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Hydrology, nutrient concentrations, and nutrient yields in nearshore areas of four lakes in northern Wisconsin, 1999-2001

The effects of shoreline development on water quality and nutrient yields in nearshore areas of four lakes in northern Wisconsin were investigated from October 1999 through September 2001. The study measured surface runoff and ground-water flows from paired developed (sites containing lawn, rooftops, sidewalks, and driveways) and undeveloped (mature and immature woods) catchments adjacent to four lakes in northern Wisconsin. Water samples from surface runoff and ground water were collected and analyzed for nutrients. Coupled with water volumes, loads and subsequent yields of selected constituents were computed for developed and undeveloped catchments. The median runoff from lawn surfaces ranged from 0.0019 to 0.059 inch over the catchment area. Median surface runoff estimates from the wooded catchments were an order of magnitude less than those from the lawn catchments. The increased water volumes from the lawn catchments resulted in greater nutrient loads and subsequent annual nutrient yields from the developed sites. Soil temperature and soil moisture were measured at two sites with mixed lawn and wooded areas. At both of these sites, the area covered with a lawn commonly was warmer than the wooded area. No consistent differences in soil moisture were found. A ground-water model was constructed to simulate the local flow systems at two of the paired catchments. Model simulations showed that much of the ground water delivered to the lake originated from distant areas that did not contribute runoff directly to the lake. Surface runoff and ground-water nutrient concentrations from the lawn and wooded catchments did not have apparent patterns. Some of the median concentrations from lawns were significantly different (at the 0.05 significance level) from those at wooded catchments. Water wells and piezometers were sampled for chemical analyses three times during the study period. Variability in the shallow ground-water chemistry over time in the lawn samples was larger than samples from the wooded areas and upgradient wells. Median nutrient yields in surface runoff from lawns always were greater than those from the wooded catchments. Runoff volumes were the most important factor in determining whether lawns or wooded catchments contribute more nutrients to the lake. The ground-water system had appreciable nutrient concentrations, and are likely an important pathway for nutrient transport to the lake. The nitrate plus nitrite nitrogen and total phosphorus yields to the ground-water system from a lawn catchment were approximately 3 to 4 times greater than those from the wooded catchment. There was no difference in the yields of dissolved inorganic phosphorus to the ground-water system from the lawn and wooded catchments. Study results demonstrate that choosing the appropriate landscape position for locating lawns in sloped areas (specifically, slopes that do not terminate at the lake or areas with intervening flat or buffer zones between lawn and lake) can help reduce the adverse effect of lawns on the shallow ground water and, ultimately, the lake. Additional information would be needed to extrapolate these results to a large drainage area of a lake.

Wisconsin↗

Multiple lines of evidence for identifying potential hazards to fish from contaminants of emerging concern in Great Lakes tributaries

Contaminants of emerging concern (CECs; e.g., pharmaceuticals, flame retardants, pesticides, and industrial chemicals) are omnipresent throughout tributaries to the Great Lakes. Furthermore, CECs are often present at concentrations that are potentially hazardous to aquatic species. Since 2010, we characterized the presence of CECs at 309 sites within 47 Great Lakes tributaries and characterized responses of fathead minnow ( Pimephales promelas ) exposed to river water at a subset of 26 sites within four tributaries. Our work resulted in three independent lines of evidence related to the potential hazards of CEC exposure to fish. First, vulnerability (where vulnerability refers to likelihood) of surface waters to CEC presence was predicted using select watershed characteristics. Second, hazard to fish (where hazard means the potential for adverse biological responses) was predicted using screening values for a subset of CECs. Third, biological responses of fathead minnow exposed to river water in streamside exposures were measured. We assessed the congruence of these three lines of evidence for identifying sites with elevated hazards to CEC exposure. Predicted vulnerability and hazards agreed at 66% of all sites. Where the two indices did not agree, vulnerability often underestimated predicted hazard. When compared with measured biological responses from streamside exposures, predicted hazards agreed for 42% of samples. Furthermore, when predicted hazards for specific effect categories were compared with similar measured biomarkers, 26% and 46% of samples agreed for reproductive and physiological effect categories, respectively. Overall, vulnerability and hazard predictions tended to overestimate the measured biological responses, providing a protective estimate of the potential hazards of CEC exposure to fish. When used together, these three approaches can help resource managers prioritize management activities in minimizing hazards of CEC exposure and can be used by researchers to prioritize studies focused on understanding the hazards of CEC exposure to fish. Integr Environ Assess Manag 2022;18:1246–1259. © 2021 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC). This article has been contributed to by US Government employees and their work is in the public domain in the USA.

Great Lakes↗

The Effect of Selected Cleaning Techniques on Berkshire Lee Marble: A Scientific Study at Philadelphia City Hall

This report describes a scientific investigation of the effects of eight different cleaning techniques on the Berkshire Lee marble component of the facade of the East Center Pavilion at Philadelphia City Hall; the study was commissioned by the city of Philadelphia. The eight cleaning techniques evaluated in this study were power wash (proprietary gel detergent followed by water rinse under pressure), misting (treatment with potable, nebulized water for 24-36 hours), gommage (proprietary Thomann-Hanry low-pressure, air-driven, small-particle, dry abrasion), combination (gommage followed by misting), Armax (sodium bicarbonate delivered under pressure in a water wash), JOS (dolomite powder delivered in a low-pressure, rotary-vortex water wash), laser (thermal ablation), and dry ice (powdered-dry-ice abrasion delivered under pressure). In our study approximately 160 cores were removed from the building for laboratory analysis. We developed a computer program to analyze scanning-electron-micrograph images for the microscale surface roughness and other morphologic parameters of the stone surface, including the near-surface fracture density of the stone. An analysis of more than 1,100 samples cut from the cores provided a statistical basis for crafting the essential elements of a reduced-form, mixed-kinetics conceptual model that represents the deterioration of calcareous stone in terms of self-organized soiling and erosion patterns. This model, in turn, provided a basis for identifying the variables that are affected by the cleaning techniques and for evaluating the extent to which such variables influence the stability of the stone. The model recognizes three classes of variables that may influence the soiling load on the stone, including such exogenous environmental variables as airborne moisture, pollutant concentrations, and local aerodynamics, and such endogenous stone variables as surface chemistry and microstructure (fracturing, roughness, and so on). This study showed that morphologic variables on the mesoscale to macroscale are not generally affected by the choice of a cleaning technique. The long-term soiling pattern on the building is independent of the cleaning technique applied. This study also showed that soluble salts do not play a significant role in the deterioration of Berkshire Lee marble. Although salts were evident in cracks and fissures of the heavily soiled stone, such salts did not penetrate the surface to a depth of more than a few hundred micrometers. The criteria used to differentiate the cleaning techniques were ultimately based on the ability of each technique to remove soiling without altering the texture of the stone surface. This study identified both the gommage and JOS techniques as appropriate for cleaning ashlar surfaces and the combination technique as appropriate for cleaning highly carved surfaces at the entablatures, cornices, and column capitals.

Professional Paper↗

Water-level altitudes and continuous and discrete water quality at and near an aquifer storage and recovery site, Bexar, Atascosa, and Wilson Counties, Texas, June 2004-September 2011

The U.S. Geological Survey (USGS), in cooperation with the San Antonio Water System (SAWS), collected data during 2004–11 to characterize the quality of native groundwater from the San Antonio segment of the Edwards aquifer (hereinafter, Edwards aquifer) and preinjection and postinjection water from the Carrizo aquifer (informal name commonly applied to the upper part of the Carrizo-Wilcox aquifer in the area) at and near an aquifer storage and recovery (ASR) site in Bexar, Atascosa, and Wilson Counties, Texas. Daily mean water-level altitude, water temperature, and specific conductance were measured continuously in a monitoring well on the ASR site to determine how injection and withdrawal at the ASR site might affect local groundwater. Groundwater samples were collected and analyzed for selected physical properties and constituents to characterize the quality of native groundwater from the Edwards aquifer and preinjection and postinjection water from the Carrizo aquifer near the ASR site to provide a better understanding of possible changes in the quality of groundwater near an active ASR site that might result from the mixing of water from different aquifers. During injection periods, the water-level altitude in the monitoring well generally increased as the amount of water being injected into all wells at the ASR site increased and decreased as the amount of water being injected into all wells at the ASR site decreased. During withdrawal periods, the water-level altitude in the monitoring well generally increased as the total volume of water being withdrawn from all wells at the ASR site decreased and generally decreased as the total volume of water being withdrawn from all wells increased. Daily mean water temperature fluctuated by less than 1 degree Celsius and was determined to be independent of injection or withdrawal conditions at the ASR site. Changes in daily mean specific-conductance values measured at four depths in the monitoring well at the ASR site occurred without regard to total ASR site injection or withdrawal volumes. No substantial differences were measured over time in major-ion, trace-element, or isotope chemistry of water samples collected from the wells that supplied water from the Edwards aquifer. Little variation in water chemistry was detected in the samples collected from four wells designed to inject and withdraw water at the ASR site, regardless of whether the ASR site was injecting or withdrawing water. The similarity of major-ion and isotope chemistry between the Edwards aquifer source wells and the four ASR wells indicates that little, if any, migration of injected water away from the ASR wells has occurred. In a well located closest to the ASR site in the direction of regional flow for the Carrizo aquifer, a greater alkalinity value and a smaller concentration of chloride were measured in the most recent sample than in all other samples collected at this well. Substantial increases in dissolved iron and manganese concentrations also were observed in this well. The increased alkalinity value and dissolved iron and manganese concentrations and the decreased chloride concentration in the well could indicate that the injected water from the Edwards aquifer had begun to move into at least a part of the strata supplying these wells and might be causing iron and manganese mobilization in the Carrizo aquifer.

Texas↗

Multiple-well monitoring site adjacent to the Midway- Sunset and Buena Vista Oil Fields, Kern County, California

Groundwater quality in and around oil fields in the Southern San Joaquin Valley is of interest to many California residents that rely heavily on groundwater for domestic, commercial, and agricultural use. To help assess the effects of historical oil-field activities and natural geologic sources on groundwater near the southwest margins of the Kern County Groundwater Subbasin, a multiple-well monitoring site was installed near the administrative boundary between the Midway-Sunset and Buena Vista Oil Fields in Kern County, California. The installation of the Midway-Sunset Buena Vista multiple-well monitoring site (MSBV) supports regional analysis of the relations of oil and gas sources to groundwater quality by providing information about the geology, hydrology, geophysical properties, and water quality of the alluvial and upper Tulare aquifers in areas where groundwater data were limited. Data collected from the site included drill cuttings, whole core samples, sidewall core samples, mud-gas analysis, borehole geophysical logs, depth to water measurements, and water quality samples. Whole cores were scanned using dual energy computed tomography. Subsamples of selected cores were analyzed for density, porosity, specific retention, and bulk minerology. Thin sections of the subsamples were prepared, photographed, and examined. Two samples were analyzed using scanning electron microscope technology to examine the microporosity of diatomite laden sediment. Instrumentation installed in the wells collect hourly depth to water measurements. Analysis of the data show there is 355 feet of alluvium overlying the Tulare Formation at the well site. The contact between the two formations is an aquitard resulting in a perched aquifer in the alluvium and unconfined aquifer in the Tulare Formation. The alluvium is more heterogenous and finer grained than the Tulare Formation resulting in markedly higher porosity in the alluvium compared to the Tulare Formation. Higher specific retention observed in the alluvium is attributed to the finer grained sediment and greater abundance of reworked diatomite (as represented by opal-CT [cristobalite-tridymite]) compared to the Tulare Formation. Total dissolved solids (TDS) approached or exceeded 10,000 milligrams per liter (mg/L) in the alluvium from approximately 176 to 242 feet below land surface and at the top of the Amnicola clay at approximately 670 feet below land surface within the Tulare Formation. Elevated TDS, chloride, and boron concentrations in the alluvium and on top of the Amnicola clay likely reflect groundwater that is mixed with oil-field water. Water chemistry and modern-aged groundwater in the alluvial monitoring well (MSBV #3) are consistent with the oil-field water in the alluvium being derived from documented historical surface disposal of oil-field water upslope (northwest) of the site. Water chemistry and pre-modern groundwater age in the deeper Tulare monitoring well (MSBV #1) on top of the Amnicola clay are consistent with oil-field fluids derived from upslope natural geologic sources or old oil wells that leak in the subsurface. Shallow groundwater in the Tulare (MSBV #2) is not affected by mixing with oil-field sources.

EarthArXiv↗

Response of aquatic macrophytes to human land use perturbations in the watersheds of Wisconsin lakes, U.S.A.

Aquatic macrophyte communities were assessed in 53 lakes in Wisconsin, U.S.A. along environmental and land use development gradients to determine effects human land use perturbations have on aquatic macrophytes at the watershed and riparian development scales. Species richness and relative frequency were surveyed in lakes from two ecoregions: the Northern Lakes and Forests Ecoregion and the Southeastern Wisconsin Till Plain Ecoregion. Lakes were selected along a gradient of watershed development ranging from undeveloped (i.e., forested), to agricultural to urban development. Land uses occurring in the watershed and in perimeters of different width (0–100, 0–200, 0–500, and 0–1000 m from shore, in the watershed) were used to assess effects on macrophyte communities. Snorkel and SCUBA were used to survey aquatic macrophyte species in 18 quadrats of 0.25 m 2 along 14 transects placed perpendicular to shore in each lake. Effects of watershed development (e.g., agriculture and/or urban) were tested at whole-lake (entire littoral zone) and near-shore (within 7 m of shore) scales using canonical correspondence analysis (CCA) and linear regression. Overall, species richness was negatively related to watershed development, while frequencies of individual species and groups differed in level of response to different land use perturbations. Effects of land use in the perimeters on macrophytes, with a few exceptions, did not provide higher correlations compared to land use at the watershed scale. In lakes with higher total watershed development levels, introduced species, particularly Myriophyllum spicatum , increased in abundance and native species, especially potamids, isoetids, and floating-leaved plants, declined in abundance. Correlations within the northern and southeastern ecoregions separately were not significant. Multivariate analyses suggested species composition is driven by environmental responses as well as human development pressures. Both water chemistry and land use variables loaded positively with the first CCA axis indicating that these factors are correlated. Land use pressures in Wisconsin are greater in the southeastern portion of the state where lakes have higher concentrations of water chemistry variables including alkalinity, conductivity, pH, calcium, magnesium, and nitrogen. This creates a complex gradient that influences species composition of macrophyte communities from lake to lake.

Wisconsin↗

Mercury accumulation in Devils Lake, North Dakota effects of environmental variation in closed-basin lakes on mercury chronologies

Sediment cores were collected from lakes in the Devils Lake Basin in North Dakota to determine if mercury (Hg) accumulation chronologies from sediment-core data are good indicators of variations in Hg accumulation rates in saline lakes. Sediment cores from Creel Bay and Main Bay, Devils Lake were selected for detailed analysis and interpretation. The maximum Hg concentration in the Creel Bay core was 0.15 micrograms per gram at 8 to 9 centimeters. The maximum Hg concentration in the Main Bay core was 0.07 micrograms per gram at 5 to 7 centimeters. The general decreases in Hg concentrations with depth are attributed to historic variations in atmospheric Hg deposition rate. Hg stratigraphies combined with 210Pb and 137Cs dating analyses yield Hg chronologies that indicate a general increase in Hg accumulation rates in Devils Lake since the middle of the 19th century. Mean modern Hg accumulation rates in Creel Bay were 4.9 nanograms per square centimeter per year, and rates in Main Bay were 1.8 nanograms per square centimeter per year. Mean preindustrial Hg accumulation rates in Creel Bay were 1.2 nanograms per square centimeter per year, and rates in Main Bay were 1.6 nanograms per square centimeter per year. Relatively low Hg concentrations in recent sediments in the Devils Lake Basin, along with similarities in Hg accumulation rates between lakes in the Devils Lake Basin and other lakes in the northern interior of North America, indicate that local sources of Hg are not important sources of Hg. Results of the study indicate that accurate Hg chronologies are discernible in sediment cores collected from saline lakes. However, spatial and temporal variations in lake level and water chemistry common to saline lakes make interpretation of radioisotopic and geochemical chronologies difficult. Hg geochemistry in Devils Lake, and presumably in other saline lakes, is dynamic. The results of this study indicate that the absolute amount of sediment transported to Devils Lake, along with the associated Hg and total organic carbon, and the distribution of sedimentation patterns in Devils Lake may be affected by changing lake levels.

Water, Air, & Soil Pollution↗

Complex mixtures, complex responses: Assessing pharmaceutical mixtures using field and laboratory approaches

Pharmaceuticals are present in low concentrations (<100&thinsp;ng/L) in most municipal wastewater effluents but may be elevated locally because of factors such as input from pharmaceutical formulation facilities. Using existing concentration data, the authors assessed pharmaceuticals in laboratory exposures of fathead minnows ( Pimephales promelas ) and added environmental complexity through effluent exposures. In the laboratory, larval and mature minnows were exposed to a simple opioid mixture (hydrocodone, methadone, and oxycodone), an opioid agonist (tramadol), a muscle relaxant (methocarbamol), a simple antidepressant mixture (fluoxetine, paroxetine, venlafaxine), a sleep aid (temazepam), or a complex mixture of all compounds. Larval minnow response to effluent exposure was not consistent. The 2010 exposures resulted in shorter exposed minnow larvae, whereas the larvae exposed in 2012 exhibited altered escape behavior. Mature minnows exhibited altered hepatosomatic indices, with the strongest effects in females and in mixture exposures. In addition, laboratory-exposed, mature male minnows exposed to all pharmaceuticals (except the selective serotonin reuptake inhibitor mixture) defended nest sites less rigorously than fish in the control group. Tramadol or antidepressant mixture exposure resulted in increased splenic T lymphocytes. Only male minnows exposed to whole effluent responded with increased plasma vitellogenin concentrations. Female minnows exposed to pharmaceuticals (except the opioid mixture) had larger livers, likely as a compensatory result of greater prominence of vacuoles in liver hepatocytes. The observed alteration of apical endpoints central to sustaining fish populations confirms that effluents containing waste streams from pharmaceutical formulation facilities can adversely impact fish populations but that the effects may not be temporally consistent. The present study highlights the importance of including diverse biological endpoints spanning levels of biological organization and life stages when assessing contaminant interactions.

Environmental Toxicology and Chemistry↗

Effects of urbanization on stream ecosystems in the Willamette River basin and surrounding area, Oregon and Washington

This report describes the effects of urbanization on physical, chemical, and biological characteristics of stream ecosystems in 28 watersheds along a gradient of urbanization in the Willamette River basin and surrounding area, Oregon and Washington, from 2003 through 2005. The study that generated the report is one of several urban-effects studies completed nationally by the U.S. Geological Survey National Water-Quality Assessment Program. Watersheds were selected to minimize natural variability caused by factors such as geology, elevation, and climate, and to maximize coverage of different stages of urban development among watersheds. Because land use or population density alone often are not a complete measure of urbanization, a combination of land use, land cover, infrastructure, and socioeconomic variables were integrated into a multimetric urban intensity index (UII) to represent the degree of urban development in each watershed. Physical characteristics studied include stream hydrology, stream temperature, and habitat; chemical characteristics studied include sulfate, chloride, nutrients, pesticides, dissolved and particulate organic and inorganic carbon, and suspended sediment; and biological characteristics studied include algal, macroinvertebrate, and fish assemblages. Semipermeable membrane devices, passive samplers that concentrate trace levels of hydrophobic organic contaminants such as polycyclic aromatic hydrocarbons and polychlorinated biphenyls, also were used. The objectives of the study were to (1) examine physical, chemical, and biological responses along the gradient of urbanization and (2) determine the major physical, chemical, and landscape variables affecting the structure of aquatic communities. Common effects documented in the literature of urbanization on instream physical, chemical, and biological characteristics, such as increased contaminants, increased streamflow flashiness, increased concentrations of chemicals, and changes in aquatic community structure toward a more tolerant community associated with organically enriched conditions, generally were observed in this study. The strongest correlations to the UII and to many of the algal, macroinvertebrate, and fish assemblage metrics and community ordination involved water-chemistry metrics including the total pesticide concentration, toxic equivalents (extract assay from semipermeable membrane devices), and dissolved oxygen. Hydrologic variability metrics, such as flashiness, that normally are considered to be one of the main processes of urban disturbance had a strong association to the algal and fish assemblages in this study; however, the hydrologic variables for macroinvertebrates were secondary to the water-chemistry metrics mentioned above. Generally, the high urban intensity sites had high abundances of eutrophic and lower dissolved oxygen-indicating diatoms, high abundances of noninsects and tolerant insects, and high abundances of nonnative fish species. On the other hand, the low urban intensity sites had higher abundances of pollution sensitive diatoms, larger numbers of the sensitive macroinvertebrate EPT taxa (Ephemeroptera, Plecoptera and Trichoptera Orders), and fish assemblages with higher abundances of sensitive salmonids. The percent salmonid and macroinvertebrate EPT richness metrics plotted against the UII indicated a possible threshold response at about 25 on the UII, which is equivalent to an impervious surface value of about 5 percent. However, due to the added agricultural land use at sites within the 25 to 60 UII range, this possible threshold probably is not solely due to urbanization, but a combination of urban and agricultural land use. The effects of agricultural and urban land use could not be distinguished from each other, yet combined they provide a good assessment of overall watershed disturbance.

Oregon, Washington↗

Surface-water-quality data to support implementation of revised freshwater aluminum water-quality criteria in Massachusetts, 2018–19

The U.S. Geological Survey, in cooperation with the Massachusetts Department of Environmental Protection, performed a study to inform the development of the department’s guidelines for the collection and use of water-chemistry data to support calculation of site-dependent aluminum criteria values. The U.S. Geological Survey collected and analyzed discrete water-quality samples at four wastewater-treatment facilities and seven water-treatment facilities in eastern and central Massachusetts from April 2018 through May 2019. For each of the 11 facilities considered, water-quality samples were collected from treatment-plant effluent and receiving-water bodies. Samples were collected for laboratory analysis of major ions (calcium and magnesium ions are used to calculate total hardness), dissolved organic carbon (DOC), total organic carbon (TOC), and total recoverable aluminum. Field parameters for pH, temperature, and specific conductance were measured in situ concurrently with sample collection. Water-quality conditions differed among monitoring stations. The highest pH values were observed for stations on the Assabet River that receive effluent discharges from wastewater-treatment facilities (the Westborough, Marlborough, Hudson, and Maynard wastewater-treatment facilities). High DOC concentrations (greater than 10 mg/L) were measured in water bodies associated with large areas of riparian wetlands—Lily Pond (Cohasset) and Third Herring Brook (Hanover), and low DOC concentrations (less than 2.5 mg/L) were measured at three water bodies in central Massachusetts—Hocomonco Pond (Westborough), Wyman Pond (Fitchburg), and Monoosnoc Brook (Leominster). Wyman Pond (Fitchburg), Monoosnoc Brook (Leominster), and Lily Pond (Cohasset) also had low pH values and low total hardness concentrations. The monthly discrete pH, DOC, and total hardness data for selected stations on receiving-water bodies were used in the U.S. Environmental Protection Agency Aluminum Criteria Calculator Version 2.0 to estimate site-dependent total recoverable aluminum concentrations that—if not exceeded—would be expected to protect fish, invertebrates, and other aquatic life from adverse effects associated with acute and chronic aluminum exposures. The U.S. Environmental Protection Agency Calculator output provides values for the acute criterion, defined as the criterion maximum concentration (CMC), an estimate of the highest aluminum concentration in surface water to which an aquatic community can be exposed briefly without resulting in an unacceptable effect. This output also provides values for the chronic criterion, defined as the criterion continuous concentration (CCC), an estimate of the highest concentration of aluminum in surface water to which an aquatic community can be exposed indefinitely without resulting in an unacceptable effect. To determine aluminum criteria values typically evaluated for use as protective water-quality criteria, the monthly instantaneous CMC and CCC values were used to calculate the minimum, 5th percentile, and 10th percentile CMC and CCC values for selected monitoring stations. The monthly instantaneous aluminum CMC and CCC values generated using the EPA Calculator varied among stations. Aluminum CMC and CCC values were highest for four ambient (upstream) stations on the Assabet River associated with wastewater-treatment facilities (Westborough, Marlboro, Hudson, and Maynard). Aluminum CMC and CCC values were lower for stations associated with water-treatment facilities, and lowest for selected ambient stations on Lily Pond, Monoosnoc Brook, and Wyman Pond associated with water-treatment facilities in Cohasset, Leominster, and Fitchburg, respectively. For many stations, the highest CMC and CCC instantaneous aluminum criteria values generated using the U.S. Environmental Protection Agency Calculator were for months during the growing season for algae and aquatic macrophytes (April or May through September or October) and the lowest values were for months during the nongrowing season (October or November through March or April), indicating the importance of collecting water-quality data during the nongrowing season. Aluminum CMC and CCC values generated by the U.S. Environmental Protection Agency Calculator are sensitive to variations in the input parameters (pH, DOC, and total hardness). Aluminum solubility is particularly affected by pH. To characterize diel and seasonal variations in pH, multiparameter water-quality monitors recording continuous (15-minute interval) water temperature and pH were installed in the receiving-water body for one station near each facility upstream from the effluent discharge (in rivers) or at a station outside the immediate effect of effluent discharge (in ponds). Continuous water temperature and pH data were collected from April or May 2018 through November or December 2018. Continuous pH data indicated that the pond stations and Assabet River stations had large diel variations in pH during the growing season. Continuous pH data were used together with discrete DOC and total hardness data to evaluate the potential effect of diel variations in pH on calculated site-dependent aluminum criteria values. For the 11 stations, diel variations in pH were determined to correspond to differences in the 10th percentile of CMC values by a median of 160 μg/L, ranging from 0 to 610 μg/L, and differences in the 10th percentile of CCC values by a median of 40 μg/L, ranging from 15 to 210 μg/L. The low monthly instantaneous CMC and CCC values that have the greatest effect on the minimum, 5th percentile, and 10th percentile aluminum values tend to result during the nongrowing season (October or November through March or April) when the range of diel variations in pH is small, thus minimizing the effect of diel variations in pH on the lowest CMC and CCC values. Historical water-quality data on organic carbon in Massachusetts streams were investigated using data retrieved from the USGS National Water Information System database. An assessment of the availability of historical pH, DOC, and hardness data indicated that more data were available for TOC than for DOC. A linear regression equation was developed for the relation between DOC and TOC concentrations to inform the potential use of available data to evaluate water-quality conditions at additional sites across Massachusetts where only pH, hardness, and TOC data are available. DOC and TOC concentrations were well correlated in the 223 samples in which both constituents were analyzed, and the equation had a coefficient of determination ( R 2 ) equal to 0.93.

Massachusetts↗

A comparison of the chemical sensitivities between in vitro and in vivo propagated juvenile freshwater mussels: Implications for standard toxicity testing

Unionid mussels are ecologically important and are globally imperiled. Toxicants contribute to mussel declines, and toxicity tests using juvenile mussels—a sensitive life stage—are valuable in determining thresholds used to set water quality criteria. In vitro culture methods provide an efficient way to propagate juveniles for toxicity testing, but their relative chemical sensitivity compared with in vivo propagated juveniles is unknown. Current testing guidelines caution against using in vitro cultured juveniles until this sensitivity is described. Our objective was to evaluate the relative sensitivity of juvenile mussels produced from both in vitro and in vivo propagation methods to selected chemicals. We conducted 96-h acute toxicity tests according to ASTM International guidelines with 3 mussel species and 6 toxicants: chloride, nickel, ammonia, and 3 copper-based compounds. Statistically significant differences between in vitro and in vivo juvenile 96-h median effect concentrations were observed in 8 of 17 tests, and in vitro juveniles were more sensitive in 6 of the 8 significant differences. At 96 h, 4 of the 8 statistically different tests for a given chemical were within a factor of 2, which is the intralaboratory variation demonstrated in a recent evaluation of mussel toxicity tests. We found that although differences in chemical sensitivity exist between in vitro and in vivo propagated juvenile mussels, they are within normal toxicity test variation. Therefore, in vitro propagated juvenile mussels may be appropriate for use in ASTM International-based toxicity testing.

Environmental Toxicology and Chemistry↗

Acute Toxicity of 4-hydroxydiphenylamine (4-HDPA) and N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone (6PPDQ), transformation products of 6PPD, to early instars of the mayfly, Neocloeon triangulifer

Our analysis of water samples collected during a rain event from two urban rivers in the Greater Toronto area, Ontario, Canada, indicated that selected transformation products (TPs) of the tire antioxidant, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), including 6PPD-quinone (6PPDQ) and 4-hydroxydiphenylamine (4-HDPA), were present at concentrations >1 µg/L. In acute (96-hr) toxicity tests with aquatic larvae of the mayfly Neocloeon triangulifer , 6PPDQ did not cause mortalities at the highest test concentration, which was just below the limit of solubility. In toxicity tests with 4-HDPA, a calculated 96-hr median lethal concentration of 339 µg/L is above environmentally relevant concentrations. However, in toxicity tests with 6PPD, there was evidence that the degradation of this tire wear compound produced unknown TPs that caused mortalities in exposed mayfly larvae. Additional work could identify other TPs of 6PPD that could be a hazard to aquatic invertebrates exposed to tire wear compounds transported into surface waters from transportation corridors.

Ontario↗

Water-Quality Conditions of Chester Creek, Anchorage, Alaska, 1998-2001

Between October 1998 and September 2001, the U.S. Geological Survey's National Water-Quality Assessment Program evaluated the water-quality conditions of Chester Creek, a stream draining forest and urban settings in Anchorage, Alaska. Data collection included water, streambed sediments, lakebed sediments, and aquatic organisms samples from urban sites along the stream. Urban land use ranged from less than 1 percent of the basin above the furthest upstream site to 46 percent above the most downstream site. Findings suggest that water quality of Chester Creek declines in the downstream direction and as urbanization in the watershed increases. Water samples were collected monthly and during storms at a site near the stream's mouth (Chester Creek at Arctic Boulevard) and analyzed for major ions and nutrients. Water samples collected during water year 1999 were analyzed for selected pesticides and volatile organic compounds. Concentrations of fecal-indicator bacteria were determined monthly during calendar year 2000. During winter, spring, and summer, four water samples were collected at a site upstream of urban development (South Branch of South Fork Chester Creek at Tank Trail) and five from an intermediate site (South Branch of South Fork Chester Creek at Boniface Parkway). Concentrations of calcium, magnesium, sodium, chloride, and sulfate in water increased in the downstream direction. Nitrate concentrations were similar at the three sites and all were less than the drinking-water standard. About one-quarter of the samples from the Arctic Boulevard site had concentrations of phosphorus that exceeded the U.S. Environmental Protection Agency (USEPA) guideline for preventing nuisance plant growth. Water samples collected at the Arctic Boulevard site contained concentrations of the insecticide carbaryl that exceeded the guideline for protecting aquatic life. Every water sample revealed a low concentration of volatile organic compounds, including benzene, toluene, tetrachloroethylene, methyl tert-butyl ether, and chloroform. No water samples contained volatile organic compounds concentrations that exceeded any USEPA drinking-water standard or guideline. Fecal-indicator bacteria concentrations in water from the Arctic Boulevard site commonly exceeded Federal and State guidelines for water-contact recreation. Concentrations of cadmium, copper, lead, and zinc in streambed sediments increased in the downstream direction. Some concentrations of arsenic, chromium, lead, and zinc in sediments were at levels that can adversely affect aquatic organisms. Analysis of sediment chemistry in successive lakebed-sediment layers from Westchester Lagoon near the stream's mouth provided a record of water-quality trends since about 1970. Concentrations of lead have decreased from peak levels in the mid-1970s, most likely because of removing lead from gasoline and lower lead content in other products. However, concen-trations in recently-deposited lakebed sediments are still about 10 times greater than measured in streambed sediments at the upstream Tank Trail site. Zinc concentrations in lakebed sediments also increased in the early 1970s to levels that exceeded guidelines to protect aquatic life and have remained at elevated but variable levels. Pyrene, benz[a]anthracene, and phenanthrene in lakebed sediments also have varied in concentrations and have exceeded protection guidelines for aquatic life since the 1970s. Concentrations of dichloro-diphenyl-trichloroethane, polychlorinated biphenyls (PCBs), or their by-products generally were highest in lakebed sediments deposited in the 1970s. More recent sediments have concentrations that vary widely and do not show distinct temporal trends. Tissue samples of whole slimy sculpin (Cottus cognatus), a non-migratory species of fish, showed con-centrations of trace elements and organic contaminants. Of the constituents analyzed, only selenium concentra-tions showed levels of potential concern for

Scientific Investigations Report↗

Properties and potential environmental applications of carbon adsorbents from waste tire rubber

The properties of tire-derived carbon adsorbents (TDCA) produced from select tire chars were compared with those derived from an Illinois coal and pistachio nut shells. Chemical analyses of the TDCA indicated that these materials contain metallic elements not present in coal-and nut shell-derived carbons. These metals, introduced during the production of tire rubber, potentially catalyze steam gasification reactions of tire char. TDCA carbons contained larger meso-and macopore volumes than their counterparts derived from coal and nut shell (on the moisture-and ash-free-basis). Adsorptive properties of the tire-derived adsorbent carbons for air separation, gas storage, and gas clean up were also evaluated and compared with those of the coal-and nut shell derived carbons as well as a commercial activated carbon. The results revealed that TDCA carbons are suitable adsorbents for removing vapor-phase mercury from combustion flue gases and hazardous organic compounds from industrial gas streams.

ACS Division of Fuel Chemistry, Preprints↗

Environmental drivers of differences in microbial community structure in crude oil reservoirs across a methanogenic gradient

Stimulating in situ microbial communities in oil reservoirs to produce natural gas is a potentially viable strategy for recovering additional fossil fuel resources following traditional recovery operations. Little is known about what geochemical parameters drive microbial population dynamics in biodegraded, methanogenic oil reservoirs. We investigated if microbial community structure was significantly impacted by the extent of crude oil biodegradation, extent of biogenic methane production, and formation water chemistry. Twenty-two oil production wells from north central Louisiana, USA, were sampled for analysis of microbial community structure and fluid geochemistry. Archaea were the dominant microbial community in the majority of the wells sampled. Methanogens, including hydrogenotrophic and methylotrophic organisms, were numerically dominant in every well, accounting for, on average, over 98% of the total Archaea present. The dominant Bacteria groups were Pseudomonas, Acinetobacter , Enterobacteriaceae, and Clostridiales, which have also been identified in other microbially-altered oil reservoirs. Comparing microbial community structure to fluid (gas, water, and oil) geochemistry revealed that the relative extent of biodegradation, salinity, and spatial location were the major drivers of microbial diversity. Archaeal relative abundance was independent of the extent of methanogenesis, but closely correlated to the extent of crude oil biodegradation; therefore, microbial community structure is likely not a good sole predictor of methanogenic activity, but may predict the extent of crude oil biodegradation. However, when the shallow, highly biodegraded, low salinity wells were excluded from the statistical analysis, no environmental parameters could explain the differences in microbial community structure. This suggests that the microbial community structure of the 5 shallow, up-dip wells was different than the 17 deeper, down-dip wells. Also, the 17 down-dip wells had statistically similar microbial communities despite significant changes in environmental parameters between oil fields. Together, this implies that no single microbial population is a reliable indicator of a reservoir's ability to degrade crude oil to methane, and that geochemistry may be a more important indicator for selecting a reservoir suitable for microbial enhancement of natural gas generation.

Louisiana↗

Evaluation of the sensitivity of a federally endangered freshwater mussel (Venustaconcha trabalis) to selected chemicals

Protection of critically endangered species requires identification of factors limiting their survival and growth. Previous studies have demonstrated that unionid mussels are sensitive to some chemicals and the sensitivity was similar among different taxonomic families and tribes of mussels. However, common species of mussels were generally used in these previous studies; little is known about the sensitivity of endangered and threatened mussels relative to common species. The objective of this study was to evaluate the sensitivity of a critically endangered mussel (Tennessee bean, Venustaconcha trabalis ) to seven chemicals with different modes of toxic action (ammonia, chloride, nitrite, potassium, cobalt, manganese, nickel) in acute 96-h exposures and to three chemicals (nitrite, cobalt, iron) in chronic 28-d exposures conducted following standard methods. A commonly tested mussel (fatmucket, Lampsilis siliquoidea ) was also tested side-by-side with Tennessee bean in chronic exposures. Test chemicals were selected based on (1) chemicals of potential concern found in a review of existing data for the river where a population of Tennessee bean occurs or was historically present, (2) chemicals to which other mussels are sensitive, or (3) chemicals that had not been previously tested with mussels. Acute 50% effect concentrations (EC50s) for the seven chemicals from the Tennessee bean tests were within or close to the range of EC50s for other mussel species tested in previous studies, and chronic 20% effect concentrations for the three chemicals were similar between Tennessee bean and fatmucket, indicating the endangered species has sensitivity similar to other tested mussel species. Inclusion of the new mussel data in existing toxicity databases for freshwater organisms would rank one or more mussel species among the four most sensitive species to ammonia, chloride, potassium, and nickel in acute exposures and to nitrite, cobalt, and iron in chronic exposures.

Environmental Toxicology and Chemistry↗

Study and interpretation of the chemical characteristics of natural water

The chemical composition of natural water is derived from many different sources of solutes, including gases and aerosols from the atmosphere, weathering and erosion of rocks and soil, solution or precipitation reactions occurring below the land surface, and cultural effects resulting from activities of man. Some of the processes of solution or precipitation of minerals can be closely evaluated by means of principles of chemical equilibrium including the law of mass action and the Nernst equation. Other processes are irreversible and require consideration of reaction mechanisms and rates. The chemical composition of the crustal rocks of the earth and the composition of the ocean and the atmosphere are significant in evaluating sources of solutes in natural fresh water. The ways in which solutes are taken up or precipitated and the amounts present in solution are influenced by many environmental factors, especially climate, structure and position: of rock strata, and biochemical effects associated with life cycles of plants and animals, both microscopic and macroscopic. Taken all together and in application with the further influence of the general circulation of all water in the hydrologic cycle, the chemical principles and environmental factors form a basis for the developing science of natural-water chemistry. Fundamental data used in the determination of water quality are obtained by the chemical analysis of water samples in the laboratory or onsite sensing of chemical properties in the field. Sampling is complicated by changes in composition of moving water and the effects of particulate suspended material. Most of the constituents determined are reported in gravimetric units, usually milligrams per liter or milliequivalents per liter. More than 60 constituents and properties are included in water analyses frequently enough to provide a basis for consideration of the sources from which each is generally derived, most probable forms of elements and ions in solution, solubility controls, expected concentration ranges and other chemical factors. Concentrations of elements that are commonly present in amounts less than a few tens of micrograms per liter cannot always be easily explained, but present information suggests many are controlled by solubility of hydroxide or carbonate or by sorption on solid particles. Chemical analyses may be grouped and statistically evaluated by averages, frequency distributions, or ion correlations to summarize large volumes of data. Graphing of analyses or of groups of analyses aids in showing chemical relationships among waters, probable sources of solutes, areal water-quality regimen, and water-resources evaluation. Graphs may show water type based on chemical composition, relationships among ions, or groups of ions in individual waters or many waters considered simultaneously. The relationships of water quality to hydrologic parameters, such as stream discharge rate or ground-water flow patterns, can be shown by mathematical equations, graphs, and maps. About 75 water analyses selected from the literature are tabulated to illustrate the relationships described, and some of these, along with many others that are not tabulated, are also utilized in demonstrating graphing and mapping techniques. Relationships of water composition to source rock type are illustrated by graphs of some of the tabulated analyses. Activities of man may modify water composition extensively through direct effects of pollution and indirect results of water development, such as intrusion of sea water in ground-water aquifiers. Water-quality standards for domestic, agricultural, and industrial use have been published by various agencies. Irrigation project requirements for water quality are particularly intricate. Fundamental knowledge of processes that control natural water composition is required for rational management of water quality.

Water Supply Paper↗

Study and interpretation of the chemical characteristics of natural water

The chemical composition of natural water is derived from many different sources of solutes, including gases and aerosols from the atmosphere, weathering and erosion of rocks and soil, solution or precipitation reactions occurring below the land surface, and cultural effects resulting from activities of man. Some of the processes of solution or precipitation of minerals can be closely evaluated by means of principles of chemical equilibrium including the law of mass action and the Nernst equation. Other processes are irreversible and require consideration of reaction mechanisms and rates. The chemical composition of the crustal rocks of the earth and the composition of the ocean and the atmosphere are significant in evaluating sources of solutes in natural fresh water. The ways in which solutes are taken up or precipitated and the amounts present in solution are influenced by many environmental factors, especially climate, structure and position: of rock strata, and biochemical effects associated with life cycles of plants and animals, both microscopic and macroscopic. Taken all together and in application with the further influence of the general circulation of all water in the hydrologic cycle, the chemical principles and environmental factors form a basis for the developing science of natural-water chemistry. Fundamental data used in the determination of water quality are obtained by the chemical analysis of water samples in the laboratory or onsite sensing of chemical properties in the field. Sampling is complicated by changes in composition of moving water and the effects of particulate suspended material. Most of the constituents determined are reported in gravimetric units, usually milligrams per liter or milliequivalents per liter. More than 60 constituents and properties are included in water analyses frequently enough to provide a basis for consideration of the sources from which each is generally derived, most probable forms of elements and ions in solution, solubility controls, expected concentration ranges and other chemical factors. Concentrations of elements that are commonly present in amounts less than a few tens of micrograms per liter cannot always be easily explained, but present information suggests many are controlled by solubility of hydroxide or carbonate or by sorption on solid particles. Chemical analyses may be grouped and statistically evaluated by averages, frequency distributions, or ion correlations to summarize large volumes of data. Graphing of analyses or of groups of analyses aids in showing chemical relationships among waters, probable sources of solutes, areal water-quality regimen, and water-resources evaluation. Graphs may show water type based on chemical composition, relationships among ions, or groups of ions in individual waters or many waters considered simultaneously. The relationships of water quality to hydrologic parameters, such as stream discharge rate or ground-water flow patterns, can be shown by mathematical equations, graphs, and maps. About 75 water analyses selected from the literature are tabulated to illustrate the relationships described, and some of these, along with many others that are not tabulated, are also utilized in demonstrating graphing and mapping techniques. Relationships of water composition to source rock type are illustrated by graphs of some of the tabulated analyses. Activities of man may modify water composition extensively through direct effects of pollution and indirect results of water development, such as intrusion of sea water in ground-water aquifiers. Water-quality standards for domestic, agricultural, and industrial use have been published by various agencies. Irrigation project requirements for water quality are particularly intricate. Fundamental knowledge of processes that control natural water composition is required for rational management of water quality.

Water Supply Paper↗