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Predicted aquatic exposure effects from a national urban stormwater study

A multi-agency study of 438 organic and 62 inorganic chemicals measured in urban stormwater during 50 total runoff events at 21 sites across the United States demonstrated that stormwater discharges can generate localized, aquatic exposures to extensive contaminant mixtures, including organics suspected to cause adverse aquatic-health effects. The aggregated risks to multiple aquatic trophic levels (fish, invertebrates, plants) of the stormwater mixture exposures, which were documented in the national study, were explored herein by calculating cumulative ratios of organic-contaminant in vitro exposure–activity cutoffs (∑ EAR ) and health-benchmark-weighted cumulative toxicity quotients (∑ TQ ). Both risk assessment approaches indicated substantial (moderate to high) risk for acute adverse effects to aquatic organisms across multiple trophic levels (fish, macroinvertebrates, non-vascular/vascular plants) at or near stormwater discharge points across the United States. The results are interpreted as potential orders of magnitude underestimates of actual aquatic risk in stormwater control wetlands or in the immediate vicinity of such discharges to surface-water receptors, because the 438 organic-compound analytical space assessed in this study is orders of magnitude less than the 350 000 parent compounds estimated to be in current commercial use globally and the incalculable chemical-space of potential metabolites and degradates.

Environmental Science: Water Research and Technolo

Exposures and potential health implications of contaminant mixtures in linked source water, finished drinking water, and tapwater from public-supply drinking water systems in Minneapolis/St. Paul area, USA

Continued improvements in drinking-water quality characterization and treatment/distribution infrastructure are required to address the expanding number of documented environmental contaminants. To better understand the variability in contaminant exposures from the drinking water resource (surface and groundwater), through the distribution process, to the point-of-use (tapwater), in 2019 a synoptic assessment of broad chemical exposures was conducted in system-specific source waters, finished drinking water and service-area tapwater from 10 drinking water treatment facilities in the greater Minneapolis/St. Paul area of Minnesota, United States. Source water, finished water (collected pre-distribution in the treatment facility), and tapwater samples were analyzed for 465 unique organic compounds, 34 inorganic constituents, and 3 field parameters as well as in vitro estrogen, androgen, and glucocorticoid bioactivities. Mixtures of organic and inorganic contaminants were prevalent in source water, finished water, and tapwater samples, indicating the continued need for broad assessments of mixed contaminant exposures to characterize potential drinking-water human health outcomes. Contaminant concentrations were similar among drinking water sources and no exceedances of Environmental Protection Agency maximum contaminant level(s) (MCL) were observed in any treated sample (finished water or tapwater) in this study. No treated sample contained estrogenic, androgenic, or glucocorticoid activity at concentrations that may cause adverse human health effects. However, there were multiple exceedances of non-enforceable MCL goal(s) (MCLG), and other health advisories combined with frequent exceedances of benchmark-based hazard indices in both finished water and tapwater samples. These results indicate that exposure to contaminant mixtures is a potential public health concern underscoring our continued efforts to assess contaminant mixture exposures at the drinking-water point of consumption using a broad analytical scope.

Minnesota

Tapwater-contaminant mixtures and risk in a biofuel-facility impacted private-well community

We assessed private-well drinking water (DW) at the point of use ( i.e. , tapwater, TW) within a rural Nebraska community around a state-closed biofuel facility, which used pesticide-treated corn seed as feedstock for ethanol production. Organic (485), inorganic (34), and microbial (13) analytes were assessed at 15 locations in June 2022, to evaluate the relative contribution of facility-consistent pesticides (seed-treatment fungicides and insecticides) to overall TW-contaminant exposures and predicted human-health risks. Thirty-three organics (12 pesticides) and 28 inorganics were detected, the former including the fungicide sedaxane, insecticide chlorantraniliprole, and multiple neonicotinoid insecticides/degradates, all consistent with seed treatment and respective biofuel-facility waste. Assessment of pesticides only at extant point-of-use (POU) treatment taps at three sites demonstrated complete elimination of all TW-pesticide detections. Based on detection of maximum pesticide concentrations in a home located downstream along a creek capturing facility runoff, pesticides only were assessed in January 2023 again at this home and at three adjacent locations, confirming results at the former and documenting decreasing TW-pesticide concentrations, including neonicotinoids, with increasing distance from the creek. Human-health DW benchmarks are not available for many detected pesticides, including the detected fungicide and insecticides, but precautionary screening levels were exceeded frequently due to multiple inorganics. The results indicate that exposures to multiple (median: 4.5; range: 1–7) co-occurring TW contaminants of potential human-health concern are common, warranting consideration of point-of-entry or POU treatment(s) throughout the community to reduce or eliminate unrecognized exposures to TW contaminants, including facility-associated pesticides in down-gradient locations. More broadly, results emphasize the importance of continued characterization of private-TW exposures, employing a environmentally informative analytical scope, to identify and mitigate risks of unrecognized exposures in private-well-dependent rural communities.

Nebraska

New Method for Electrical Conductivity Temperature Compensation

Electrical conductivity (κ) measurements of natural waters are typically referenced to 25 °C (κ 25 ) using standard temperature compensation factors (α). For acidic waters (pH < 4), this can result in a large κ 25 error (δκ 25 ). The more the sample temperature departs from 25 °C, the larger the potential δκ 25 . For pH < 4, the hydrogen ion transport number becomes substantial and its mode of transport is different from most other ions resulting in a different α. A new method for determining α as a function of pH and temperature is presented. Samples with varying amounts of H 2 SO 4 and NaCl were used to develop the new α, which was then applied to 65 natural water samples including acid mine waters, geothermal waters, seawater, and stream waters. For each sample, the κ and pH were measured at several temperatures from 5 to 90 °C and κ 25 was calculated. The δκ 25 ranged from −11 to 9% for the new method as compared to −42 to 25% and −53 to 27% for the constant α (0.019) and ISO-7888 methods, respectively. The new method for determining α is a substantial improvement for acidic waters and performs as well as or better than the standard methods for circumneutral waters.

Environmental Science & Technology

From the 1988 drought to the 1993 flood: Transport of halogenated organic compounds with the Mississippi river suspended sediment at Thebes, Illinois

Suspended sediment was isolated from water samples collected from the Mississippi River at Thebes, IL, eight times over a 5-year period from May 1988 through September 1993 in order to evaluate the transport of lipophilic halogenated organic compounds associated with the suspended sediment. Two hydrologic extremes were included-the 1988 drought and the 1993 flood. Halogenated organic compounds included polychlorinated biphenyls (PCBs), hexachlorobenzene, pentachloroanisole, DCPA (dacthal), trifluralin, aldrin, dieldrin, and chlordane components. Sediment transport of most of these organic compounds was substantially higher during the 1993 flood then at other sampling times. The extreme transports during the flood were due to unusually high concentrations of some contaminants on the suspended sediment, low to average concentrations of suspended sediment being transported, and unusually high water discharges.

Illinois

Partnership of Environmental Education and Research-A compilation of student research, 1999-2008

The U.S. Geological Survey (USGS) Tennessee Water Science Center and the College of Engineering and Technology at Tennessee State University developed a Partnership in Environmental Education and Research (PEER) to support environmental research at TSU and to expand the environmental research capabilities of the USGS in Tennessee. The PEER program is driven by the research needs to better define the occurrence, fate, and transport of contaminants in groundwater and surface water. Research in the PEER program has primarily focused on the transport and remediation of organic contamination in karst settings. Research conducted through the program has also expanded to a variety of media and settings. Research areas include contaminant occurrence and transport, natural and enhanced bioremediation, geochemical conditions in karst aquifers, mathematical modeling for contaminant transport and degradation, new methods to evaluate groundwater contamination, the resuspension of bacteria from sediment in streams, the use of bioluminescence and chemiluminescence to identify the presence of contaminants, and contaminant remediation in wetlands. The PEER program has increased research and education opportunities for students in the College of Engineering, Technology, and Computer Science and has provided students with experience in presenting the results of their research. Students in the program have participated in state, regional, national and international conferences with more than 140 presentations since 1998 and more than 40 student awards. The PEER program also supports TSU outreach activities and efforts to increase minority participation in environmental and earth science programs at the undergraduate and graduate levels. TSU students and USGS staff participate in the TSU summer programs for elementary and high school students to promote earth sciences. The 2007 summer camps included more than 130 students from 20 different States and Washington DC.

Tennessee

Gas-film coefficients for the volatilization of ethylene dibromide from water

Gas-film coefficients for the volatilization of ethylene dibromide (EDB) and water were determined in the laboratory as a function of wind speed and temperature. The ratio of the coefficients was independent of wind speed and increased slightly with temperature. Use of this ratio with an environmentally determined gas-film coefficient for the evaporation of water permits determination of the gas-film coefficient for the volatilization of EDB from environmental waters.

Environmental Science & Technology

Real-time PCR detection and quantification of nine potential sources of fecal contamination by analysis of mitochondrial Cytochrome b targets

We designed and tested real-time PCR probe/primer sets to detect and quantify Cytochrome b sequences of mitochondrial DNA (mtDNA) from nine vertebrate species of pet (dog), farm (cow, chicken, sheep, horse, pig), wildlife (Canada goose, white-tailed deer), and human. Linear ranges of the assays were from 101 to 108 copies/??l. To formally test the performance of the assays, twenty blinded fecal suspension samples were analyzed by real-time PCR to identify the source of the feces. Sixteen of the twenty samples were correctly and unambiguously identified. Average sensitivity was calculated to be 0.850, while average specificity was found to be 0.994. One beef cow sample was not detected, but mtDNA from 11 other beef cattle of both sexes and varying physiological states was found in concentrations similar (3.45 ?? 107 copies/g) to thatfound in human feces (1.1 ?? 107 copies/g). Thus, environmental conditions and sample handling are probably important factors for successful detection of fecal mtDNA. When sewage samples were analyzed, only human mtDNA (7.2 ?? 104 copies/100 mL) was detected. With a detection threshold of 250 copies/reaction, an efficient concentration and purification method resulted in a final detection limit for human feces of 1.8 mg/100 mL water.

Environmental Science & Technology

Preliminary preview for a geographic and monitoring program project; a review of point source-nonpoint source effluent trading/offset systems in watersheds

Watershed-based trading and offset systems are being developed to improve policy-maker?s and regulator?s ability to assess nonpoint source impacts in watersheds and to evaluate the efficacy of using market-incentive programs for preserving environmental quality. An overview of the history of successful and failed trading programs throughout the United States suggests that certain political, economic, and scientific conditions within a temporal and spatial setting help meet water quality standards. The current lack of spontaneous trading among dischargers does not mean that a marketable permit trading system is an inherently inefficient regulatory approach. Rather, its infrequent use is the result of institutional and informational barriers. Improving and refining the earth science information and technologies may help determine whether trading is a suitable policy for improving water quality. However, it is debatable whether or not environmental information is the limiting factor. This paper reviews additional factors affecting the potential for instituting a trading policy. The motivation for investigating and reviewing the history of offsets and trading was inspired by a project in the preliminary stages being developed by U.S. Geological Survey Western Geographic Science Center and the Environmental Protection Agency Region IX. An offset feasibility study will be an integrated, map-based approach that incorporates environmental, economic, and statistical information to investigate the potential for using offsets to meet mercury Total Maximum Daily Loads in the Sacramento River watershed. A regional water-quality offset program is being studied that may help known point sources reduce mercury loading more cost effectively by the remediation of abandoned mines or other diffuse sources as opposed to more costly treatment at their own sites. An efficient offset program requires both a scientific basis and methods to translate that science into a regulatory decision framework.

Open-File Report

Limitations in the use of commercial humic acids in water and soil research

Seven samples of commercial "humic acids", purchased from five different suppliers, were studied, and their characteristics were compared with humic and fulvic acids isolated from streams, soils, peat, leonardite, and a dopplerite sample. Cross-polarization and magic-angle spinning 13C NMR spectroscopy clearly shows pronounced differences between the commercial materials and all other samples. Elemental and infrared spectroscopic data do not show such clear-cut differences but can be used as supportive evidence, with the 13C NMR data, to substantiate the above distinctions. As a result of these differences and due to the general lack of information relating to the source, method of isolation, or other pretreatment of the commercial materials, these commercial products are not considered to be appropriate for use as analogues of true soil and water humic substances, in experiments designed to evaluate the nature and reactivity of humic substances in natural waters and soils.

Environmental Science & Technology

Uptake, elimination, and relative distribution of perchlorate in various tissues of channel catfish

This study was undertaken to determine the kinetics of uptake and elimination of perchlorate in channel catfish, Ictalurus punctatus. Perchlorate - an oxidizer used in solid fuel rockets, fireworks, and illuminating munitions - has been shown to effect thyroid function, causing hormone disruption and potential perturbations of metabolic activities. For the uptake study, catfish were exposed to 100 mg/L sodium perchlorate for 12 h to 5 d in the laboratory. Perchlorate in tissues was analyzed using ion chromatography. The highest perchlorate concentrations were found in the head and fillet, indicating that these tissues are the most important tissues to analyze when determining perchlorate uptake into large fish. To calculate uptake and elimination rate constants for fillet, gills, G-I tract, liver, and head, fish were exposed to 100 ppm sodium perchlorate for 5 days, and allowed to depurate in clean water for up to 20 days. The animals rapidly eliminated the perchlorate accumulated showing the highest elimination in fillet (Ke = 1.67 day -1) and lowest elimination in liver (Ke = 0.79 day -1). ?? 2007 American Chemical Society.

Environmental Science & Technology

Assessing the lead solubility potential of untreated groundwater of the United States

In the U.S., about 44 million people rely on self-supplied groundwater for drinking water. Because most self-supplied homeowners do not treat their water to control corrosion, drinking water can be susceptible to lead (Pb) contamination from metal plumbing. To assess the types and locations of susceptible groundwater, a geochemical reaction model that included pure Pb minerals and solid solutions of calcite (Ca x Pb 1– x CO 3 ) and apatite [Ca x Pb 5-x (PO 4 ) 3 (OH; Cl; F)] was developed to estimate the lead solubility potential (LSP) for over 8300 untreated groundwater samples collected from domestic and public-supply sites between 2000 and 2016 in the U.S. The LSP is the calculated amount of Pb metal that could dissolve at 25 °C before a Pb-bearing mineral precipitates. About 33% of untreated groundwater samples had LSP greater than 15 μg/L—the USEPA action level for dissolved plus particulate forms of Pb. Five percent of samples had high LSP (above 300 μg/L) and tended to occur in the eastern and southeastern U.S. Measured Pb concentrations above 15 μg/L were rarely detected (<1%) but always coincided with high LSP values. Future work will provide a better understanding of the relation between water chemistry, Pb-mineral formation, and dissolved Pb concentrations in tap water.

Environmental Science & Technology

Partition coefficients of organic compounds in lipid-water systems and correlations with fish bioconcentration factors

Triolein-water partition coefficients (KtW) have been determined for 38 slightly water-soluble organic compounds, and their magnitudes have been compared with the corresponding octanol-water partition coefficients (KOW). In the absence of major solvent-solute interaction effects in the organic solvent phase, the conventional treatment (based on Raoult's law) predicts sharply lower partition coefficients for most of the solutes in triolein because of its considerably higher molecular weight, whereas the Flory-Huggins treatment predicts higher partition coefficients with triolein. The data are in much better agreement with the Flory-Huggins model. As expected from the similarity in the partition coefficients, the water solubility (which was previously found to be the major determinant of the KOW) is also the major determinant for the Ktw. When the published BCF values (bioconcentration factors) of organic compounds in fish are based on the lipid content rather than on total mass, they are approximately equal to the Ktw, which suggests at least near equilibrium for solute partitioning between water and fish lipid. The close correlation between Ktw and Kow suggests that Kow is also a good predictor for lipid-water partition coefficients and bioconcentration factors.

Environmental Science & Technology

Binding of pyrene to aquatic and commercial humic substances: The role of molecular weight and aromaticity

The binding of pyrene to a number of humic substances isolated from various aquatic sources and a commercial humic acid was measured using the solubility enhancement method. The humic materials used in this study were characterized by various spectroscopic and liquid chromatography methods. A strong correlation was observed between the pyrene binding coefficient, K(doc), and the molecular weights, molar absorptivities at 280 nm, and aromaticity of the aquatic humic substances. Binding of pyrene to the commercial humic acid, however, was significantly stronger and did not obey the relationships observed between K(doc) and the chemical properties of the aquatic humic substrates. These results suggest that the molecular weight and the aromatic content of the humic substrates exert influences on the binding of nonpolar and planar aromatic molecules and that the physicochemical properties of both humic materials and organic solutes are important in controlling the speciation of nonpolar organic contaminants in natural waters.

Environmental Science & Technology