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At least 109 records · Page 6Linked to original sources

Photochemical changes in cyanide speciation in drainage from a precious metal ore heap

In drainage from an inactive ore heap at a former gold mine, the speciation of cyanide and the concentrations of several metals were found to follow diurnal cycles. Concentrations of the hexacyanoferrate complex, iron, manganese, and ammonium were higher at night than during the day, whereas weak-acid-dissociable cyanide, silver, gold, copper, nitrite, and pH displayed the reverse behavior. The changes in cyanide speciation, iron, and trace metals can be explained by photodissociation of iron and cobalt cyanocomplexes as the solutions emerged from the heap into sunlight-exposed channels. At midday, environmentally significant concentrations of free cyanide were produced in a matter of minutes, causing trace copper, silver, and gold to be mobilized as cyanocomplexes from solids. Whether rapid photodissociation is a general phenomenon common to other sites will be important to determine in reaching a general understanding of the environmental risks posed by routine or accidental water discharges from precious metal mining facilities.

Environmental Science & Technology

Use of ICP/MS with ultrasonic nebulizer for routine determination of uranium activity ratios in natural water

A method is described that allows precise determination of 234 U/ 238 U activity ratios (UAR) in most natural waters using commonly available inductively coupled plasma/mass spectrometry (ICP/MS) instrumentation and accessories. The precision achieved by this technique (±0.5% RSD, 1 sigma) is intermediate between thermal ionization mass spectrometry (±0.25% RSD, 1 sigma) and alpha particle spectrometry (±5% RSD, 1 sigma). It is precise and rapid enough to allow analysis of a large number of samples in a short period of time at low cost using standard, commercially available quadrupole instrumentation with ultrasonic nebulizer and desolvator accessories. UARs have been analyzed successfully in fresh to moderately saline waters with U concentrations of from less than 1 μg/L to nearly 100 μg/L. An example of the uses of these data is shown for a study of surface-water mixing in the North Platte River in western Nebraska. This rapid and easy technique should encourage the wider use of uranium isotopes in surface-water and groundwater investigations, both for qualitative (e.g. identifying sources of water) and quantitative (e.g. determining end-member mixing ratios purposes.

Environmental Science & Technology

Temporal changes in surface-water insecticide concentrations after the phaseout of diazinon and chlorpyrifos

The recent (late 2001) federally mandated phaseout of diazinon and chlorpyrifos insecticide use in outdoor urban settings has resulted in a rapid decline in concentrations of these insecticides in urban streams and rivers in the northeastern and midwestern United States. Assessment of temporal insecticide trends at 20 sites showed that significant step decreases in diazinon concentrations occurred at 90% of the sites after the phaseout, with concentrations generally decreasing by over 50% in summer samples. Chlorpyrifos concentrations showed significant step decreases in at least 1 season at 3 of the 4 sites with sufficient data for analysis. The decrease in diazinon concentrations in response to the phaseout resulted in a decline in the frequency of concentrations exceeding the acute invertebrate water-quality benchmark of 0.1 μg/L from 10% of pre-phaseout summer samples to fewer than 1% of post-phaseout summer samples. Although some studies have indicated an increase in concentrations of carbaryl in response to the organophosphorous phaseout, carbaryl concentrations only increased at 1 site after the phaseout. A full assessment of the effect of the phaseout of diazinon and chlorpyrifos on surface water will require data on other insecticides used to replace these compounds.

Environmental Science & Technology

Growth of coal mining operations in the Elk River Valley (Canada) linked to increasing solute transport of Se, NO3-, and SO42- into the transboundary Koocanusa Reservoir (USA-Canada)

Koocanusa Reservoir (KOC) is a waterbody that spans the United States (U.S.) and Canadian border. Increasing concentrations of total selenium (Se), nitrate + nitrite (NO 3 – , nitrite is insignificant or not present), and sulfate (SO 4 2– ) in KOC and downstream in the Kootenai River (Kootenay River in Canada) are tied to expanding coal mining operations in the Elk River Watershed, Canada. Using a paired watershed approach, trends in flow-normalized concentrations and loads were evaluated for Se, NO 3 – , and SO 4 2– for the two largest tributaries, the Kootenay and Elk Rivers, Canada. Increases in concentration (SO 4 2– 120%, Se 581%, NO 3 – 784%) and load (SO 4 2– 129%, Se 443%, NO 3 – 697%) in the Elk River (1979–2022 for NO 3 – , 1984–2022 for Se and SO 4 2– ) are among the largest documented increases in the primary literature, while only a small magnitude increase in SO 4 2– (7.7% concentration) and decreases in Se (−10%) and NO 3 – (−8.5%) were observed in the Kootenay River. Between 2009 and 2019, the Elk River contributed, on average, 29% of the combined flow, 95% of the Se, 76% of the NO 3 – , and 38% of the SO 4 2– entering the reservoir from these two major tributaries. The largest increase in solute concentrations occurred during baseflows, indicating a change in solute transport and delivery dynamics in the Elk River Watershed, which may be attributable to altered landscapes from coal mining operations including altered groundwater flow paths and increased chemical weathering in waste rock dumps. More recently there is evidence of surface water treatment operations providing some reduction in concentrations during low flow times of year; however, these appear to have a limited effect on annual loads entering KOC. These findings imply that current mine water treatment, which is focused on surface waters, may not sufficiently reduce the influence of mine-waste-derived solutes in the Elk River to allow constituent concentrations in KOC to meet U.S. water-quality standards.

Environmental Science and Technology

PFAS river export analysis highlights the urgent need for catchment-scale mass loading data

Source apportionment of per- and polyfluoroalkyl substances (PFAS) requires an understanding of the mass loading of these compounds in river basins. However, there is a lack of temporally variable and catchment-scale mass loading data, meaning identification and prioritization of sources of PFAS to rivers for management interventions can be difficult. Here, we analyze PFAS concentrations and loads in the River Mersey to provide the first temporally robust estimates of PFAS export for a European river system and the first estimates of the contribution of wastewater treatment works (WwTWs) to total river PFAS export. We estimate an annual PFAS export of 68.1 kg for the River Mersey and report that the yield of perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) in the catchment is among the highest recorded globally. Analysis of river and WwTW loads indicates approximately one-third of PFOA emitted from WwTWs is potentially stored in the catchment and approximately half of PFOS transported by the River Mersey may not originate from WwTWs. As governments move toward regulation of PFAS in WwTW effluents, our findings highlight the complexity of PFAS source apportionment and the need for catchment-scale mass loading data. This study indicates that strategies for reducing PFAS loading that focus solely on WwTW effluents may not achieve river water quality targets.

Environmental Science & Technology Letters

Post-Depositional Behavior of Cu in a Metal-Mining Polishing Pond (East Lake, Canada)

The post-depositional behavior of Cu in a gold-mining polishing pond (East Lake, Canada) was assessed after mine closure by examination of porewater chemistry and mineralogy. The near-surface (upper 1.5 cm) sediments are enriched in Cu, with values ranging from 0.4 to 2 wt %. Mineralogical examination revealed that the bulk of the Cu inventory is present as authigenic copper sulfides. Optical microscopy, energy-dispersion spectra, and X-ray data indicate that the main Cu sulfide is covellite (CuS). The formation of authigenic Cu-S phases is supported by the porewater data, which demonstrate that the sediments are serving as a sink for dissolved Cu below sub-bottom depths of 1-2 cm. The zone of Cu removal is consistent with the occurrence of detectable sulfide and the consumption of sulfate. The sediments can be viewed as a passive bioreactor that permanently removes Cu as insoluble copper sulfides. This process is not unlike that which occurs in other forms of bioremediation, such as wetlands and permeable reactive barriers. Above the zone of Cu removal, dissolved Cu maxima in the interfacial porewaters range from 150 to 450 ??g L-1 and reflect the dissolution of a Cu-bearing phase in the surface sediments. The reactive phase is thought to be a component of treatment sludges delivered to the lake as part of cyanide treatment. Flux calculations indicate that the efflux of dissolved Cu from the sediments to the water column (14-51 ??g cm-2 yr-1) can account for the elevated levels of dissolved Cu in lake waters (???50 ??g L-1). Implications for lake recovery are discussed.

Environmental Science & Technology

Economic and health risk trade-offs of swim closures at a Lake Michigan beach

This paper presents a framework for analyzing the economic, health, and recreation implications of swim closures related to high fecal indicator bacteria (FIB) levels. The framework utilizes benefit transfer policy analysis to provide a practical procedure for estimating the effectiveness of recreational water quality policies. Evaluation criteria include the rates of intended and unintended management outcomes, whether the chosen protocols generate closures with positive net economic benefits to swimmers, and the number of predicted illnesses the policy is able to prevent. We demonstrate the framework through a case study of a Lake Michigan freshwater beach using existing water quality and visitor data from 1998 to 2001. We find that a typical closure causes a net economic loss among would-be swimmers totaling $1274-37 030/ day, depending on the value assumptions used. Unnecessary closures, caused by high indicator variability and a 24-h time delay between when samples are taken and the management decision can be made, occurred on 14 (12%) out of 118 monitored summer days. Days with high FIB levels when the swim area is open are also common but do relatively little economic harm in comparison. Also, even if the closure policy could be implemented daily and perfectly without error, only about 42% of predicted illnesses would be avoided. These conclusions were sensitive to the relative values and risk preferences that swimmers have for recreation access and avoiding health effects, suggesting a need for further study of the impacts of recreational water quality policies on individuals.

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

Factors associated with sources, transport, and fate of chloroform and three other trihalomethanes in untreated groundwater used for drinking water

Multiple lines of evidence for indicating factors associated with the sources, transport, and fate of chloroform and three other trihalomethanes (THMs) in untreated groundwater were revealed by evaluating low-level analytical results and logistic regression results for THMs. Samples of untreated groundwater from wells used for drinking water were collected from 1996-2007 from 2492 wells across the United States and analyzed for chloroform, bromodichloromethane, dibromochloromethane, and bromoform by a low-level analytical method implemented in April 1996. Using an assessment level of 0.02 μg/L, chloroform was detected in 36.5% of public-well samples and 17.6% of domestic-well samples, with most concentrations less than 1 μg/L. Brominated THMs occurred less frequently than chloroform but more frequently in public-well samples than domestic-well samples. For both public and domestic wells, THMs occurred most frequently in urban areas. Logistic regression analyses showed that the occurrence of THMs was related to nonpoint sources such as urban land use and to point sources like septic systems. The frequent occurrence and concentration distribution pattern of THMs, as well as their frequent co-occurrence with other organic compounds and nitrate, all known to have anthropogenic sources, and the positive associations between THM occurrence and dissolved oxygen and recharge indicate the recycling of water that contains THMs and other anthropogenic contaminants.

Environmental Science & Technology

Decreased atmospheric sulfur deposition across the southeastern U.S.: When will watersheds release stored sulfate?

Emissions of sulfur dioxide (SO 2 ) to the atmosphere lead to atmospheric deposition of sulfate (SO 4 2- ), which is the dominant strong acid anion causing acidification of surface waters and soils in the eastern United States (U.S.). Since passage of the Clean Air Act and its Amendments, atmospheric deposition of SO 2 in this region has declined by over 80%, but few corresponding decreases in stream-water SO 4 2- concentrations have been observed in unglaciated watersheds. We calculated SO 4 2- mass balances for 27 forested, unglaciated watersheds from Pennsylvania to Georgia, by using total atmospheric deposition (wet plus dry) as input. Many of these watersheds still retain SO 4 2- , unlike their counterparts in the northeastern U.S. and southern Canada. Our analysis showed that many of these watersheds should convert from retaining to releasing SO 4 2- over the next two decades. The specific years when the watersheds crossover from retaining to releasing SO 4 2- correspond to a general geographical pattern of later net watershed release from north to south. The single most important variable that explained the crossover year was the runoff ratio, defined as the ratio of annual mean stream discharge to precipitation. Percent clay content and mean soil depth were secondary factors in predicting crossover year. The conversion of watersheds from net SO 4 2- retention to release anticipates more widespread reductions in stream-water SO 4 2- concentrations in this region.

Environmental Science & Technology

Mobilization and transport of soil particles during infiltration experiments in an agricultural field, Shenandoah Valley, Virginia

Evidence that fine particles mobilized and transported in soils and aquifers can have a profound influence on contaminant migration has spawned much interest recently in understanding colloid transport in natural materials. Repeated infiltration experiments on an initially dry field soil were conducted to evaluate rates of mobilization of fine particles over time and to investigate the importance of transient-flow events on particle transport. Water flow was measured in zero-tension lysimeters at 25 cm depth. For repeated infiltration events and for all plots, water flow sharply increased shortly after initial ponding of water at the soil surface, maintained a relatively steady level during the period of ponding, and decreased gradually thereafter. Particle concentrations measured in the pan lysimeters ranged from 7 mg L - 1 to 265 mg L - 1 and were typically on the order of 10 to 100 mg L - 1 . Greatest particle mass flux was observed during the initial infiltration experiment on each plot. During four subsequent infiltration experiments, all conducted within 250 min of the first event, steady mass fluxes were observed that were approximately 70% of the average value seen in the first flush of water through a dry soil, indicating that the supply of mobile soil particles is only sparingly reduced over closely spaced infiltration events. All peak particle concentrations and mass fluxes occurred near either the rising limb or the falling limb of the water flux hydrograph, presumably reflecting the movement of air−water interfaces during imbibition and drainage.

Virginia

Differences in neonicotinoid and metabolite sorption to activated carbon are driven by alterations to the insecticidal pharmacophore

Widespread application of neonicotinoids has led to their proliferation in waters. Despite low neonicotinoid hydrophobicity, our prior studies implicated granular activated carbon (GAC) in neonicotinoid removal. Based on known receptor binding characteristics, we hypothesized that the insecticidal pharmacophore influences neonicotinoid sorption. Our objectives were to illuminate drivers of neonicotinoid sorption for parent neonicotinoids (imidacloprid, clothianidin, thiamethoxam, and thiacloprid) and pharmacophore-altered metabolites (desnitro-imidacloprid and imidacloprid urea) to GAC, powdered activated carbon, and carbon nanotubes (CNTs). Neonicotinoid sorption to GAC was extensive and largely irreversible, with significantly greater sorption of imidacloprid than desnitro-imidacloprid. Imidacloprid and imidacloprid urea (electronegative pharmacophores) sorbed most extensively to nonfunctionalized CNTs, whereas desnitro-imidacloprid (positive pharmacophore) sorbed most to COOH-CNTs, indicating the importance of charge interactions and/or hydrogen bonding between the pharmacophore and carbon surface. Water chemistry parameters (temperature, alkalinity, ionic strength, and humic acid) inhibited overall neonicotinoid sorption, suggesting that pharmacophore-driven sorption in real waters may be diminished. Analysis of a full-scale drinking water treatment plant GAC filter influent, effluent, and spent GAC attributes neonicotinoid/metabolite removal to GAC under real-world conditions for the first time. Our results demonstrate that the neonicotinoid pharmacophore not only confers insecticide selectivity but also impacts sorption behavior, leading to less effective removal of metabolites by GAC filters in water treatment.

Environmental Science and Technology

Vertical distribution of microplastics in the water column and surficial sediment from the Milwaukee River basin to Lake Michigan

Microplastic contamination was studied along a freshwater continuum from inland streams to the Milwaukee River estuary to Lake Michigan, and vertically from the water surface, water subsurface and sediment. Microplastics were detected in all 96 water samples and nine sediment samples collected. Results indicated a gradient of polymer presence with depth: low-density particles decreased from water surface to subsurface to sediment, and high-density particles had the opposite result. Polymer identification results indicated water surface and subsurface samples were dominated by low-density polypropylene particles and sediment samples were dominated by more dense polyethylene terephthalate particles. Of the five particle-type categories (fragments, films, foams, pellets/beads and fibers/lines), fibers/lines were the most common particle type and were present in every water and sediment sample collected. Fibers represented 45% of all particles in water samples and were distributed vertically throughout the water column regardless of density. Sediment samples were dominated by black foams (66%, identified as styrene-butadiene rubber, SBR) and to a lesser extent fibers/lines (29%) with approximately 89% of all the sediment particles coming from polymers with densities greater than 1.1 g cm-3. Results demonstrated polymer density influenced partitioning between water surface and subsurface and the underlying surficial sediment and the common practice of sampling only the water surface can result in substantial bias, especially in estuarine, harbor and lake locations where water surface concentrations tend to overestimate mean water column concentrations.

Wisconsin

Measurement of in situ rates of selenate removal by dissimilatory bacterial reduction in sediments

A radioisotope method for measurement of bacteria respiratory reduction of selenate to elemental selenium in aquatic sediments was devised. Sediments were labeled with [75Se]selenate, incubated, and washed, and 75Se0(s) was determined as counts remaining in the sediments. Core profiles of selenate reduction, sulfate reduction, and denitrification were made simultaneously in the sediments of an agricultural wastewater evaporation pond. Most of the in situ selenate reduction (85%) and all the denitrificatation activities were confined to the upper 4-8 cm of the profile, whereas sulfate reduction was greatest below 8 cm (89% of total). The integrated areal rate of selenate reduction was 301 mol m-2 day-1, which results in a turnover of water column selenate in 82.4 days.

Environmental Science & Technology

Spectroscopic evidence for uranium bearing precipitates in vadose zone sediments at the Hanford 300-area site

Uranium (U) solid-state speciation in vadose zone sediments collected beneath the former North Process Pond (NPP) in the 300 Area of the Hanford site (Washington) was investigated using multi-scale techniques. In 30 day batch experiments, only a small fraction of total U (???7.4%) was released to artificial groundwater solutions equilibrated with 1% pCO2. Synchrotron-based micro-X-ray fluorescence spectroscopy analyses showed that U was distributed among at least two types of species: (i) U discrete grains associated with Cu and (ii) areas with intermediate U concentrations on grains and grain coatings. Metatorbernite (Cu[UO2]2[PO 4]2??8H2O) and uranophane (Ca[UO 2]2[SiO3(OH)]2?? 5H 2O) at some U discrete grains, and muscovite at U intermediate concentration areas, were identified in synchrotron-based micro-X-ray diffraction. Scanning electron microscopy/energy dispersive X-ray analyses revealed 8-10 ??m size metatorbernite particles that were embedded in C-, Al-, and Si-rich coatings on quartz and albite grains. In ??- and bulk-X-ray absorption structure (??-XAS and XAS) spectroscopy analyses, the structure of metatorbernite with additional U-C and U-U coordination environments was consistently observed at U discrete grains with high U concentrations. The consistency of the ??- and bulk-XAS analyses suggests that metatorbernite may comprise a significant fraction of the total U in the sample. The entrapped, micrometer-sized metatorbernite particles in C-, Al-, and Si-rich coatings, along with the more soluble precipitated uranyl carbonates and uranophane, likely control the long-term release of U to water associated with the vadose zone sediments. ?? 2007 American Chemical Society.

Environmental Science & Technology

Methane emissions from artificial waterbodies dominate the carbon footprint of irrigation: A study of transitions in the food-energy-water-climate nexus (Spain, 1900-2014)

Irrigation in the Mediterranean region has been used for millennia and has greatly expanded with industrialization. Irrigation is critical for climate change adaptation, but it is also an important source of greenhouse gas emissions. This study analyzes the carbon (C) footprint of irrigation in Spain, covering the complete historical process of mechanization. A 21-fold total, 6-fold area-based, and 4-fold product-based increase in the carbon footprint was observed during the 20th century, despite an increase in water use efficiency. CH 4 emissions from waterbodies, which had not previously been considered in the C footprint of irrigation systems, dominated the emission budget during most of the analyzed period. Technologies to save water and tap new water resources greatly increased energy and infrastructure demand, while improvements in power generation efficiency had a limited influence on irrigation emissions. Electricity production from irrigation dams may contribute to climate change mitigation, but the amount produced in relation to that consumed in irrigation has greatly declined. High uncertainty in CH 4 emission estimates from waterbodies stresses a need for more spatially resolved data and an improved empirical knowledge of the links between water quality, water level fluctuations, and emissions at the regional scale.

Environmental Science & Technology