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At least 325 records · Page 18Linked to original sources

Method development for analysis of urban dust using scanning electron microscopy with energy dispersive x-ray spectrometry to detect the possible presence of world trade center dust constituents

The collapse of the World Trade Center Towers on September 11, 2001, sent dust and debris across much of Manhattan and in the surrounding areas. Indoor and outdoor dust samples were collected and characterized by U.S. Geological Survey (USGS) scientists using scanning electron microscopy with energy-dispersive spectrometry (SEM/EDS). From this characterization, the U.S. Environmental Protection Agency and USGS developed a particulate screening method to determine the presence of residual World Trade Center dust in the indoor environment using slag wool as a primary "signature". The method describes a procedure that includes splitting, ashing, and sieving of collected dust. From one split, a 10 mg/mL dust/ isopropanol suspension was prepared and 10-30 ??L aliquots of the suspension placed on an SEM substrate. Analyses were performed using SEM/EDS manual point counting for slag wool fibers. Poisson regression was used to identify some of the sources of uncertainty, which are directly related to the small number of fibers present on each sample stub. Preliminary results indicate that the procedure is promising for screening urban background dust for the presence of WTC dust. Consistent sample preparation of reference materials and samples must be performed by each laboratory wishing to use this method to obtain meaningful and accurate results. ?? 2009 American Chemical Society.

Environmental Science & Technology↗

Susceptibility of synthetic long-chain alkylbenzenes to degradation in reducing marine sediments

Long-chain alkylbenzenes (LCABs) synthesized for production of alkylbenzene sulfonate surfactants have been used as molecular markers of anthropogenic waste for 25 years. Synthetic LCABs comprise two classes, the tetrapropylene-based alkylbenzenes (TABs) and the linear alkylbenzenes (LABs). LABs supplanted TABs in the mid-1960s because of improved biodegradability of their sulfonated analogs. Use of LCABs for molecular stratigraphy depends on their preservation in sediments over decadal time scales. Most laboratory and field studies suggest that LABs degrade rapidly under aerobic conditions but are resistant to degradation when oxygen is absent. However, recent work indicates that LABs may not be as persistent under reducing conditions as previously thought. To assess the potential for degradation of LCABs in reducing sediments, box cores collected in 1992 and 2003 near a submarine wastewater outfall system were analyzed using gas chromatography/mass spectrometry. The TABs were effectively preserved; differences between whole-core inventories were within analytical error. By contrast, whole-core inventories of the LABs decreased by about 50−60% during the same time interval. Based on direct comparison of chemical inventories in coeval core sections, LAB transformation rates are estimated at 0.07 ± 0.01 yr −1 . These results indicate that caution should be exercised when using synthetic LCABs for reconstruction of depositional records.

Environmental Science & Technology↗

Model predictions of realgar precipitation by reaction of As(III) with synthetic mackinawite under anoxic conditions

This study investigates the removal of As(III) from solution using mackinawite, a nanoparticulate reduced iron sulfide. Mackinawite suspensions (0.1−40 g/L) effectively lower initial concentrations of 1.3×10 −5 M As(III) from pH 5−10, with maximum removal occurring under acidic conditions. Based on E h measurements, it was found that the redox state of the system depended on the mackinawite solids concentration and pH. Higher initial mackinawite concentrations and alkaline pH resulted in a more reducing redox condition. Given this, the pH edge data were modeled thermodynamically using pe (−log[e − ]) as a fitting parameter and linear pe−pH relationships within the range of measured E h values as a function of pH and mackinawite concentration. The model predicts removal of As(III) from solution by precipitation of realgar with the formation of secondary oxidation products, greigite or a mixed-valence iron oxide phase, depending on pH. This study demonstrates that mackinawite is an effective sequestration agent for As(III) and highlights the importance of incorporating redox into models describing the As−Fe−S−H 2 O system.

Environmental Science & Technology↗

Mercury cycling in stream ecosystems. 3. Trophic dynamics and methylmercury bioaccumulation

Trophic dynamics (community composition and feeding relationships) have been identified as important drivers of methylmercury (MeHg) bioaccumulation in lakes, reservoirs, and marine ecosystems. The relative importance of trophic dynamics and geochemical controls on MeHg bioaccumulation in streams, however, remains poorly characterized. MeHg bioaccumulation was evaluated in eight stream ecosystems across the United States (Oregon, Wisconsin, and Florida) spanning large ranges in climate, landscape characteristics, atmospheric Hg deposition, and stream chemistry. Across all geographic regions and all streams, concentrations of total Hg (THg) in top predator fish and forage fish, and MeHg in invertebrates, were strongly positively correlated to concentrations of filtered THg (FTHg), filtered MeHg (FMeHg), and dissolved organic carbon (DOC); to DOC complexity (as measured by specific ultraviolet absorbance); and to percent wetland in the stream basins. Correlations were strongest for nonurban streams. Although regressions of log[Hg] versus δ 15 N indicate that Hg in biota increased significantly with increasing trophic position within seven of eight individual streams, Hg concentrations in top predator fish (including cutthroat, rainbow, and brown trout; green sunfish; and largemouth bass) were not strongly influenced by differences in relative trophic position. Slopes of log[Hg] versus δ 15 N, an indicator of the efficiency of trophic enrichment, ranged from 0.14 to 0.27 for all streams. These data suggest that, across the large ranges in FTHg (0.14−14.2 ng L −1 ), FMeHg (0.023−1.03 ng L −1 ), and DOC (0.50−61.0 mg L −1 ) found in this study, Hg contamination in top predator fish in streams likely is dominated by the amount of MeHg available for uptake at the base of the food web rather than by differences in the trophic position of top predator fish.

Environmental Science & Technology↗

Fate of sulfamethoxazole, 4-nonylphenol, and 17β-estradiol in groundwater contaminated by wastewater treatment plant effluent

Organic wastewater contaminants (OWCs) were measured in samples collected from monitoring wells located along a 4.5-km transect of a plume of groundwater contaminated by 60 years of continuous rapid infiltration disposal of wastewater treatment plant effluent. Fifteen percent of the 212 OWCs analyzed were detected, including the antibiotic sulfamethoxazole (SX), the nonionic surfactant degradation product 4-nonylphenol (NP), the solvent tetrachloroethene (PCE), and the disinfectant 1,4-dichlorobenzene (DCB). Comparison of the 2005 sampling results to data collected from the same wells in 1985 indicates that PCE and DCB are transported more rapidly in the aquifer than NP, consistent with predictions based on compound hydrophobicity. Natural gradient in situ tracer experiments were conducted to evaluate the subsurface behavior of SX, NP, and the female sex hormone 17β-estradiol (E2) in two oxic zones in the aquifer: (1) a downgradient transition zone at the interface between the contamination plume and the overlying uncontaminated groundwater and (2) a contaminated zone located beneath the infiltration beds, which have not been loaded for 10 years. In both zones, breakthrough curves for the conservative tracer bromide (Br − ) and SX were nearly coincident, whereas NP and E2 were retarded relative to Br − and showed mass loss. Retardation was greater in the contaminated zone than in the transition zone. Attenuation of NP and E2 in the aquifer was attributed to biotransformation, and oxic laboratory microcosm experiments using sediments from the transition and contaminated zones show that uniform-ring-labeled 14 C 4-normal-NP was biodegraded more rapidly (30−60% recovered as 14 CO 2 in 13 days) than 4- 14 C E2 (20−90% recovered as 14 CO 2 in 54 days). There was little difference in mineralization potential between sites.

Massachusetts↗

Semivolatile organic compounds in residential air along the Arizona - Mexico border

Concerns about indoor air quality and the potential effects on people living in these environments are increasing as more reports about the toxicities and the potential indoor air exposure levels of household-use chemicals and chemicals fromhousingandfurnishingmanufactureinairarebeingassessed. Gas chromatography/mass spectrometry was used to confirm numerous airborne contaminants obtained from the analysis of semipermeable membrane devices deployed inside of 52 homes situated along the border between Arizona and Mexico. We also describe nontarget analytes in the organochlorine pesticide fractions of 12 of these homes; this fraction is also the most likelytocontainthebroadestscopeofbioconcentratablechemicals accumulated from the indoor air. Approximately 400 individual components were identified, ranging from pesticides to a wide array of hydrocarbons, fragrances such as the musk xylenes, flavors relating to spices, aldehydes, alcohols, esters and phthalate esters, and other miscellaneous types of chemicals. The results presented in this study demonstrate unequivocally that the mixture of airborne chemicals present indoors is far more complex than previously demonstrated. ?? 2009 American Chemical Society.

Environmental Science & Technology↗

Application of a rule-based model to estimate mercury exchange for three background biomes in the continental United States

Ecosystems that have low mercury (Hg) concentrations (i.e., not enriched or impactedbygeologic or anthropogenic processes) cover most of the terrestrial surface area of the earth yet their role as a net source or sink for atmospheric Hg is uncertain. Here we use empirical data to develop a rule-based model implemented within a geographic information system framework to estimate the spatial and temporal patterns of Hg flux for semiarid deserts, grasslands, and deciduous forests representing 45% of the continental United States. This exercise provides an indication of whether these ecosystems are a net source or sink for atmospheric Hg as well as a basis for recommendation of data to collect in future field sampling campaigns. Results indicated that soil alone was a small net source of atmospheric Hg and that emitted Hg could be accounted for based on Hg input by wet deposition. When foliar assimilation and wet deposition are added to the area estimate of soil Hg flux these biomes are a sink for atmospheric Hg. ?? 2009 American Chemical Society.

Environmental Science & Technology↗

Predicting dietborne metal toxicity from metal influxes

Dietborne metal uptake prevails for many species in nature. However, the links between dietary metal exposure and toxicity are not well understood. Sources of uncertainty include the lack of suitable tracers to quantify exposure for metals such as copper, the difficulty to assess dietary processes such as food ingestion rate, and the complexity to link metal bioaccumulation and effects. We characterized dietborne copper, nickel, and cadmium influxes in a freshwater gastropod exposed to diatoms labeled with enriched stable metal isotopes. Metal influxes in Lymnaea stagnalis correlated linearly with dietborne metal concentrations over a range encompassing most environmental exposures. Dietary Cd and Ni uptake rate constants (k uf ) were, respectively, 3.3 and 2.3 times higher than that for Cu. Detoxification rate constants (k detox ) were similar among metals and appeared 100 times higher than efflux rate constants (k e ). Extremely high Cu concentrations reduced feeding rates, causing the relationship between exposure and influx to deviate from linearity; i.e., Cu uptake rates leveled off between 1500 and 1800 nmol g -1 day -1 . L. stagnalis rapidly takes up Cu, Cd, and Ni from food but detoxifies the accumulated metals, instead of reducing uptake or intensifying excretion. Above a threshold uptake rate, however, the detoxification capabilities of L. stagnalis are overwhelmed.

Environmental Science & Technology↗

Emerging opportunities in management of selenium contamination

The metalloid selenium (Se) has the diverse reactivity characteristic of the chalcogens in addition to organometallic behavior. Laboratory measurements indicate that Se is an acute reproductive toxicant, which makes it a concern for the environment. Yet to date, a lack of understanding on how Se species distribute through food webs—bioaccumulation not seeming to conform to dissolved concentrations—has made for very heterogeneous regulation across jurisdictions. In this Feature, Luoma and Presser review Se’s idiosyncrasies to provide an outlook for more realistic ecotoxicologically based regulation.

Environmental Science & Technology↗

Federal land management, carbon sequestration, and climate change in the Southeastern U.S.: a case study with fort benning

Land use activities can have a major impact on the temporal trendsandspatialpatternsofregionalland-atmosphereexchange of carbon. Federal lands generally have substantially different land management strategies from surrounding areas, and the carbon consequences have rarely been quantified and assessed. Using the Fort Benning Installation as a case study, we used the General Ensemble biogeochemical Modeling System (GEMS) to simulate and compare ecosystem carbon sequestration between the U.S. Army's Fort Benning and surrounding areas from 1992 to 2050. Our results indicate that the military installation sequestered more carbon than surrounding areas from 1992 to 2007 (76.7 vs 18.5 g C m -2 yr -1 ), and is projected to continue sequestering more carbon from 2008 to 2050 (75.7 vs 25.6 g C m -2 yr -1 ), mostly because of the proactive management approaches adopted on military training lands. Our results suggest that federal lands might play a positive and important role in sequestering and conserving atmospheric carbon because some anthropogenic disturbances (e.g., urbanization, forest harvesting, and agriculture) can be minimized or prevented on federal lands

Georgia↗

Arsenite and ferrous iron oxidation linked to chemolithotrophic denitrification for the immobilization of arsenic in anoxic environments

The objective of this study was to explore a bioremediation strategy based on injecting NO 3 − to support the anoxic oxidation of ferrous iron (Fe(II)) and arsenite (As(III)) in the subsurface as a means to immobilize As in the form of arsenate (As(V)) adsorbed onto biogenic ferric (Fe(III)) (hydr)oxides. Continuous flow sand filled columns were used to simulate a natural anaerobic groundwater and sediment system with co-occurring As(III) and Fe(II) in the presence (column SF1) or absence (column SF2) of nitrate, respectively. During operation for 250 days, the average influent arsenic concentration of 567 μg L −1 was reduced to 10.6 (±9.6) μg L −1 in the effluent of column SF1. The cumulative removal of Fe(II) and As(III) in SF1 was 6.5 to 10-fold higher than that in SF2. Extraction and measurement of the mass of iron and arsenic immobilized on the sand packing of the columns were close to the iron and arsenic removed from the aqueous phase during column operation. The dominant speciation of the immobilized iron and arsenic was Fe(III) and As(V) in SF1, compared with Fe(II) and As(III) in SF2. The speciation was confirmed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results indicate that microbial oxidation of As(III) and Fe(II) linked to denitrification resulted in the enhanced immobilization of aqueous arsenic in anaerobic environments by forming Fe(III) (hydr)oxide coated sands with adsorbed As(V).

Environmental Science & Technology↗

Fipronil and its degradates in indoor and outdoor dust

Fipronil is a potent insecticide used for control of termites, fleas, roaches, ants, and other pests. We measured fipronil, fipronil sulfide, and desulfinyl fipronil concentrations in indoor and outdoor dust from 24 residences in Austin, Texas. At least one of these three fipronil compounds was detected in every sample. Fipronil accounted for most of the total fipronil (T-fipronil; fipronil+desulfinyl fipronil+fipronil sulfide), followed by desulfinyl fipronil and fipronil sulfide. Nineteen of 24 samples of indoor dust had T-fipronil concentrations less than 270 ??g/kg; the remaining five had concentrations from 1320 to 14,200 ??g/kg. All three of the residences with a dog on which a flea-control product containing fipronil was used were among the five residences with elevated fipronil concentrations. In outdoor dust, all concentrations of T-fipronil were less than 70??g/kg with one exception (430??g/kg). For every residence, the concentration of T-fipronil in indoor dust exceeded that in outdoor dust, and the median concentration of T-fipronil was 15 times higher indoors than outdoors.

Environmental Science & Technology↗

Trends in concentrations and use of agricultural herbicides for Corn Belt rivers, 1996-2006

Trends in the concentrations and agricultural use of four herbicides (atrazine, acetochlor, metolachlor, and alachlor) were evaluated for major rivers of the Corn Belt for two partially overlapping time periods: 1996-2002 and 2000-2006. Trends were analyzed for 11 sites on the mainstems and selected tributaries in the Ohio, Upper Mississippi, and Missouri River Basins. Concentration trends were determined using a parametric regression model designed for analyzing seasonal variability, flow-related variability, and trends in pesticide concentrations(SEAWAVE-Q).TheSEAWAVE-Qmodel accounts for the effect of changing flow conditions in order to separate changes caused by hydrologic conditions from changes caused by other factors, such as pesticide use. Most of the trends in atrazine and acetochlor concentrations for both time periods were relatively small and nonsignificant, but metolachlor and alachlor were dominated by varying magnitudes of concentration downtrends. Overall, with trends expressed as a percent change per year, trends in herbicide concentrations were consistent with trends in agricultural use; 84 of 88 comparisons for different sites, herbicides, and time periods showed no significant difference between concentration trends and agricultural use trends. Results indicate that decreasing use appears to have been the primary cause for the concentration downtrends during 1996-2006 and that, while there is some evidence that nonuse management factors may have reduced concentrations in some rivers, reliably evaluating the influence of these factors on pesticides in large streams and rivers will require improved, basin-specific information on both management practices and use over time. ?? 2009 American Chemical Society.

Environmental Science & Technology↗

Surface complexation modeling of U(VI) adsorption by aquifer sediments from a former mill tailings site at Rifle, Colorado

A study of U(VI) adsorption by aquifer sediment samples from a former uranium mill tailings site at Rifle, Colorado, was conducted under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Batch adsorption experiments were performed using <2mm size sediment fractions, a sand-sized fraction, and artificial groundwater solutions prepared to simulate the field groundwater composition. To encompass the geochemical conditions of the alluvial aquifer at the site, the experimental conditions ranged from 6.8 ?? 10 -8 to 10 -5 M in [U(VI)]tot, 7.2 to 8.0 in pH, 3.0 ?? 10 -3 to 6.0 ?? 10 -3 M in [Ca 2+ ], and 0.05 to 2.6% in partial pressure of carbon dioxide. Surface area normalized U(VI) adsorption Kd values for the sand and <2 mm sediment fraction were similar, suggesting a similar reactive surface coating on both fractions. A two-site two-reaction, nonelectrostatic generalized composite surface complexation model was developed and successfully simulated the U(VI) adsorption data. The model successfully predicted U(VI) adsorption observed from a multilevel sampling well installed at the site. A comparison of the model with the one developed previously for a uranium mill tailings site at Naturita, Colorado, indicated that possible calcite nonequilibrium of dissolved calcium concentration should be evaluated. The modeling results also illustrate the importance of the range of data used in deriving the best fit model parameters. ?? 2009 American Chemical Society.

Environmental Science & Technology↗

Transformation of chiral polychlorinated biphenyls (PCBs) in a stream food web

The enantiomeric composition of chiral PCB congeners was determined in Twelvemile Creek (Clemson, SC) to examine potential mechanisms of biotransformation in a stream food web. We measured enantiomeric fractions (EFs) of six PCB atropisomers (PCBs 84, 91, 95, 136, 149, and 174) in surface sediment, fine benthic organic matter (FBOM), coarse particulate organic matter (CPOM), periphyton, Asian clam, mayflies, yellowfin shiner, and semipermeable membrane devices (SPMDs) using gas chromatography (GC-ECD). Nonracemic EFs of PCBs 91, 95, 136, and 149 were measured in almost all samples. Enantiomeric compositions of PCBs 84 and 174 were infrequently detected with racemic EFs measured in samples except for a nonracemic EF of PCB 84 in clams. Nonracemic EFs of PCBs 91, 136, and 149 in SPMDs may be due to desorption of nonracemic residues from FBOM. EFs for some atropisomers were significantly different among FBOM, CPOM, and periphyton, suggesting that their microbial communities have different biotransformation processes. Nonracemic EFs in clams and fish suggest both in vivo biotransformation and uptake of nonracemic residues from their food sources. Longitudinal variability in EFs was generally low among congeners observed in matrices. ?? 2010 American Chemical Society.

Environmental Science & Technology↗

Spider-mediated flux of PCBs from contaminated sediments to terrestrial ecosystems and potential risks to arachnivorous birds

We investigated aquatic insect utilization and PCB exposure in riparian spiders at the Lake Hartwell Superfund site (Clemson, SC). We sampled sediments, adult chironomids, terrestrial insects, riparian spiders (Tetragnathidae, Araneidae, and Mecynogea lemniscata), and upland spiders (Araneidae) along a sediment contamination gradient. Stable isotopes (? 13 C, ? 15 N) indicated that riparian spiders primarily consumed aquatic insects whereas upland spiders consumed terrestrial insects. PCBs in chironomids (mean 1240 ng/g among sites) were 2 orders of magnitude higher than terrestrial insects (15.2 ng/g), similar to differences between riparian (820?2012 ng/g) and upland spiders (30 ng/g). Riparian spider PCBs were positively correlated with sediment concentrations for all taxa (r 2 = 0.44?0.87). We calculated spider-based wildlife values (WVs, the minimum spider PCB concentrations causing physiologically significant doses in consumers) to assess exposure risks for arachnivorous birds. Spider concentrations exceeded WVs for most birds at heavily contaminated sites and were ?14-fold higher for the most sensitive species (chickadee nestlings, Poecile spp.). Spiders are abundant and ubiquitous in riparian habitats, where they depend on aquatic insect prey. These traits, along with the high degree of spatial correlation between spider and sediment concentrations we observed, suggest that they are model indicator species for monitoring contaminated sediment sites and assessing risks associated with contaminant flux into terrestrial ecosystems. ?? This article not subject to U.S. Copyright. Published 2009 by the American Chemical Society.

Environmental Science & Technology↗

Biogeochemical redox processes and their impact on contaminant dynamics

Life and element cycling on Earth is directly related to electron transfer (or redox) reactions. An understanding of biogeochemical redox processes is crucial for predicting and protecting environmental health and can provide new opportunities for engineered remediation strategies. Energy can be released and stored by means of redox reactions via the oxidation of labile organic carbon or inorganic compounds (electron donors) by microorganisms coupled to the reduction of electron acceptors including humic substances, iron-bearing minerals, transition metals, metalloids, and actinides. Environmental redox processes play key roles in the formation and dissolution of mineral phases. Redox cycling of naturally occurring trace elements and their host minerals often controls the release or sequestration of inorganic contaminants. Redox processes control the chemical speciation, bioavailability, toxicity, and mobility of many major and trace elements including Fe, Mn, C, P, N, S, Cr, Cu, Co, As, Sb, Se, Hg, Tc, and U. Redox-active humic substances and mineral surfaces can catalyze the redox transformation and degradation of organic contaminants. In this review article, we highlight recent advances in our understanding of biogeochemical redox processes and their impact on contaminant fate and transport, including future research needs.

Environmental Science & Technology↗