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At least 721 records · Page 40Linked to original sources
USGS2009

Isotopic variability of mercury in ore, mine-waste calcine, and leachates of mine-waste calcine from areas mined for mercury

The isotopic composition of mercury (Hg) was determined in cinnabar ore, mine-waste calcine (retorted ore), and leachates obtained from water leaching experiments of calcine from two large Hg mining districts in the U.S. This study is the first to report significant mass-dependent Hg isotopic fractionation between cinnabar ore and resultant calcine. Data indicate that ?? 202 Hg values relative to NIST 3133 of calcine (up to 1.52???) in the Terlingua district, Texas, are as much as 3.24??? heavier than cinnabar (-1.72???) prior to retorting. In addition, ?? 202 Hg values obtained from leachates of Terlingua district calcines are isotopically similar to, or as much as 1.17??? heavier than associated calcines, most likely due to leaching of soluble, byproduct Hg compounds formed during ore retorting that are a minor component in the calcines. As a result of the large fractionation found between cinnabar and calcine, and because calcine is the dominant source of Hg contamination from the mines studied, ?? 202 Hg values of calcine may be more environmentally important in these mined areas than the primary cinnabar ore. Measurement of the Hg isotopic composition of calcine is necessary when using Hg isotopes for tracing Hg sources from areas mined for Hg, especially mine water runoff. ?? 2009 American Chemical Society.

Environmental Science & Technology↗
USGS2009

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↗
USGS2009

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↗
USGS2010

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↗
USGS2009

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↗
USGS2009

Chlorine-36 as a tracer of perchlorate origin

Perchlorate (ClO 4 − ) is ubiquitous in the environment. It is produced naturally by atmospheric photochemical reactions, and also is synthesized in large quantities for military, aerospace, and industrial applications. Nitrate-enriched salt deposits of the Atacama Desert (Chile) contain high concentrations of natural ClO 4 − , and have been exported worldwide since the mid-1800s for use in agriculture. The widespread introduction of synthetic and agricultural ClO 4 − into the environment has contaminated numerous municipal water supplies. Stable isotope ratio measurements of Cl and O have been applied for discrimination of different ClO 4 − sources in the environment. This study explores the potential of 36 Cl measurements for further improving the discrimination of ClO 4 − sources. Groundwater and desert soil samples from the southwestern United States (U.S.) contain ClO 4 − having high 36 Cl abundances ( 36 Cl/Cl = 3100 × 10 −15 to 28,800 × 10 −15 ), compared with those from the Atacama Desert ( 36 Cl/Cl = 0.9 × 10 −15 to 590 × 10 −15 ) and synthetic ClO 4 − reagents and products ( 36 Cl/Cl = 0.0 × 10 −15 to 40 × 10 −15 ). In conjunction with stable Cl and O isotope ratios, 36 Cl data provide a clear distinction among three principal ClO 4 − source types in the environment of the southwestern U.S.

Environmental Science & Technology↗
USGS2009

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↗
USGS2009

Surface complexation of carboxylate adheres Cryptosporidium parvum öocysts to the hematite-water interface

The interaction of viable Cryptosporidium parvum öocysts at the hematite (α-Fe 2 O 3 )−water interface was examined over a wide range in solution chemistry using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Spectra for hematite-sorbed öocysts showed distinct changes in carboxylate group vibrations relative to spectra obtained in the absence of hematite, indicative of direct chemical bonding between carboxylate groups and Fe metal centers of the hematite surface. The data also indicate that complexation modes vary with solution chemistry. In NaCl solution, öocysts are bound to hematite via monodentate and binuclear bidentate complexes. The former predominates at low pH, whereas the latter becomes increasingly prevalent with increasing pH. In a CaCl 2 solution, only binuclear bidentate complexes are observed. When solution pH is above the point of zero net proton charge (PZNPC) of hematite, öocyst surface carboxylate groups are bound to the mineral surface via outer-sphere complexes in both electrolyte solutions.

Environmental Science & Technology↗
USGS2009

Rapid changes in small fish mercury concentrations in estuarine wetlands: Implications for wildlife risk and monitoring programs

Small fish are commonly used to assess mercury (Hg) risk to wildlife and monitor Hg in wetlands. However, limited research has evaluated short-term Hg variability in small fish, which can have important implications for monitoring programs and risk assessment. We conducted a time-series study of Hg concentrations in two small fish species representing benthic (longjaw mudsuckers [Gillichthys mirabilis]) and pelagic (threespine sticklebacks [Gasterosteus aculeatus]) food-webs within three wetland habitats in San Francisco Bay Estuary. We simultaneously monitored prey deliveries, nest initiation, and chick hatching dates of breeding Forster's terns (Sterna forsteri), the most abundant nesting piscivore in the region. Mudsuckers and sticklebacks were the predominant prey fish, comprising 36% and 25% of tern diet, and Hg concentrations averaged (geometric mean ?? SE, ??g/g dw) 0.44 ?? 0.01 and 0.68 ?? 0.03, respectively. Fish Hg concentrations varied substantially over time following a quadratic form in both species, increasing 40% between March and May then decreasing 40% between May and July. Importantly, Forster's terns initiated 68% of nests and 31% of chicks hatched during the period of peak Hg concentrations in prey fish. These results illustrate the importance of short-term temporal variation in small fish Hg concentrations for both Hg monitoring programs and assessing wildlife risk.

Environmental Science & Technology↗
USGS2009

Measurement and modeling of polychlorinated biphenyl bioaccumulation from sediment for the marine polychaete neanthes arenaceodentata and response to sorbent amendment

Bioaccumulation rates of polychlorinated biphenyls (PCBs) for the marine polychaete Neanthes arenaceodentata were characterized, including PCB uptake rates from water and sediment, and the effect of sorbent amendment to the sediment on PCB bioavailability, organism growth, and lipid content. Physiological parameters were incorporated into a biodynamic model to predict contaminant uptake. The results indicate rapid PCB uptake from contaminated sediment and significant organism growth dilution during time-series exposure studies. PCB uptake from the aqueous phase accounted for less than 3% of the total uptake for this deposit-feeder. Proportional increase of gut residence time and assimilation efficiency as a consequence of the organism's growth was assessed by PCB uptake and a reactor theory model of gut architecture. Pulse-chase feeding and multilabeled stable isotope tracing techniques proved high sediment ingestion rates (i.e., 6?10 times of dry body weight per day) indicating that such deposit-feeders are promising biological indicators for sediment risk assessment. Activated carbon amendment reduced PCB uptake by 95% in laboratory experiments with no observed adverse growth effects on the marine polychaete. Biodynamic modeling explained the observed PCB body burdens for N. arenaceodentata, with and without sorbent amendment.

Environmental Science & Technology↗
USGS2009

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↗
USGS2009

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↗
USGS2010

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↗
USGS2009

Budget analysis of Escherichia coli at a southern Lake Michigan Beach

Escherichia coli (EC) concentrations at two beaches impacted by river plume dynamics in southern Lake Michigan were analyzed using three-dimensional hydrodynamic and transport models. The relative importance of various physical and biological processes influencing the fate and transport of EC were examined via budget analysis and a first-order sensitivity analysis of model parameters. The along-shore advective fluxofEC(CFU/m 2 ·s)was found to be higher compared to its crossshore counterpart; however, the sum of diffusive and advective components was of a comparable magnitude in both directions showing the importance of cross-shore exchange in EC transport. Examination of individual terms in the EC mass balance equation showed that vertical turbulent mixing in the water column dominated the overall EC transport for the summer conditions simulated. Dilution due to advection and diffusion accounted for a large portion of the total EC budget in the nearshore, and the net EC loss rate within the water column (CFU/m 3 ·s) was an order of magnitude smaller compared to the horizontal and vertical transport rates. This result has important implications for modeling EC at recreational beaches; however, the assessment of the magnitude of EC loss rate is complicated due to the strong coupling between vertical exchange and depth-dependent EC loss processes such as sunlight inactivation and settling. Sensitivity analysis indicated that solar inactivation has the greatest impact on EC loss rates. Although these results are site-specific, they clearly bring out the relative importance of various processes involved.

Environmental Science & Technology↗
USGS2010

Evaluation of the use of performance reference compounds in an oasis-HLB adsorbent based passive sampler for improving water concentration estimates of polar herbicides in freshwater

Passive samplers such as the Polar Organic Chemical Integrative Sampler (POCIS) are useful tools for monitoring trace levels of polar organic chemicals in aquatic environments. The use of performance reference compounds (PRC) spiked into the POCIS adsorbent for in situ calibration may improve the semiquantitative nature of water concentration estimates based on this type of sampler. In this work, deuterium labeled atrazine-desisopropyl (DIA-d5) was chosen as PRC because of its relatively high fugacity from Oasis HLB (the POCIS adsorbent used) and our earlier evidence of its isotropic exchange. In situ calibration of POCIS spiked with DIA-d5was performed, and the resulting time-weighted average concentration estimates were compared with similar values from an automatic sampler equipped with Oasis HLB cartridges. Before PRC correction, water concentration estimates based on POCIS data sampling ratesfrom a laboratory calibration exposure were systematically lower than the reference concentrations obtained with the automatic sampler. Use of the DIA-d5 PRC data to correct POCIS sampling rates narrowed differences between corresponding values derived from the two methods. Application of PRCs for in situ calibration seems promising for improving POCIS-derived concentration estimates of polar pesticides. However, careful attention must be paid to the minimization of matrix effects when the quantification is performed by HPLC-ESI-MS/MS. ?? 2010 American Chemical Society.

Environmental Science & Technology↗
USGS2010

Antidepressant pharmaceuticals in two U.S. effluent-impacted streams: Occurrence and fate in water and sediment and selective uptake in fish neural tissue

Antidepressant pharmaceuticals are widely prescribed in the United States; release of municipal wastewater effluent is a primary route introducing them to aquatic environments, where little is known about their distribution and fate. Water, bed sediment, and brain tissue from native white suckers (Catostomus commersoni)were collected upstream and atpoints progressively downstream from outfalls discharging to two effluentimpacted streams, Boulder Creek (Colorado) and Fourmile Creek (Iowa). A liquid chromatography/tandem mass spectrometry method was used to quantify antidepressants, including fluoxetine, norfluoxetine (degradate), sertraline, norsertraline (degradate), paroxetine, Citalopram, fluvoxamine, duloxetine, venlafaxine, and bupropion in all three sample matrices. Antidepressants were not present above the limit of quantitation in water samples upstream from the effluent outfalls but were present at points downstream at ng/L concentrations, even at the farthest downstream sampling site 8.4 km downstream from the outfall. The antidepressants with the highest measured concentrations in both streams were venlafaxine, bupropion, and Citalopram and typically were observed at concentrations of at least an order of magnitude greater than the more commonly investigated antidepressants fluoxetine and sertraline. Concentrations of antidepressants in bed sediment were measured at ng/g levels; venlafaxine and fluoxetine were the predominant chemicals observed. Fluoxetine, sertraline, and their degradates were the principal antidepressants observed in fish brain tissue, typically at low ng/g concentrations. Aqualitatively different antidepressant profile was observed in brain tissue compared to streamwater samples. This study documents that wastewater effluent can be a point source of antidepressants to stream ecosystems and that the qualitative composition of antidepressants in brain tissue from exposed fish differs substantially from the compositions observed in streamwater and sediment, suggesting selective uptake.

Colorado, Iowa↗
USGS2009

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↗
USGS2010

Coal-tar-based parking lot sealcoat: An unrecognized source of PAH to settled house dust

Despite much speculation, the principal factors controlling concentrations of polycyclic aromatic hydrocarbons (PAH) in settled house dust (SHD) have not yet been identified. In response to recent reports that dust from pavement with coaltar-based sealcoat contains extremely high concentrations of PAH, we measured PAH in SHD from 23 apartments and in dust from their associated parking lots, one-half of which had coal-tar-based sealcoat (CT). The median concentration of total PAH (T-PAH) in dust from CT parking lots (4760 ??g/g, n = 11) was 530 times higher than that from parking lots with other pavement surface types (asphalt-based sealcoat, unsealed asphalt, concrete [median 9.0 ??g/g, n = 12]). T-PAH in SHD from apartments with CT parking lots (median 129 ??g/g) was 25 times higher than that in SHD from apartments with parking lots with other pavement surface types (median 5.1 ??g/g). Presence or absence of CT on a parking lot explained 48% of the variance in log-transformed T-PAH in SHD. Urban land-use intensity near the residence also had a significant but weaker relation to T-PAH. No other variables tested, including carpeting, frequency of vacuuming, and indoor burning, were significant. ?? 2010 American Chemical Society.

Environmental Science & Technology↗