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Response to comment on "Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. streams, 1999-2000: A national reconnaissance"

We concur with the response of Eckel to our recent publication in this Journal (1). As the author notes, the topic of emerging contaminants is currently receiving extensive media coverage and scientific notice, but there are earlier reports that foreshadow this current interest. Eckel’s comment regarding the detection of pharmaceuticals and other organic wastewater contaminants (OWC) at a Superfund landfill site (2) is well taken, as other reports confirm the presence of such compounds at waste-disposal and landfill sites (3). In fact, literature from more than 20 years ago documented the occurrence of OWCs in the environment (4-7). A significant difference between these reports and our study is that we have systematically documented the frequent presence and low concentrations of a broad suite of OWCs in a wide variety of streams across the United States.

Environmental Science & Technology↗

Response to comment on "Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. streams, 1999-2000: A national reconnaissance"

We thank Ericson et al. (1) for their careful review and thoughtful comments on the synthetic hormone data presented in our recent publication summarizing the results from the USGS nationwide reconnaissance for pharmaceuticals and other organic wastewater contaminants (2). Their efforts have helped raise the awareness of the difficulties in accurately measuring these compounds at the low concentrations that occur in the environment and reinforce the need for continued research in the area of analytical methods development for synthetic hormones

Environmental Science & Technology↗

Response to comment on "Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. streams, 1999-2000: A national reconnaissance"

Till (1) raised concerns that several aspects of how we handled the data in our study (2) may have caused unintended bias. First, Till (1) considers the “median detectable concentrations” listed in Table 1 (2) to be misleading because “higher median concentrations than is actually the case” were suggested. We interpret this concern raised by Till (1) to be that some readers may misinterpret our median detectable concentration to be an overall median concentration. Our intention was to provide the reader with information that could not easily be determined independently. For example, by examining the frequency of detection (2), it could easily be determined that the overall median concentration was less than the reporting level for all but six compounds (those having a detection frequency of>50%). Our goal for providing a median detectable concentration was to give a better sense of the concentrations when a particular compound was detected. Thus, we felt the combination of frequency of detection (how often a compound was found), median detectable concentration (median concentration when a compound was detected), and maximum concentration (highest concentration measured) would provide the greatest benefit to the readers. In future reports, we will modify the table headings to ensure that overall median concentration and median detectable concentration are clearly differentiated.

Environmental Science & Technology↗

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

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

Environmental Science & Technology↗

Field evidence for a protistan role in an organically-contaminated aquifer

The association between protists, bacteria, and dissolved organic carbon (DOC) in an oxygen-depleted, 6 km-long wastewater contaminant plume within a sandy aquifer (Cape Cod, MA) was investigated by comparing abundance patterns along longitudinal and vertical transects and at a control site. Strong linear correlations were observed between unattached bacterial abundance and DOC for much of the upgradient-half of the plume (0.1−2.5 km downgradient from the source) that is characterized by quasi-steady state chemistry. However, a logarithmic decrease was observed between the number of protists supported per mg of DOC and the estimated age of the DOC within the plume. The relatively labile dissolved organic contaminants that characterize the groundwater sampled from the plume ≤0.1 km downgradient from the contaminant source appeared to indirectly support 3−4 times as many protists (per mg of DOC) as the older, more recalcitrant DOC in the alkylbenzene sulfonate (ABS)-contaminated zone at 3 km downgradient (∼30 years travel time). Substantive numbers of protists (>10 4 /cm 3 ) were recovered from suboxic zones of the plume. The higher than expected ratios of protists to unattached bacteria (10 to 100:1) observed in much of the plume suggest that protists may be grazing upon both surface-associated and unattached bacterial communities to meet their nutritional requirements. In closed bottle incubation experiments, the presence of protists caused an increase in bacterial growth rate, which became more apparent at higher amendments of labile DOC (3−20 mgC/L). The presence of protists resulted in an increase in the apparent substrate saturation level for the unattached bacterial community, suggesting an important role for protists in the fate of more-labile aquifer organic contaminants.

Massachusetts↗

Natural background concentrations of nutrients in streams and rivers of the conterminous United States

Determining natural background concentrations of nutrients in watersheds in the developed world has been hampered by a lack of pristine sampling sites covering a range of climatic conditions and basin sizes. Using data from 63 minimally impacted U.S. Geological Survey reference basins, we developed empirical models of the background yield of total nitrogen (TN) and total phosphorus (TP) from small watersheds as functions of annual runoff, basin size, atmospheric nitrogen deposition rate, and region-specific factors. We applied previously estimated in-stream loss rates to yields from the small watershed models to obtain estimates of background TN and TP yield and concentration throughout the stream/river network in 14 ecoregions of the conterminous United States. Background TN concentration varies from less than 0.02 mg L-1 in the xeric west to more than 0.5 mg L-1 along the southeastern coastal plain. Background TP concentration varies from less than 0.006 mg L-1 in the xeric west to more than 0.08 mg L-1 in the great plains. TN concentrations in U.S. streams and rivers currently exceed natural background levels by a much larger factor (6.4) than do TP concentrations (2.0). Because of local variation in runoff and other factors, the range of background nutrient concentrations is very large within some nutrient ecoregions. It is likely that background concentrations in some streams in these regions exceed proposed nutrient criteria.

Environmental Science & Technology↗

Characterization and copper binding of humic and nonhumic organic matter isolated from the South Platte River: Evidence for the presence of nitrogenous binding site

Humic substances typically constitute 40−60% of the dissolved organic matter (DOM) in surface waters. However, little information is available regarding the metal binding properties of the nonhumic hydrophilic portion of the DOM. In this study, humic and nonhumic DOM samples were isolated from the South Platte River (Colorado, DOC = 2.6 mg·L - 1 , SUVA 254 = 2.4 L/mg·m) using a two-column array of XAD-8 and XAD-4 resins. The three major isolated fractions of DOM, which accounted for 57% of the bulk DOM, were characterized using a variety of analytical tools. Proton and copper binding properties were studied for each fraction. The main objective of this work was to compare the structural and chemical characteristics of the isolated fractions and test models describing DOM reactivity toward metal ions. The characterization work showed significant structural differences between the three isolated fractions of DOM. The hydrophobic acid fraction (i.e., humic substances isolated from the XAD-8 resin) gave the largest C/H, C/O, and C/N ratios and aromatic carbon content among the three isolated fractions. The transphilic acid (TPHA) fraction (“transphilic” meaning fraction of intermediate polarity isolated from the XAD-4 resin) was found to incorporate the highest proportion of polysaccharides, whereas the transphilic neutral (TPHN) fraction was almost entirely proteinaceous. The gradual increase of the charge with pH for the three DOM fractions is most likely caused by a large distribution of proton affinity constants for the carboxylic groups, as well as a second type of group more generally considered to be phenolic. In the case of the DOM fraction enriched in proteinaceous material (i.e., TPHN fraction), the results showed that the amino groups are responsible for the charge reversal. For low copper concentrations, nitrogen-containing functional groups similar to those of amino acids are likely to be involved in complexation, in agreement with previously published data.

Colorado↗

Escherichia coli and enterococci at beaches in the Grand Traverse Bay, Lake Michigan: Sources, characteristics, and environmental pathways

This study quantified Escherichia coli(EC) and enterococci (ENT) in beach waters and dominant source materials, correlated these with ambient conditions, and determined selected EC genotypes and ENT phenotypes. Bathing-water ENT criteria were exceeded more frequently than EC criteria, providing conflicting interpretations of water quality. Dominant sources of EC and ENT were bird feces (108/d/bird), storm drains (107/d), and river water (1011/d); beach sands, shallow groundwater and detritus were additional sources. Beach-water EC genotypes and ENT phenotypes formed clusters with those from all source types, reflecting diffuse inputs. Some ENT isolates had phenotypes similar to those of human pathogens and/or exhibited high-level resistance to human-use antibiotics. EC and ENT concentrations were influenced by collection time and wind direction. There was a 48-72-h lag between rainfall and elevated EC concentrations at three southern shoreline beaches, but no such lag at western and eastern shoreline beaches, reflecting the influence of beach orientation with respect to cyclic (3-5 d) summer weather patterns. In addition to local contamination sources and processes, conceptual or predictive models of Great Lakes beach water quality should consider regional weather patterns, lake hydrodynamics, and the influence of monitoring method variables (time of day, frequency).

Grand Traverse Bay↗

Binding of mercury(II) to dissolved organic matter: The role of the mercury-to-DOM concentration ratio

The binding of Hg(II) to dissolved organic matter (DOM; hydrophobic acids isolated from the Florida Everglades by XAD-8 resin) was measured at a wide range of Hg-to-DOM concentration ratios using an equilibrium dialysis ligand exchange method. Conditional distribution coefficients ( K DOM ‘) determined by this method were strongly affected by the Hg/DOM concentration ratio. At Hg/DOM ratios below approximately 1 μg of Hg/mg of DOM, we observed very strong interactions ( K DOM ‘ = 10 23.2 ± 1.0 L kg - 1 at pH = 7.0 and I = 0.1), indicative of mercury−thiol bonds. Hg/DOM ratios above approximately 10 μg of Hg/mg of DOM, as used in most studies that have determined Hg−DOM binding constants, gave much lower K DOM ‘ values (10 10.7 ± 1.0 L kg - 1 at pH = 4.9−5.6 and I = 0.1), consistent with Hg binding mainly to oxygen functional groups. These results suggest that the binding of Hg to DOM under natural conditions (very low Hg/DOM ratios) is controlled by a small fraction of DOM molecules containing a reactive thiol functional group. Therefore, Hg/DOM distribution coefficients used for modeling the biogeochemical behavior of Hg in natural systems need to be determined at low Hg/DOM ratios.

Environmental Science & Technology↗

Anthropogenic sources of arsenic and copper to sediments in a suburban lake, Northern Virginia

Mass balances of total arsenic and copper for a suburban lake in densely populated northern Virginia were calculated using data collected during 1998. Mass-balance terms were precipitation; stream inflow, including road runoff; stream outflow; and contributions from leaching of pressure-treated lumber. More mass of arsenic and copper was input to the lake than was output; the 1998 lake-retention rates were 70% for arsenic and 20% for copper. The arsenic mass balance compared well with a calculated annual mass accumulation in the top 1 cm of the lake sediments; however, the calculated contribution of copper to the lake was insufficient to account for the amount of copper in this zone. Leaching experiments were conducted on lumber treated with chromated copper arsenate (CCA) to quantify approximate amounts of arsenic and copper contributed by this source. Sources to lake sediments included leaching of CCA-treated lumber (arsenic, 50%; copper, 4%), streamwater (arsenic, 50%; copper, 90%), and atmospheric deposition (arsenic, 1%; copper, 3%). Results of this study suggest that CCA-treated lumber and road runoff could be significant nonpoint sources of arsenic and copper, respectively, in suburban catchments.

Virginia↗

Scale-dependent temporal variations in stream water geochemistry

A year-long study of four western Montana streams (two impacted by mining and two “pristine”) evaluated surface water geochemical dynamics on various time scales (monthly, daily, and bi-hourly). Monthly changes were dominated by snowmelt and precipitation dynamics. On the daily scale, post-rain surges in some solute and particulate concentra tions were similar to those of early spring runoff flushing characteristics on the monthly scale. On the bi-hourly scale, we observed diel (diurnal−nocturnal) cycling for pH, dissolved oxygen, water temperature, dissolved inorganic carbon, total suspended sediment, and some total recoverable metals at some or all sites. A comparison of the cumulative geochemical variability within each of the temporal groups reveals that for many water quality parameters there were large overlaps of concentration ranges among groups. We found that short-term (daily and bi-hourly) variations of some geochemical parameters covered large proportions of the variations found on a much longer term (monthly) time scale. These results show the importance of nesting short-term studies within long-term geochemical study designs to separate signals of environmental change from natural variability.

Montana↗

Bioreactors for removing methyl bromide following contained fumigations

Use of methyl bromide (MeBr) as a quarantine, commodity, or structural fumigant is under scrutiny because its release to the atmosphere contributes to the depletion of stratospheric ozone. A closed-system bioreactor consisting of 0.5 L of a growing culture of a previously described bacterium, strain IMB-1, removed MeBr (>110 μmol L -1 ) from recirculating air. Strain IMB-1 grew slowly to high cell densities in the bioreactor using MeBr as its sole carbon and energy source. Bacterial oxidation of MeBr produced CO 2 and hydrobromic acid (HBr), which required continuous neutralization with NaOH for the system to operate effectively. Strain IMB-1 was capable of sustained oxidation of large amounts of MeBr (170 mmol in 46 d). In an open-system bioreactor (10-L fermenter), strain IMB-1 oxidized a continuous supply of MeBr (220 μmol L -1 in air). Growth was continuous, and 0.5 mol of MeBr was removed from the air supply in 14 d. The specific rate of MeBr oxidation was 7 × 10 -16 mol cell -1 h -1 . Bioreactors such as these can therefore be used to remove large quantities of contaminant MeBr, which opens the possibility of biodegradation as a practical means for its disposal.

Environmental Science & Technology↗

Arsenic in groundwater in eastern New England: Occurrence, controls, and human health implications

In eastern New England, high concentrations (greater than 10 ??g/L) of arsenic occur in groundwater. Privately supplied drinking water from bedrock aquifers often has arsenic concentrations at levels of concern to human health, whereas drinking water from unconsolidated aquifers is least affected by arsenic contamination. Water from wells in metasedimentary bedrock units, primarily in Maine and New Hampshire, has the highest arsenic concentrations - nearly 30% of wells in these aquifers produce water with arsenic concentrations greater than 10 ??g/L. Arsenic was also found at concentrations of 3-40 mg/kg in whole rock samples in these formations, suggesting a possible geologic source. Arsenic is most common in groundwater with high pH. High pH is related to groundwater age and possibly the presence of calcite in bedrock. Ion exchange in areas formerly inundated by seawater also may increase pH. Wells sampled twice during periods of 1-10 months have similar arsenic concentrations (slope = 0.89; r-squared = 0.97). On the basis of water-use information for the aquifers studied, about 103 000 people with private wells could have water supplies with arsenic at levels of concern (greater than 10 ??g/L) for human health.

Environmental Science & Technology↗

Environmental fate of roxarsone in poultry litter. I. Degradation of roxarsone during composting

Roxarsone, 3-nitro-4-hydroxyphenylarsonic acid, is an organoarsenic compound that is used extensively in the feed of broiler poultryto control coccidial intestinal parasites, improve feed efficiency, and promote rapid growth. Nearly all the roxarsone in the feed is excreted unchanged in the manure. Poultry litter composed of the manure and bedding material has a high nutrient content and is used routinely as a fertilizer on cropland and pasture. Investigations were conducted to determine the fate of poultrylitter roxarsone in the environment. Experiments indicated that roxarsone was stable in fresh dried litter; the primary arsenic species extracted with water from dried litter was roxarsone. However, when water was added to litter at about 50 wt % and the mixture was allowed to compost at 40 o C, the speciation of arsenic shifted from roxarsone to primarily arsenate in about 30 days. Increasing the amount of water increased the rate of degradation. Experiments also suggested that the degradation process most likely was biotic in nature. The rate of degradation was directly proportional to the incubation temperature; heat sterilization eliminated the degradation. Biotic degradation also was supported by results from enterobacteriaceae growth media that were inoculated with litter slurry to enhance the biotic processes and to reduce the concomitant abiotic effects from the complex litter solution. Samples collected from a variety of litter windrows in Arkansas, Oklahoma, and Maryland also showed that roxarsone originally present had been converted to arsenate.

Environmental Science & Technology↗

Environmental fate of roxarsone in poultry litter. Part II. Mobility of arsenic in soils amended with poultry litter

Poultry litter often contains arsenic as a result of organo-arsenical feed additives. When the poultry litter is applied to agricultural fields, the arsenic is released to the environment and may result in increased arsenic in surface and groundwater and increased uptake by plants. The release of arsenic from poultry litter, litter-amended soils, and soils without litter amendment was examined by extraction with water and strong acids (HCI and HN03). The extracts were analyzed for As, C, P, Cu, Zn, and Fe. Copper, zinc, and iron are also poultry feed additives. Soils with a known history of litter application and controlled application rate of arsenic-containing poultry litter were obtained from the University of Maryland Agricultural Experiment Station. Soils from fields with long-term application of poultry litter were obtained from a tilled field on the Delmarva Peninsula (MD) and an untilled Oklahoma pasture. Samples from an adjacent forest or nearby pasture that had no history of litter application were used as controls. Depth profiles were sampled for the Oklahoma pasture soils. Analysis of the poultry litter showed that 75% of the arsenic was readily soluble in water. Extraction of soils shows that weakly bound arsenic mobilized by water correlates positively with C, P, Cu, and Zn in amended fields and appears to come primarily from the litter. Strongly bound arsenic correlates positively with Fe in amended fields and suggests sorption or coprecipitation of As and Fe in the soil column.

Environmental Science & Technology↗

Effects of daily precipitation and evapotranspiration patterns on flow and VOC transport to groundwater along a watershed flow path

MTBE and other volatile organic compounds (VOCs) are widely observed in shallow groundwater in the United States, especially in urban areas. Previous studies suggest that the atmosphere and/or nonpoint surficial sources could be responsible for some of those VOCs, especially in areas where there is net recharge to groundwater. However, in semi-arid locations where annual potential evapotranspiration can exceed annual precipitation, VOC detections in groundwater can be frequent. VOC transport to groundwater under net discharge conditions has not previously been examined. A numerical model is used here to demonstrate that daily precipitation and evapotranspiration (ET) patterns can have a significant effect on recharge to groundwater, water table elevations, and VOC transport. Ten-year precipitation/ET scenarios from six sites in the United States are examined using both actual daily observed values and “average” pulsed precipitation. MTBE and tetrachloroethylene transport, including gas-phase diffusion, are considered. The effects of the precipitation/ET scenarios on net recharge and groundwater flow are significant and complicated, especially under low-precipitation conditions when pulsed precipitation can significantly underestimate transport to groundwater. In addition to precipitation and evapotranspiration effects, location of VOC entry into the subsurface within the watershed is important for transport in groundwater. This is caused by groundwater hydraulics at the watershed scale as well as variations in ET within the watershed. The model results indicate that it is important to consider both daily precipitation/ET patterns and location within the watershed in order to interpret VOC occurrence in groundwater, especially in low-precipitation settings.

Environmental Science & Technology↗

Binding of mercury(II) to aquatic humic substances: Influence of pH and source of humic substances

Conditional distribution coefficients ( K DOM ‘) for Hg(II) binding to seven dissolved organic matter (DOM) isolates were measured at environmentally relevant ratios of Hg(II) to DOM. The results show that K DOM ‘ values for different types of samples (humic acids, fulvic acids, hydrophobic acids) isolated from diverse aquatic environments were all within 1 order of magnitude (10 22.5 ± 1.0 −10 23.5 ± 1.0 L kg - 1 ), suggesting similar Hg(II) binding environments, presumably involving thiol groups, for the different isolates. K DOM ‘ values decreased at low pHs (4) compared to values at pH 7, indicating proton competition for the strong Hg(II) binding sites. Chemical modeling of Hg(II)−DOM binding at different pH values was consistent with bidentate binding of Hg(II) by one thiol group (p K a = 10.3) and one other group (p K a = 6.3) in the DOM, which is in agreement with recent results on the structure of Hg(II)−DOM bonds obtained by extended X-ray absorption fine structure spectroscopy (EXAFS).

Environmental Science & Technology↗

Interactions of organic contaminants with mineral-adsorbed surfactants

Sorption of organic contaminants (phenol, p-nitrophenol, and naphthalene) to natural solids (soils and bentonite) with and without myristylpyridinium bromide (MPB) cationic surfactant was studied to provide novel insight to interactions of contaminants with the mineral-adsorbed surfactant. Contaminant sorption coefficients with mineral-adsorbed surfactants, Kss, show a strong dependence on surfactant loading in the solid. At low surfactant levels, the Kss values increased with increasing sorbed surfactant mass, reached a maximum, and then decreased with increasing surfactant loading. The Kss values for contaminants were always higher than respective partition coefficients with surfactant micelles (Kmc) and natural organic matter (Koc). At examined MPB concentrations in water the three organic contaminants showed little solubility enhancement by MPB. At low sorbed-surfactant levels, the resulting mineral-adsorbed surfactant via the cation-exchange process appears to form a thin organic film, which effectively "adsorbs" the contaminants, resulting in very high Kss values. At high surfactant levels, the sorbed surfactant on minerals appears to form a bulklike medium that behaves essentially as a partition phase (rather than an adsorptive surface), with the resulting Kss being significantly decreased and less dependent on the MPB loading. The results provide a reference to the use of surfactants for remediation of contaminated soils/sediments or groundwater in engineered surfactant-enhanced washing.

Environmental Science & Technology↗