pollutants vary across time and space requires long-term monitoring and robust statistical approaches. Traditional methods, however, often struggle to account for streamflow variability, seasonality, and nonlinear responses. Introduced in 2010, the Weighted Regressions on Time, Discharge, and Season (WRTDS) method offers a flexible, data-driven framework that generates both observed and flow-normalized estimates of concentration and load. Over the past 15 years, WRTDS has become a state-of-the-art tool for water-quality science and management, with applications spanning a wide range of hydrologic, climatic, and policy contexts─including major watersheds across North America, Europe, Asia, Australia, and the Arctic. In this review of WRTDS, we document the method’s major advancements, examine its expanding geographic and thematic applications, and summarize its relevance to water-quality management programs and policies worldwide. We also discuss its performance relative to other regression and machine-learning approaches. Finally, we identify key priorities for future development to support the continued evolution of WRTDS as a trusted and practical tool for scientists and managers working to protect and sustain water resources.

Environmental Science and Technology

Inputs of fossil carbon from wastewater treatment plants to U.S. Rivers and oceans

Every day more than 500 million cubic meters of treated wastewater are discharged into rivers, estuaries, and oceans, an amount slightly less than the average flow of the Danube River. Typically, wastewaters have high organic carbon (OC) concentrations and represent a large fraction of total river flow and a higher fraction of river OC in densely populated watersheds. Here, we report the first direct measurements of radiocarbon ( 14 C) in municipal wastewater treatment plant (WWTP) effluent. The radiocarbon ages of particulate and dissolved organic carbon (POC and DOC) in effluent are old and relatively uniform across a range of WWTPs in New York and Connecticut. Wastewater DOC has a mean radiocarbon age of 1630 ?? 500 years B.P. and a mean ?? 13 C of -26.0 ?? 1???. Mass balance calculations indicate that 25% of wastewater DOC is fossil carbon, which is likely derived from petroleumbased household products such as detergents and pharmaceuticals. Thesefindings warrant reevaluation of the "apparent age" of riverine DOC, the total flux of petroleum carbon to U.S. oceans, and OC source assignments in waters impacted by sewage. ?? 2009 American Chemical Society.

Environmental Science & Technology

Selected applications of hydrologic science and research in Maryland, Delaware, and Washington, D.C., 2001-2003

One of the roles of the U.S. Geological Survey (USGS) is to provide reliable water data and unbiased water science needed to describe and understand the Nation?s water resources. This fact sheet describes selected techniques that were used by the USGS to collect, transmit, evaluate, or interpret data, in support of investigations that describe the quantity and quality of water resources in Maryland (MD), Delaware (DE), and the District of Columbia (D.C.). These hydrologic investigations generally were performed in cooperation with universities, research centers, and other Federal, State, and local Government agencies. The applications of hydrologic science and research that were selected for this fact sheet were used or tested in the MD-DE-DC District from 2001 through 2003, and include established methods, new approaches, and preliminary research. The USGS usually relies on standard methods or protocols when conducting water-resources research. Occasionally, traditional methods must be modified to address difficult environmental questions or challenging sampling conditions. Technologies developed for other purposes can sometimes be successfully applied to the collection or dissemination of water-resources data. The USGS is continually exploring new ways to collect, transmit, evaluate, and interpret data. The following applications of hydrologic science and research illustrate a few of the recent advances made by scientists working for and with the USGS.

Fact Sheet

Effect of redox conditions on MTBE biodegradation in surface water Sediments

Microbial degradation of methyl tert-butyl ether (MTBE) was observed in surface water-sediment microcosms under anaerobic conditions. The efficiency and products of anaerobic MTBE biodegradation were dependent on the predominant terminal electron-accepting conditions. In the presence of substantial methanogenic activity, MTBE biodegradation was nominal and involved reduction of MTBE to the toxic product, tert-butyl alcohol (TBA). In the absence of significant methanogenic activity, accumulation of [14C]TBA generally decreased, and mineralization of [U-14C]MTBE to 14CO2 generally increased as the oxidative potential of the predominant terminal electron acceptor increased in the order of SO4, Fe(III), Mn(IV) < NO3 < O2. Microbial mineralization of MTBE to CO2 under Mn(IV)or SO4-reducing conditions has not been reported previously. The results of this study indicate that microorganisms inhabiting the sediments of streams and lakes can degrade MTBE effectively under a range of anaerobic terminal electron-accepting conditions. Thus, anaerobic bed sediment microbial processes may provide a significant environmental sink for MTBE in surface water systems throughout the United States.

Environmental Science & Technology

Applications of fluorescence spectroscopy for predicting percent wastewater in an urban stream

Dissolved organic carbon (DOC) is a significant organic carbon reservoir in many ecosystems, and its characteristics and sources determine many aspects of ecosystem health and water quality. Fluorescence spectroscopy methods can quantify and characterize the subset of the DOC pool that can absorb and re-emit electromagnetic energy as fluorescence and thus provide a rapid technique for environmental monitoring of DOC in lakes and rivers. Using high resolution fluorescence techniques, we characterized DOC in the Tualatin River watershed near Portland, Oregon, and identified fluorescence parameters associated with effluent from two wastewater treatment plants and samples from sites within and outside the urban region. Using a variety of statistical approaches, we developed and validated a multivariate linear regression model to predict the amount of wastewater in the river as a function of the relative abundance of specific fluorescence excitation/emission pairs. The model was tested with independent data and predicts the percentage of wastewater in a sample within 80% confidence. Model results can be used to develop in situ instrumentation, inform monitoring programs, and develop additional water quality indicators for aquatic systems.

Oregon

Fate and transport of linear alkylbenzenesulfonate in a sewage- contaminated aquifer: A comparison of natural-gradient pulsed tracer tests

Two natural-gradient tracer tests were conducted to determine the transport and biodegradation behavior of linear alkylbenzenesulfonate (LAS) surfactant under in situ conditions in a sewage-contaminated aquifer. The tests were conducted in two biogeochemically distinct zones of the aquifer: (1) an aerobic uncontaminated zone (oxic zone) and (2) a moderately aerobic, sewage-contaminated zone (transition zone). Chromatographic separation of the surfactant mixture was observed in both zones and attributed to the retardation of the longer alkyl chain homologues during transport. No significant loss of IAS mass was observed for the oxic zone while 20% of the LAS mass injected into the transition zone was removed due to biodegradation. Biodegradation preferentially removed the longer alkyl chain homologues and the external isomers (i.e., 2- and 3-phenyl). The removal of LAS mass coincided with a decrease in dissolved oxygen concentrations, the appearance of LAS metabolites, and an increase in the number of free-living bacteria with a concomitant change in bacteria morphology. The formation of LAS metabolites accounted for 86% of the LAS mass removed in the transition zone. Over the duration of the test, sorption and biodegradation enriched the LAS mixture in the more water-soluble and biologically resistant components.Two natural-gradient tracer tests were conducted to determine the transport and biodegradation behavior of linear alkylbenzenesulfonate (LAS) surfactant under in situ conditions in a sewage-contaminated aquifer. The tests were conducted in two biogeochemically distinct zones of the aquifer: (1) an aerobic uncontaminated zone (oxic zone) and (2) a moderately aerobic, sewage-contaminated zone (transition zone). Chromatographic separation of the surfactant mixture was observed in both zones and attributed to the retardation of the longer alkyl chain homologues during transport. No significant loss of LAS mass was observed for the oxic zone while 20% of the LAS mass injected into the transition zone was removed due to biodegradation. Biodegradation preferentially removed the longer alkyl chain homologues and the external isomers (i.e., 2- and 3-phenyl). The removal of LAS mass coincided with a decrease in dissolved oxygen concentrations, the appearance of LAS metabolites, and an increase in the number of free-living bacteria with a concomitant change in bacteria morphology. The formation of LAS metabolites accounted for 86% of the LAS mass removed in the transition zone. Over the duration of the test, sorption and biodegradation enriched the LAS mixture in the more water-soluble and biologically resistant components.

Environmental Science & Technology

Potential for intrinsic bioremediation of a DNT-contaminated aquifer

Microorganisms indigenous to a shallow aquifer, which underlies an explosives-contaminated site, mineralized 28% of [U-ring- 14 C] 2,4–dinitrotoluene to 14 CO 2 within 28 days under aerobic conditions. Approximately 20% of added 2,4–dinitrotoluene remained undegraded at the end of the incubation while approximately 22% and 6% were transformed to 4–amino-2–nitrotoluene and 2–amino-4–nitrotoluene, respectively. In aquifer microcosms containing 2,6–dinitrotoluene, approximately 67% of the substrate remained undegraded and approximately 14% was transformed to 2–amino-6–nitrotoluene. The radiolabeled study indicated that about 8% of the 2,6–dinotrotoluene was mineralized to CO 2 . The demonstrated degradation and subsequent mineralization of dinitrotoluene compounds by aquifer microorganisms are consistent with the decline in dissolved dinitrotoluene concentrations observed along the general ground-water flowpath at the site. The results indicate that intrinsic bioremediation may be a viable alternative for remediating contaminated ground water at this site.

Environmental Science & Technology