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At least 505 records · Page 28Linked to original sources
USGS2006

Regional patterns in the isotopic composition of natural and anthropogenic nitrate in groundwater, High Plains, U.S.A.

Mobilization of natural nitrate (NO 3 - ) deposits in the subsoil by irrigation water in arid and semiarid regions has the potential to produce large groundwater NO 3 - concentrations. The use of isotopes to distinguish between natural and anthropogenic NO 3 - sources in these settings could be complicated by the wide range in δ 15 N values of natural NO 3 - . An ∼10 000 year record of paleorecharge from the regionally extensive High Plains aquifer indicates that δ 15 N values for NO 3 - derived from natural sources ranged from 1.3 to 12.3‰ and increased systematically from the northern to the southern High Plains. This collective range in δ 15 N values spans the range that might be interpreted as evidence for fertilizer and animal-waste sources of NO 3 - ; however, the δ 15 N values for NO 3 - in modern recharge ( less than 50 years) under irrigated fields were, for the most part, distinctly different from those of paleorecharge when viewed in the overall regional context. An inverse relation was observed between the δ 15 N[NO 3 - ] values and the NO 3 - /Cl - ratios in paleorecharge that is qualitatively consistent with fractionating losses of N increasing from north to south in the High Plains. N and O isotope data for NO 3 - are consistent with both NH 3 volatilization and denitrification, having contributed to fractionating losses of N prior to recharge. The relative importance of different isotope fractionating processes may be influenced by regional climate patterns as well as by local variation in soils, vegetation, topography, and moisture conditions.

Environmental Science & Technology↗
USGS2006

Atmospheric deposition of current-use and historic-use pesticides in snow at National Parks in the Western United States

The United States (U.S.) National Park Service has initiated research on the atmospheric deposition and fate of semi-volatile organic compounds in its alpine, sub-Arctic, and Arctic ecosystems in the Western U.S. Results for the analysis of pesticides in seasonal snowpack samples collected in spring 2003 from seven national parks are presented herein. From a target analyte list of 47 pesticides and degradation products, the most frequently detected current-use pesticides were dacthal, chlorpyrifos, endosulfan, and ??- hexachlorocyclohexane, whereas the most frequently detected historic-use pesticides were dieldrin, ??-hexachlorocyclohexane, chlordane, and hexachlorobenzene. Correlation analysis with latitude, temperature, elevation, particulate matter, and two indicators of regional pesticide use reveal that regional current and historic agricultural practices are largely responsible for the distribution of pesticides in the national parks in this study. Pesticide deposition in the Alaskan parks is attributed to long-range transport because there are no significant regional pesticide sources. The percentage of total pesticide concentration due to regional transport (%RT) was calculated for the other parks. %RT was highest at parks with higher regional cropland intensity and for pesticides with lower vapor pressures and shorter half-lives in air. ?? 2006 American Chemical Society.

Environmental Science & Technology↗
USGS2006

Investigating ebullition in a sand column using dissolved gas analysis and reactive transport modeling

Ebullition of gas bubbles through saturated sediments can enhance the migration of gases through the subsurface, affect the rate of biogeochemical processes, and potentially enhance the emission of important greenhouse gases to the atmosphere. To better understand the parameters controlling ebullition, methanogenic conditions were produced in a column experiment and ebullition through the column was monitored and quantified through dissolved gas analysis and reactive transport modeling. Dissolved gas analysis showed rapid transport of CH 4 vertically through the column at rates several times faster than the bromide tracer and the more soluble gas CO 2 , indicating that ebullition was the main transport mechanism for CH 4 . An empirically derived formulation describing ebullition was integrated into the reactive transport code MIN3P allowing this process to be investigated on the REV scale in a complex geochemical framework. The simulations provided insights into the parameters controlling ebullition and show that, over the duration of the experiment, 36% of the CH 4 and 19% of the CO 2 produced were transported to the top of the column through ebullition.

Environmental Science & Technology↗
USGS2006

Modeling the transport and inactivation of E. coli and enterococci in the near-shore region of Lake Michigan

To investigate the transport and fate of fecal pollution at Great Lakes beaches and the health risks associated with swimming, the near-shore waters of Lake Michigan and two tributaries discharging into it were examined for bacterial indicators of human fecal pollution. The enterococcus human fecal pollution marker, which targets a putative virulence factor the enterococcal surface protein (esp) in Enterococcus faecium , was detected in 2/28 samples (7%) in the tributaries draining into Lake Michigan and in 6/30 samples (20%) in Lake Michigan beaches. This was indicative of human fecal pollution being transported in the tributaries and occurrence at Lake Michigan beaches. To understand the relative importance of different processes influencing pollution transport and inactivation, a finite-element model of surf-zone hydrodynamics (coupled with models for temperature, E. coli and enterococci) was used. Enterococci appear to survive longer than E. coli , which was described using an overall first-order inactivation coefficient in the range 0.5−2.0 per day. Our analysis suggests that the majority of fecal indicator bacteria variation can be explained based on loadings from the tributaries. Sunlight is a major contributor to inactivation in the surf-zone and the formulation based on sunlight, temperature and sedimentation is preferred over the first-order inactivation formulation.

Environmental Science & Technology↗
USGS2006

Investigation of mercury exchange between forest canopy vegetation and the atmosphere using a new dynamic chamber

This paper presents the design of a dynamic chamber system that allows full transmission of PAR and UV radiation and permits enclosed intact foliage to maintain normal physiological function while Hg(0) flux rates are quantified in the field. Black spruce and jack pine foliage both emitted and absorbed Hg(0), exhibiting compensation points near atmospheric Hg(0) concentrations of ∼2−3 ng m - 3 . Using enriched stable Hg isotope spikes, patterns of spike Hg(II) retention on foliage were investigated. Hg(0) evasion rates from foliage were simultaneously measured using the chamber to determine if the decline of foliar spike Hg(II) concentrations over time could be explained by the photoreduction and re-emission of spike Hg to the atmosphere. This mass balance approach suggested that spike Hg(0) fluxes alone could not account for the measured decrease in spike Hg(II) on foliage following application, implying that either the chamber underestimates the true photoreduction of Hg(II) to Hg(0) on foliage, or other mechanisms of Hg(II) loss from foliage, such as cuticle weathering, are in effect. The radiation spectrum responsible for the photoreduction of newly deposited Hg(II) on foliage was also investigated. Our spike experiments suggest that some of the Hg(II) in wet deposition retained by the forest canopy may be rapidly photoreduced to Hg(0) and re-emitted back to the atmosphere, while another portion may be retained by foliage at the end of the growing season, with some being deposited in litterfall. This finding has implications for the estimation of Hg dry deposition based on throughfall and litterfall fluxes.

Environmental Science & Technology↗
USGS2006

Occurrence and fate of organic contaminants during onsite wastewater treatment

Onsite wastewater treatment systems serve approximately 25% of the U.S. population. However, little is known regarding the occurrence and fate of organic wastewater contaminants (OWCs), including endocrine disrupting compounds, during onsite treatment. A range of OWCs including surfactant metabolites, steroids, stimulants, metal-chelating agents, disinfectants, antimicrobial agents, and pharmaceutical compounds was quantified in wastewater from 30 onsite treatment systems in Summit and Jefferson Counties, CO. The onsite systems represent a range of residential and nonresidential sources. Eighty eight percent of the 24 target compounds were detected in one or more samples, and several compounds were detected in every wastewater sampled. The wastewater matrices were complex and showed unique differences between source types due to differences in water and consumer product use. Nonresidential sources generally had more OWCs at higher concentrations than residential sources. Additional aerobic biofilter-based treatment beyond the traditional anaerobic tank-based treatment enhanced removal for many OWCs. Removal mechanisms included volatilization, biotransformation, and sorption with efficiencies from <1% to >99% depending on treatment type and physico chemical properties of the compound. Even with high removal rates during confined unit onsite treatment, OWCs are discharged to soil dispersal units at loadings up to 20 mg/m 2 /d, emphasizing the importance of understanding removal mechanisms and efficiencies in onsite treatment systems that discharge to the soil and water environments.

Environmental Science & Technology↗
USGS2006

Hyporheic exchange and fulvic acid redox reactions in an alpine stream/wetland ecosystem, Colorado front range

The influence of hyporheic zone interactions on the redox state of fulvic acids and other redox active species was investigated in an alpine stream and adjacent wetland, which is a more reducing environment. A tracer injection experiment using bromide (Br - ) was conducted in the stream system. Simulations with a transport model showed that rates of exchange between the stream and hyporheic zone were rapid (α ≈ 10 - 3 s -1 ). Parallel factor analysis of fluorescence spectra was used to quantify the redox state of dissolved fulvic acids. The rate coefficient for oxidation of reduced fulvic acids (λ = 6.5 × 10 - 3 s -1 ) in the stream indicates that electron-transfer reactions occur over short time scales. The rate coefficients for decay of ammonium (λ = 1.2 × 10 - 3 s -1 ) and production of nitrate (λ = −1.0 × 10 - 3 s -1 ) were opposite in sign but almost equal in magnitude. Our results suggest that fulvic acids are involved in rapid electron-transfer processes in and near the stream channel and may be important in determining ecological energy flow at the catchment scale.

Colorado↗
USGS2006

Vulnerability of shallow groundwater and drinking-water wells to nitrate in the United States

Two nonlinear models were developed at the national scale to (1) predict contamination of shallow ground water (typically < 5 m deep) by nitrate from nonpoint sources and (2) to predict ambient nitrate concentration in deeper supplies used for drinking. The new models have several advantages over previous national-scale approaches. First, they predict nitrate concentration (rather than probability of occurrence), which can be directly compared with water-quality criteria. Second, the models share a mechanistic structure that segregates nitrogen (N) sources and physical factors that enhance or restrict nitrate transport and accumulation in ground water. Finally, data were spatially averaged to minimize small-scale variability so that the large-scale influences of N loading, climate, and aquifer characteristics could more readily be identified. Results indicate that areas with high N application, high water input, well-drained soils, fractured rocks or those with high effective porosity, and lack of attenuation processes have the highest predicted nitrate concentration. The shallow groundwater model (mean square error or MSE = 2.96) yielded a coefficient of determination ( R 2 ) of 0.801, indicating that much of the variation in nitrate concentration is explained by the model. Moderate to severe nitrate contamination is predicted to occur in the High Plains, northern Midwest, and selected other areas. The drinking-water model performed comparably (MSE = 2.00, R 2 = 0.767) and predicts that the number of users on private wells and residing in moderately contaminated areas (>5 to ≤10 mg/L nitrate) decreases by 12% when simulation depth increases from 10 to 50 m.

Environmental Science & Technology↗
USGS2006

Effects of hurricanes Katrina and Rita on the chemistry of bottom sediments in Lake Pontchartrain, Louisiana, USA

The effects of Hurricanes Katrina and Rita and the subsequent unwatering of New Orleans, Louisiana, on the sediment chemistry of Lake Pontchartrain were evaluated by chemical analysis of samples of street mud and suspended and bottom sediments. The highest concentrations of urban-related elements and compounds (e.g., Pb, Zn, polycyclic aromatic hydrocarbons, and chlordane) in bottom sediments exceeded median concentrations in U.S. urban lakes and sediment-quality guidelines. The extent of the elevated concentrations was limited, however, to within a few hundred meters of the mouth of the 17th Street Canal, similar to results of historical assessments. Chemical and radionuclide analysis of pre- and post-Hurricane Rita samples indicates that remobilization of near-shore sediment by lake currents and storms is an ongoing process. The effects of Hurricanes Katrina and Rita on the sediment chemistry of Lake Pontchartrain are limited spatially and are most likely transitory.

Environmental Science & Technology↗
USGS2006

Acid rain effects on aluminum mobilization clarified by inclusion of strong organic acids

Assessments of acidic deposition effects on aquatic ecosystems have often been hindered by complications from naturally occurring organic acidity. Measurements of pH and ANCG, the most commonly used indicators of chemical effects, can be substantially influenced by the presence of organic acids. Relationships between pH and inorganic Al, which is toxic to many forms of aquatic biota, are also altered by organic acids. However, when inorganic Al concentrations are plotted against ANC (the sum of Ca2+, Mg 2+, Na+, and K+, minus SO42-, NO3-, and Cl-), a distinct threshold for Al mobilization becomes apparent. If the concentration of strong organic anions is included as a negative component of ANC, the threshold occurs at an ANC value of approximately zero, the value expected from theoretical charge balance constraints. This adjusted ANC is termed the base-cation surplus. The threshold relationship between the base-cation surplus and Al was shown with data from approximately 200 streams in the Adirondack region of New York, during periods with low and high dissolved organic carbon concentrations, and for an additional stream from the Catskill region of New York. These results indicate that (1) strong organic anions can contribute to the mobilization of inorganic Al in combination with SO42- and NO 3-, and (2) the presence of inorganic Al in surface waters is an unambiguous indication of acidic deposition effects. ?? 2007 American Chemical Society.

Environmental Science & Technology↗
USGS2006

Chlorinated solvents in groundwater of the United States

Four chlorinated solvents-methylene chloride, perchloroethene (PCE), 1,1,1-trichloroethane, and trichloroethene (TCE)-were analyzed in samples of groundwater taken throughout the conterminous United States by the U.S. Geological Survey. The samples were collected between 1985 and 2002 from more than 5,000 wells. Of 55 volatile organic compounds (VOCs) analyzed in groundwater samples, solvents were among the most frequently detected. Mixtures of solvents in groundwater were common and may be the result of common usage of solvents or degradation of one solvent to another. Relative to other VOCs with Maximum Contaminant Levels (MCLs), PCE and TCE ranked high in terms of the frequencies of concentrations greater than or near MCLs. The probability of occurrence of solvents in groundwater was associated with dissolved oxygen content of groundwater, sources such as urban land use and population density, and hydraulic properties of the aquifer. The results reinforce the importance of understanding the redox conditions of aquifers and the hydraulic properties of the saturated and vadose zones in determining the intrinsic susceptibility of groundwater to contamination by solvents. The results also reinforce the importance of controlling sources of solvents to groundwater. ?? 2007 American Chemical Society.

Environmental Science & Technology↗
USGS2007

Role of sediment resuspension in the remobilization of particulate-phase metals from coastal sediments

The release of particulate-phase trace metals due to sediment resuspension has been investigated by combining erosion chamber experiments that apply a range of shear stresses typically encountered in coastal environments with a shear stress record simulated by a hydrodynamic model. Two sites with contrasting sediment chemistry were investigated. Sediment particles enriched in silver, copper, and lead, 4−50 times greater than the bulk surface-sediment content, were the first particles to be eroded. As the shear-stress level was increased in the chamber, the total mass eroded increased, but the enrichment of these trace metals fell, approaching the bulk-sediment content. From the temporal distribution of shear stress generated by the hydrodynamic model for a site in Boston Harbor, resuspension fluxes were estimated. The erosion threshold of this site is exceeded during spring tides, releasing the particles enriched in trace metals into the water column. Due to the higher trace metal content and the regularity of resuspension, low-energy resuspension events (up to a shear stress of 0.2 N/m 2 ) contribute up to 60% of the resuspension metal flux in an average year. The estimated annual quantity of copper and lead resuspended into the water column is higher than estimates of the total riverine flux for these metals. These results indicate that sediment resuspension is a very important mechanism for releasing metals into the water column and provide new insight into the chemical and physical processes controlling the long-term fate of trace metals in contaminated sediments.

Massachusetts↗
USGS2007

Slightly weathered Exxon Valdez oil persists in Gulf of Alaska beach sediments after 16 years

Oil stranded by the 1989 Exxon Valdez spill has persisted in subsurface sediments of exposed shores for 16 years. With annualized loss rates declining from &sim;68% yr -1 prior to 1992 to &sim;4% yr -1 after 2001, weathering processes are retarded in both sediments and residual emulsified oil (&ldquo;oil mousse&rdquo;), and retention of toxic polycyclic aromatic hydrocarbons is prolonged. The n -alkanes, typically very readily oxidized by microbes, instead remain abundant in many stranded emulsified oil samples from the Gulf of Alaska. They are less abundant in Prince William Sound samples, where stranded oil was less viscous. Our results indicate that, at some locations, remaining subsurface oil may persist for decades with little change.

Environmental Science & Technology↗
USGS2007

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↗
USGS2007

Revisiting the cape cod bacteria injection experiment using a stochastic modeling approach

Bromide and resting-cell bacteria tracer tests conducted in a sandy aquifer at the U.S. Geological Survey Cape Cod site in 1987 were reinterpreted using a three-dimensional stochastic approach. Bacteria transport was coupled to colloid filtration theory through functional dependence of local-scale colloid transport parameters upon hydraulic conductivity and seepage velocity in a stochastic advection - dispersion/attachment - detachment model. Geostatistical information on the hydraulic conductivity (K) field that was unavailable at the time of the original test was utilized as input. Using geostatistical parameters, a groundwater flow and particle-tracking model of conservative solute transport was calibrated to the bromide-tracer breakthrough data. An optimization routine was employed over 100 realizations to adjust the mean and variance ofthe natural-logarithm of hydraulic conductivity (InK) field to achieve best fit of a simulated, average bromide breakthrough curve. A stochastic particle-tracking model for the bacteria was run without adjustments to the local-scale colloid transport parameters. Good predictions of mean bacteria breakthrough were achieved using several approaches for modeling components of the system. Simulations incorporating the recent Tufenkji and Elimelech (Environ. Sci. Technol. 2004, 38, 529-536) correlation equation for estimating single collector efficiency were compared to those using the older Rajagopalan and Tien (AIChE J. 1976, 22, 523-533) model. Both appeared to work equally well at predicting mean bacteria breakthrough using a constant mean bacteria diameter for this set of field conditions. Simulations using a distribution of bacterial cell diameters available from original field notes yielded a slight improvement in the model and data agreement compared to simulations using an average bacterial diameter. The stochastic approach based on estimates of local-scale parameters for the bacteria-transport process reasonably captured the mean bacteria transport behavior and calculated an envelope of uncertainty that bracketed the observations in most simulation cases.

Massachusetts↗
USGS2007

Widespread natural perchlorate in unsaturated zones of the southwest United States

A substantial reservoir (up to 1 kg ha -1 ) of natural perchlorate is present in diverse unsaturated zones of the arid and semi-arid southwestern United States. The perchlorate co-occurs with meteoric chloride that has accumulated in these soils throughout the Holocene [0 to 10−15 ka (thousand years ago)] and possibly longer periods. Previously, natural perchlorate widely believed to be limited to the Atacama Desert, now appears widespread in steppe-to-desert ecoregions. The perchlorate reservoir becomes sufficiently large to affect groundwater when recharge from irrigation or climate change flushes accumulated salts from the unsaturated zone. This new source may help explain increasing reports of perchlorate in dry region agricultural products and should be considered when evaluating overall source contributions.

Environmental Science & Technology↗
USGS2007

Mercury speciation in piscivorous fish from mining-impacted reservoirs

Guadalupe Reservoir (GUA), California, and Lahontan Reservoir (LAH), Nevada, U.S. are both affected either directly or indirectly by the legacy of gold and silver mining in the Sierra Nevada during the nineteenth century. Analysis of total mercury in fish from these lentic systems consistently indicate elevated concentrations (>1 μg·g-1 wet weight; hereinafter, all concentrations are reported as wet weight unless indicated otherwise) well above the U.S. Environmenal Protection Agency's human consumption advisory level for fish (<0.3 μg·g-1). Replicate X-ray absorption near edge structure (XANES) analyses on largemouth bass and hybrid striped bass from GUA and LAH were performed to determine predominant chemical species of mercury accumulated by these high-trophic-level piscivores that are exposed to elevated mercury through trophic transfer in mining-impacted lentic systems. Despite distinct differences in mercury source, the proximity of the source, and concentrations of complexing ligands, results of XANES analysis clearly indicated that mercury accumulated in these individual fish from the two reservoirs were dominated by methylmercury cysteine complexes. These findings are consistent with results from commercial fish species inhabiting marine environments which are presumed to include differing mercury sources (e.g., atmospheric, hydrothermal, or benthic). The dominance of methylmercury cysteine complexes in muscle tissues of fish obtained from such contrasting environments and exposure conditions suggests that a generic toxicological model for the consumption of fish could be applicable over a wide range of ecologic settings.

Environmental Science & Technology↗