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Widespread potential for microbial MTBE degradation in surface-water sediments

Microorganisms indigenous to stream and lake bed sediments, collected from 11 sites throughout the United States, demonstrated significant mineralization of the fuel oxygenate, methyl-tert-butyl ether (MTBE). Mineralization of [U-14C]MTBE to 14CO2 ranged from 15 to 66% over 50 days and did not differ significantly between sediments collected from MTBE contaminated sites and from sites with no history of MTBE exposure. This result suggests that even the microbial communities indigenous to newly contaminated surface water systems will exhibit some innate ability to attenuate MTBE under aerobic conditions. The magnitude of MTBE mineralization was related to the sediment grain size distribution. A pronounced, inverse correlation (p < 0.001; r2 = 0.73) was observed between the final recovery of 14CO2 and the percentage content of silt and clay sized grains (grain diameter < 0.125 mm). The results of this study indicate that the microorganisms that inhabit the bed sediments of streams and lakes can degrade MTBE efficiently and that this capability is widespread in the environment. Thus aerobic bed sediment microbial processes may provide a significant environmental sink for MTBE in surface water systems throughout the United States and may contribute to the reported transience of MTBE in some surface waters.

Environmental Science & Technology

Volatilization of ethylene dibromide from water

Overall mass-transfer coefficients for the volatilization of ethylene dibromide from water were measured simultaneously with the oxygen absorption coefficient in a laboratory stirred tank. Coefficients were measured as a function of mixing conditions in the water for two windspeeds. The ethylene dibromide mass-transfer coefficient depended on windspeed; the ethylene dibromide liquid-film coefficient did not, in agreement with theory. A constant relation existed between the liquid-film coefficients for ethylene dibromide and oxygen.

Environmental Science & Technology

Interaction of acid mine drainage with waters and sediments of West Squaw Creek in the West Shasta Mining District, California

Acid mine drainage has acidified large volumes of water and added high concentrations of dissolved heavy metals to West Squaw Creek, a California stream draining igneous rocks of low acid-neutralizing capacity. During mixing of the acid sulfate stream waters in the South Fork of West Squaw Creek with an almost equal volume of dilute uncontaminated water, Cu, Zn, Mn, and Al remained in solution rather than precipitating or adsorbing on solid phases. Changes in the concentration of these generally conservative metals could be used to determine relative flow volumes of acid tributaries and the main stream. An amorphous orange precipitate (probably ferric hydroxides or a mixture of ferric hydroxides and jarosite) was ubiquitous in the acid stream beds and was intimately associated with algae at the most acid sites. Relative sorption of cations decreased with decreasing water pH. However, arsenic was almost completely scavenged from solution within a short distance from the sulfide sources.

California

National-scale, field-based evaluation of the biota - Sediment accumulation factor model

The biota - sediment accumulation factor (BSAF) model has been suggested as a simple tool to predict bioaccumulation of hydrophobic organic compounds (HOCs)in fish and other aquatic biota from measured concentrations in sediment based on equilibrium partitioning between the sediment organic carbon and biotic lipid pools. Currently, evaluation of this model as a predictive tool has been limited to laboratory studies and small-scale field studies, using a limited number of biotic species. This study evaluates the model, from field data, for a suite of organochlorine HOCs from paired fluvial sediment and biota (fish and bivalves) samples throughout the United States and over a large range of biotic species. These data represent a real-world, worst-case scenario of the model because environmental variables are not controlled. Median BSAF values for fish (3.3) and bivalves (2.8) were not statistically different but are higher than theoretically predicted values (1-2). BSAF values varied significantly in a few species. Differences in chemical-specific BSAF values were not observed in bivalves but were statistically significant in fish. The HOCs with differing BSAF values were those known to be biotransformed. Sediment organic carbon content and biota lipid content had no effect on BSAF values in fish and only a weak effect in bivalves. This study suggests that the BSAF model could be useful under in situ riverine conditions as a first-level screening tool for predicting bioaccumulation; however, variability in BSAF values may impose limits on its utility.

Environmental Science & Technology

Hausmannite (Mn 3 O 4 ) conversion to manganite (γ-MnOOH) in dilute oxalate solution

Oxalic acid retards the alteration of Mn3O4 to &gamma;-MnOOH during aging at pH 7.4 ?? 0.2 in well-aerated, abiotic suspensions that contain 4.4 ?? 10-3 M total Mn. In solutions of 1.25 ?? 10-3 M oxalate and greater, about 15% of the initial Mn3O4 altered to ??-MnOOH by day 10, and in solutions of 6.7 ?? 10-4 M oxalate, about 45% altered to ??-MnOOH by day 67. Although precipitation continued through day 365, the degree of conversion remained the same as at day 10 and day 67, respectively. In oxalate-free suspensions, the conversion was about 80% complete by day 67 and 100% by day 109. Oxalate complexed most of the dissolved divalent Mn, lowered the free Mn(II) and MnSO40 concentrations, but increased the total dissolved Mn. Steric hindrance of surface reactions by a suggested manganese oxalate layer on the Mn3O4 surface may explain the blockage of the oxidation cycle.

Environmental Science & Technology

Sorption of vapors of some organic liquids on soil humic acid and its relation to partitioning of organic compounds in soil organic matter

Vapor sorption of water, ethanol, benzene, hexane, carbon tetrachloride, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethylene, and 1,2-dibromoethane on (Sanhedron) soil humic acid has been determined at room temperature. Isotherms for all organic liquids are highly linear over a wide range of relative pressure, characteristic of the partitioning (dissolution) of the organic compounds in soil humic acid. Polar liquids exhibit markedly greater sorption capacities on soil humic acid than relatively nonpolar liquids, in keeping with the polar nature of the soil humic acid as a partition medium. The limiting sorption (partition) capacities of relatively non-polar liquids are remarkably similar when expressed in terms of volumes per unit weight of soil humic acid. The soil humic acid is found to be about half as effective as soil organic matter in sorption of relatively nonpolar organic compounds. The nearly constant limiting sorption capacity for nonpolar organic liquids with soil humic acid on a volume-to-weight basis and its efficiency in sorption relative to soil organic matter provide a basis for predicting the approximate sorption (partition) coefficients of similar compounds in uptake by soil in aqueous systems.

Environmental Science & Technology

Contamination of estuarine water, biota, and sediment by halogenated organic compounds: A field study

Studies conducted in the vicinity of an industrial outfall in the Calcasieu River estuary, Louisiana, have shown that water, bottom and suspended sediment, and four different species of biota are contaminated with halogenated organic compounds (HOC) including haloarenes. A "salting-out" effect in the estuary moderately enhanced the partitioning tendency of the contaminants into biota and sediments. Contaminant concentrations in water, suspended sediments, and biota were found to be far below the values predicted on the basis of the assumption of phase equilibria with respect to concentrations in bottom sediment. Relative concentration factors of HOC between biota (catfish) and bottom sediment increased with increasing octanol/estuarine water partition coefficients (Kow*), maximizing at log Kow* of about 5, although these ratios were considerably less than equilibrium values. In contrast, contaminant concentrations in water, biota, and suspended sediments were much closer to equilibrium values. Bioconcentration factors of HOC determined on the basis of lipid content for four different biotic species correlated reasonably well with equilibrium triolein/water partition coefficients (Ktw).

Louisiana

Transport of microspheres and indigenous bacteria through a sandy aquifer: Results of natural- and forced-gradient tracer experiments

Transport of indigenous bacteria through sandy aquifer sediments was investigated in forced- and natural-gradient tracer teste. A diverse population of bacteria was collected and concentrated from groundwater at the site, stained with a DNA-specific fluorochrome, and injected back into the aquifer. Included with the injectate were a conservative tracer (Br- or Cl-) and bacteria-sized (0.2-1.3-??m) microspheres having carboxylated, carbonyl, or neutral surfaces. Transport of stained bacteria and all types and size classes of microspheres was evident. In the natural-gradient test, both surface characteristics and size of microspheres affected attenuation. Surface characteristics had the greatest effect upon retardation. Peak break-through of DAPI-stained bacteria (forced-gradient experiment) occurred well in advance of bromide at the more distal sampler. Transport behavior of bacteria was substantially different from that of carboxylated microspheres of comparable size.

Environmental Science & Technology

Effects of sulfur impregnation temperature on the properties and mercury adsorption capacities of activated carbon fibers (ACFs)

Laboratory studies were conducted to determine the role of sulfur functional groups and micropore surface area of carbon-based adsorbents on the adsorption of Hg0 from simulated coal combustion flue gases. In this study, raw activated carbon fibers that are microporous (ACF-20) were impregnated with elemental sulfur between 250 and 650 ??C. The resulting samples were saturated with respect to sulfur content. Total sulfur content of the sulfur impregnated ACF samples decreased with increasing impregnation temperatures from 250 and 500 ??C and then remained constant to 650 ??C. Results from sulfur K-edge X-ray absorption near-edge structure (S-XANES) spectroscopy showed that sulfur impregnated on the ACF samples was in both elemental and organic forms. As sulfur impregnation temperature increased, however, the relative amounts of elemental sulfur decreased with a concomitant increase in the amount of organic sulfur. Thermal analyses and mass spectrometry revealed that sulfur functional groups formed at higher impregnation temperatures were more thermally stable. In general, sulfur impregnation decreased surface area and increased equilibrium Hg0 adsorption capacity when compared to the raw ACF sample. The ACF sample treated with sulfur at 400 ??C had a surface area of only 94 m2/g compared to the raw ACF sample's surface area of 1971 m2/g, but at least 86% of this sample's surface area existed as micropores and it had the largest equilibrium Hg0adsorption capacities (2211-11343 ??g/g). Such a result indicates that 400 ??C is potentially an optimal sulfur impregnation temperature for this ACF. Sulfur impregnated on the ACF that was treated at 400 ??C was in both elemental and organic forms. Thermal analyses and CS2extraction tests suggested that elemental sulfur was the main form of sulfur affecting the Hg0 adsorption capacity. These findings indicate that both the presence of elemental sulfur on the adsorbent and a microporous structure are important properties for improving the performance of carbon-based adsorbents for the removal of Hg0 from coal combustion flue gases.

Environmental Science & Technology

Acidic deposition to streams: A geology-based method predicts their sensitivity

All water that reaches watershed systems comes directly or indirectly from precipitation. Normally, this water contains very small amounts of dissolved solids and is only slightly acidic. As a result of chemical reactions in watersheds, however, stream water generated from precipitation normally is less acidic and contains larger concentrations of dissolved solids than does the precipitation falling onto the watershed.

Environmental Science & Technology

Enantiomeric composition of chiral polychlorinated biphenyl atropisomers in aquatic and riparian biota

The enantiomeric composition of polychlorinated biphenyl (PCB) atropisomers was measured in river and riparian biota (fish, bivalves, crayfish, water snakes, barn swallows) from selected sites throughout the United States by using chiral gas chromatography/mass spectrometry. Nonracemic enantiomeric fractions (EFs) were observed for PCBs 91, 95, 136, and 149 for aquatic and riparian biota from Lake Hartwell, SC, a reservoir heavily contaminated with PCBs, and for these congeners and PCBs 132, 174, 176, and 183 in river fish and bivalves nationwide. Fish and bivalves showed marked differences in EFs as compared to sediment found at the same sampling sites, thus suggesting that PCBs are bioprocessed in biota in a different manner from those found in sediment (e.g., reductive dechlorination). Species-dependent patterns in PCB EFs were observed, which suggest differences in the ability of different species to bioprocess PCBs enantioselectively, most likely by metabolism. The presence of nonracemic PCBs in fish and bivalves suggests greater metabolic degradation of PCBs in these organisms than indicated from previous achiral studies and underscores the powerful potential of chiral analysis as a tracer of environmental bioprocesses.

Environmental Science & Technology

Nature and chlorine reactivity of organic constituents from reclaimed water in groundwater, Los Angeles County, California

The nature and chlorine reactivity of organic constituents in reclaimed water (tertiary-treated municipal wastewater) before, during, and after recharge into groundwater at the Montebello Forebay in Los Angeles County, CA, was the focus of this study. Dissolved organic matter (DOM) in reclaimed water from this site is primarily a mixture of aromatic sulfonates from anionic surfactant degradation, N-acetyl amino sugars and proteins from bacterial activity, and natural fulvic acid, whereas DOM from native groundwaters in the aquifer to which reclaimed water was recharged consists of natural fulvic acids. The hydrophilic neutral N-acetyl amino sugars that constitute 40% of the DOM in reclaimed water are removed during the first 3 m of vertical infiltration in the recharge basin. Groundwater age dating with 3H and 3He isotopes, and determinations of organic and inorganic C isotopes, enabled clear differentiation of recent recharged water from older native groundwater. Phenol structures in natural fulvic acids in DOM isolated from groundwater produced significant trihalomethanes (THM) and total organic halogen (TOX) yields upon chlorination, and these structures also were responsible for the enhanced SUVA and specific fluorescence characteristics relative to DOM in reclaimed water. Aromatic sulfonates and fulvic acids in reclaimed water DOM produced minimal THM and TOX yields.

California

Perfluorooctane sulfonate in fish-eating water birds including bald eagles and albatrosses

Perfluorooctane sulfonate (PFOS) was measured in 161 samples of liver, kidney, blood, or egg yolk from 21 species of fish-eating water birds collected in the United States including albatrosses from Sand Island, Midway Atoll, in the central North Pacific Ocean. Concentrations of PFOS in the blood plasma of bald eagles collected from the midwestern United States ranged from 13 to 2220 ng/mL (mean: 330 ng/mL), except one sample that did not contain quantifiable concentrations of PFOS. Concentrations of PFOS were greater in blood plasma than in whole blood. Among 82 livers from various species of birds from inland or coastal U.S. locations, Brandt's cormorant from San Diego, CA, contained the greatest concentration of PFOS (1780 ng/g, wet wt). PFOS was also found in the sera of albatrosses from the central North Pacific Ocean at concentrations ranging from 3 to 34 ng/mL. Occurrence of PFOS in birds from remote marine locations suggests widespread distribution of PFOS and related fluorochemicals in the environment.

Environmental Science & Technology

MTBE; to what extent will past releases contaminate community water supply wells?(Brief Article)

The increasing frequency of detection of the widely used gasoline additive methyl tertbutyl ether (MTBE) in both ground- and surface waters is receiving much attention from the media, environmental scientists, state environmental agencies, and federal agencies. At the national level, the September 15,1999, Report of the Blue Ribbon Panel on Oxygenates in Gasoline (i) )tates that between 5 and 10% of community drinking water supplies in high MTBE use areas show at least detectable concentrations of MTBE, and about 1% of those systems are characterized by levels of this compound that are above 20 pg/L. In Maine, a desire to determine the extent of MTBE contamination led to a 1998 study (2) that revealed that this compound is found at levels above 0.1 pg/L in 16% of 951 randomly selected household wells and in 16% of the 793 community water systems tested in that state (37 wells were not tested). The study also suggested that between 1400 and 5200 household wells may have levels above 35 pg/L, although no community water supplies were found to be above that concentration. For comparison, Maryland, New Hampshire, New York, and California have set MTBE remediation "action levels" at or below 20 pg/L, and EPA has set its advisory level for taste and odor at 20-40 pg/L (3).

Environmental Science & Technology