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Chemicals of emerging concern in water and bottom sediment in the Great Lakes Basin, 2012: collection methods, analytical methods, quality assurance, and study data
In synoptic surveys of surface-water quality across the United States, a large group of organic chemicals associated with agricultural, household, and industrial waste have been detected. These chemicals are referred to collectively as chemicals of emerging concern (CECs) and include prescription drugs and antibiotics, over-the-counter medications, reproductive hormones, personal-care products, detergent metabolites, and flame retardants. The U.S. Geological Survey (USGS) collaborated with the U.S. Fish and Wildlife Service and the U.S. Environmental Protection Agency on a study to identify the presence of CECs in water and bottom-sediment samples collected during 2012 at 66 sites throughout the Great Lakes Basin. The 2012 effort is part of a long-term study that was initiated in 2010. The purposes of this report are to document the collection and analytical methods, provide the quality-assurance data and analyses, and provide the water and bottom-sediment data for this study of CECs in the Great Lakes Basin for 2012. A previous report documents data collected during 2010 and 2011. The methods used for chemical analyses were identical between the 2010–11 and 2012 studies, with the exception that a method to determine nontarget chemicals was used during 2010–11. The data from this study are published as a USGS Data Series Report to ensure adequate documentation of the original methods and provide a citable source for study data. This report contains no interpretations of the study data. The chemical data are as reported by the laboratory and have not been censored or adjusted unless otherwise noted. Field measurements were recorded and samples were collected in April and May and in September 2012, by U.S. Geological Survey, U.S. Fish and Wildlife Service, and U.S. Environmental Protection Agency personnel. Study sites included tributaries to the Great Lakes located near Duluth, Minnesota; King, Wisconsin; Green Bay, Wis.; Detroit, Michigan; Monroe, Mich.; Toledo, Ohio, and Rochester, New York. Water and bottom-sediment samples were analyzed at the USGS National Water Quality Laboratory in Denver, Colorado, for a broad suite of CECs. During this 2012 study, 140 environmental and 8 field duplicate samples of surface water and wastewater effluent, 1 field blank water sample, and 5 field spike water samples were collected or prepared. Water samples were analyzed at the USGS National Water Quality Laboratory using laboratory schedule 4433 for wastewater indicators, research method 8244 for pharmaceuticals, and laboratory schedule 4434 for steroid hormones, sterols, and bisphenol A. For wastewater indicators in unfiltered water, 61 of the 68 chemicals analyzed using laboratory schedule 4433 had detectable concentrations ranging from 0.002 to 64.4 micrograms per liter. Thirty-eight of the 48 chemicals analyzed using research method 8244 for pharmaceuticals in unfiltered water had detectable concentrations ranging from 0.002 to 3.32 micrograms per liter. Twelve of the 20 chemicals analyzed using laboratory schedule 4434 for steroid hormones, sterols, and bisphenol A in unfiltered water had detectable concentrations ranging from 0.43 to 120,000 nanograms per liter. During this study, 53 environmental samples, 4 field duplicate samples, and 8 field spike samples of bottom sediment and laboratory matrix-spike samples were analyzed for a wide variety of CECs at the USGS National Water Quality Laboratory using laboratory schedule 5433 for wastewater indicators; research method 6434 for steroid hormones, sterols, and bisphenol A; and research method 9008 for human-use pharmaceuticals and antidepressants. Forty of the 57 chemicals analyzed using laboratory schedule 5433 had detectable concentrations ranging from 1 to 49,000 micrograms per kilogram. Fourteen of the 20 chemicals analyzed using research method 6434 had detectable concentrations ranging from 0.04 to 24,940 nanograms per gram. Ten of the 20 chemicals analyzed using research method 9008 had detectable concentrations ranging from 0.59 to 197.5 micrograms per kilogram. Five of the 11 chemicals analyzed using research method 9008 had detectable concentrations ranging from 1.16 to 25.0 micrograms per kilogram.
Pesticides in near-surface aquifers: An assessment using highly sensitive analytical methods and tritium
In 1992, the U.S. Geological Survey (USGS) determined the distribution of pesticides in near-surface aquifers of the midwestern USA to be much more widespread than originally determined during a 1991 USGS study. The frequency of pesticide detection increased from 28.4% during the 1991 study to 59.0% during the 1992 study. This increase in pesticide detection was primarily the result of a more sensitive analytical method that used reporting limits as much as 20 times lower than previously available and a threefold increase in the number of pesticide metabolites analyzed. No pesticide concentrations exceeded the U.S. Environmental Protection Agency's (USEPAs) maximum contaminant levels or health advisory levels for drinking water. However, five of the six most frequently detected compounds during 1992 were pesticide metabolites that currently do not have drinking water standards determined. The frequent presence of pesticide metabolites for this study documents the importance of obtaining information on these compounds to understand the fate and transport of pesticides in the hydrologic system. It appears that the 56 parent compounds analyzed follow similar pathways through the hydrologic system as atrazine. When atrazine was detected by routine or sensitive analytical methods, there was an increased likelihood of detecting additional parent compounds. As expected, the frequency of pesticide detection was highly dependent on the analytical reporting limit. The number of atrazine detections more than doubled as the reporting limit decreased from 0.10 to 0.01 µg/L. The 1992 data provided no indication that the frequency of pesticide detection would level off as improved analytical methods provide concentrations below 0.003 µg/L. A relation was determined between groundwater age and the frequency of pesticide detection, with 15.8% of the samples composed of pre-1953 water and 70.3% of the samples of post-1953 water having a detection of at least one pesticide or metabolite. Pre-1953 water is less likely to contain pesticides because it tends to predate the use of pesticides to increase crop production in the Midwest. Pre-1953 water was more likely to occur in the near-surface bedrock aquifers (50.0%) than in the near-surface unconsolidated aquifers (9.1%) sampled.
Sediment studies in the Assabet River, central Massachusetts, 2003
From its headwaters in Westborough, Massachusetts, to its confluence with the Sudbury River, the 53-kilometer-long Assabet River passes through a series of small towns and mixed land-use areas. Along the way, wastewater-treatment plants release nutrient-rich effluents that contribute to the eutrophic state of this waterway. This condition is most obvious where the river is impounded by a series of dams that have sequestered large amounts of sediment and support rooted and floating macrophytes and epiphytic algae. The water in parts of these impoundments may also have low concentrations of dissolved oxygen, another symptom of eutrophication. All of the impoundments had relatively shallow maximum water depths, which ranged from approximately 2.4 to 3.4 meters, and all had extensive shallow areas. Sediment volumes estimated for the six impoundments ranged from approximately 380 cubic meters in the Aluminum City impoundment to 580,000 cubic meters in the Ben Smith impoundment. The other impoundments had sediment volumes of 120,000 cubic meters (Powdermill), 67,000 cubic meters (Gleasondale), 55,000 cubic meters (Hudson), and 42,000 cubic meters (Allen Street). The principal objective of this study was the determination of sediment volume, extent, and chemistry, in particular, the characterization of toxic inorganic and organic chemicals in the sediments. To determine the bulk-sediment chemical-constituent concentrations, more than one hundred sediment cores were collected in pairs from the six impoundments. One core from each pair was sampled for inorganic constituents and the other for organic constituents. Most of the cores analyzed for inorganics were sectioned to provide information on the vertical distribution of analytes; a subset of the cores analyzed for organics was also sectioned. Approximately 200 samples were analyzed for inorganic constituents and 100 for organics; more than 10 percent were quality-control replicate or blank samples. Maximum bulk-sediment phosphorus concentrations in surface samples from the impoundments increased along a downstream gradient, with the exception of samples from the last impoundment, where the concentrations decreased. In addition, the highest phosphorus concentrations were generally in the surface samples; this finding may prove helpful if surface dredging is selected as a means to control phosphorus release from sediments. There is no known relation, however, between bulk-sediment concentration of phosphorus and the concentrations of phosphorus available to biota. Potentially toxic metals, including arsenic, cadmium, chromium, copper, nickel, lead, and zinc were frequently measured at concentrations that exceeded U.S. Environmental Protection Agency sediment-quality guidelines for the protection of aquatic life and that occasionally exceeded Massachusetts Department of Environmental Protection guidelines governing landfill disposal (reuse). Due to the effects of matrix interference and sample dilution on laboratory analyses, neither pesticides nor volatile organic compounds were detected at any sites. However, samples collected in other studies from nearby streams indicated the possibility that pesticides might have been detected in the impoundments if not for these analytical problems. Although polychlorinated biphenyl concentrations, as individual Aroclors, generally exceeded published U.S. Environmental Protection Agency guideline concentrations for potential effects on aquatic life, the U.S. Environmental Protection Agency guideline concentrations for human contact or the Massachusetts guidelines for landfill reuse were rarely exceeded. Concentrations of polycyclic aromatic hydrocarbons, both individually and total, frequently were greater than guideline concentrations. Concentrations of total extractable petroleum hydrocarbons did not exceed Massachusetts guideline concentrations in any samples. When the sediment analytes from surface samples are considered togethe
Prioritizing pesticide compounds for analytical methods development
The U.S. Geological Survey (USGS) has a periodic need to re-evaluate pesticide compounds in terms of priorities for inclusion in monitoring and studies and, thus, must also assess the current analytical capabilities for pesticide detection. To meet this need, a strategy has been developed to prioritize pesticides and degradates for analytical methods development. Screening procedures were developed to separately prioritize pesticide compounds in water and sediment. The procedures evaluate pesticide compounds in existing USGS analytical methods for water and sediment and compounds for which recent agricultural-use information was available. Measured occurrence (detection frequency and concentrations) in water and sediment, predicted concentrations in water and predicted likelihood of occurrence in sediment, potential toxicity to aquatic life or humans, and priorities of other agencies or organizations, regulatory or otherwise, were considered. Several existing strategies for prioritizing chemicals for various purposes were reviewed, including those that identify and prioritize persistent, bioaccumulative, and toxic compounds, and those that determine candidates for future regulation of drinking-water contaminants. The systematic procedures developed and used in this study rely on concepts common to many previously established strategies. The evaluation of pesticide compounds resulted in the classification of compounds into three groups: Tier 1 for high priority compounds, Tier 2 for moderate priority compounds, and Tier 3 for low priority compounds. For water, a total of 247 pesticide compounds were classified as Tier 1 and, thus, are high priority for inclusion in analytical methods for monitoring and studies. Of these, about three-quarters are included in some USGS analytical method; however, many of these compounds are included on research methods that are expensive and for which there are few data on environmental samples. The remaining quarter of Tier 1 compounds are high priority as new analytes. The objective for analytical methods development is to design an integrated analytical strategy that includes as many of the Tier 1 pesticide compounds as possible in a relatively few, cost-effective methods. More than 60 percent of the Tier 1 compounds are high priority because they are anticipated to be present at concentrations approaching levels that could be of concern to human health or aquatic life in surface water or groundwater. An additional 17 percent of Tier 1 compounds were frequently detected in monitoring studies, but either were not measured at levels potentially relevant to humans or aquatic organisms, or do not have benchmarks available with which to compare concentrations. The remaining 21 percent are pesticide degradates that were included because their parent pesticides were in Tier 1. Tier 1 pesticide compounds for water span all major pesticide use groups and a diverse range of chemical classes, with herbicides and their degradates composing half of compounds. Many of the high priority pesticide compounds also are in several national regulatory programs for water, including those that are regulated in drinking water by the U.S. Environmental Protection Agency under the Safe Drinking Water Act and those that are on the latest Contaminant Candidate List. For sediment, a total of 175 pesticide compounds were classified as Tier 1 and, thus, are high priority for inclusion in analytical methods available for monitoring and studies. More than 60 percent of these compounds are included in some USGS analytical method; however, some are spread across several research methods that are expensive to perform, and monitoring data are not extensive for many compounds. The remaining Tier 1 compounds for sediment are high priority as new analytes. The objective for analytical methods development for sediment is to enhance an existing analytical method that currently includes nearly half of the pesticide compounds in Tier 1 by adding as many additional Tier 1 compounds as are analytically compatible. About 35 percent of the Tier 1 compounds for sediment are high priority on the basis of measured occurrence. A total of 74 compounds, or 42 percent, are high priority on the basis of predicted likelihood of occurrence according to physical-chemical properties, and either have potential toxicity to aquatic life, high pesticide useage, or both. The remaining 22 percent of Tier 1 pesticide compounds were either degradates of Tier 1 parent compounds or included for other reasons. As with water, the Tier 1 pesticide compounds for sediment are distributed across the major pesticide-use groups; insecticides and their degradates are the largest fraction, making up 45 percent of Tier 1. In contrast to water, organochlorines, at 17 percent, are the largest chemical class for Tier 1 in sediment, which is to be expected because there is continued widespread detection in sediments of persistent organochlorine pesticides and their degradates at concentrations high enough for potential effects on aquatic life. Compared to water, there are fewer available benchmarks with which to compare contaminant concentrations in sediment, but a total of 19 Tier 1 compounds have at least one sediment benchmark or screening value for aquatic organisms. Of the 175 compounds in Tier 1, 77 percent have high aquatic-life toxicity, as defined for this process. This evaluation of pesticides and degradates resulted in two lists of compounds that are priorities for USGS analytical methods development, one for water and one for sediment. These lists will be used as the basis for redesigning and enhancing USGS analytical capabilities for pesticides in order to capture as many high-priority pesticide compounds as possible using an economically feasible approach.
Characterization of Ground-Water Quality, Upper Republican Natural Resources District, Nebraska, 1998-2001
Nearly all rural inhabitants and livestock in the Upper Republican Natural Resources District (URNRD) in southwestern Nebraska use ground water that can be affected by elevated nitrate concentrations. The development of ground-water irrigation in this area has increased the vulnerability of ground water to the introduction of fertilizers and other agricultural chemicals. In 1998, the U.S. Geological Survey, in cooperation with the Upper Republican Natural Resources District, began a study to characterize the quality of ground water in the Upper Republican Natural Resources District area with respect to physical properties and concentrations of major ions, coliform bacteria, nitrate, and pesticides, and to assess the presence of nitrogen concentrations in the unsaturated zone. At selected well sites, the ground-water characterization also included tritium and nitrogen-isotope analyses to provide information about the approximate age of the ground water and potential sources of nitrogen detected in ground-water samples, respectively. In 1998, ground-water samples were collected from 101 randomly selected domestic-well sites. Of the 101 samples collected, 26 tested positive for total coliform bacteria, exceeding the U.S. Environmental Protection Agency's Maximum Contaminant Level (MCL) of zero colonies. In 1999, ground-water samples were collected from 31 of the 101 well sites, and 16 tested positive for coliform bacteria. Nitrates were detected in ground water from all domestic-well samples and from all but four of the irrigation-well samples collected from 1998 to 2001. Eight percent of the domestic-well samples and 3 percent of the irrigation-well samples had nitrate concentrations exceeding the U.S. Environmental Protection Agency's MCL for drinking water of 10 milligrams per liter. Areas with nitrate concentrations exceeding 6 milligrams per liter, the URNRD's ground-water management-plan action level, were found predominantly in north-central Chase, western and south-central Dundy, and south-central Perkins Counties. Generally, these concentrations were detected in samples from wells located in upland areas with permeable soils and a high percentage of cropland. In 1999, 31 of the ground-water samples collected from irrigation wells were analyzed for pesticides, and 14 samples (45 percent) had detectable concentrations of at least one pesticide compound. In 2000, all of the 23 irrigation-well samples analyzed had one or more pesticides present at detectable concentrations. In 2001, 12 of 26 domestic-well samples (46 percent) had detectable concentrations. Although the analytical method used during the study was changed to increase the number of pesticides included in the analyses, the pesticides detected in the ground-water samples from domestic and irrigation wells were limited to the commonly used herbicide compounds acetochlor, alachlor, atrazine, metolachlor, prometon, propachlor, propazine, trifluralin, and the atrazine degradation product deethylatrazine. Of the compounds detected, only atrazine (3.0 micrograms per liter) and alachlor (2.0 micrograms per liter) have MCLs established by the U.S. Environmental Protection Agency. None of the ground-water samples from the URNRD study area had concentrations that exceeded either MCL. Tritium age-dating analyses indicate water from about one-third of the sites entered the ground-water system prior to 1952. Because the increase in agricultural practices occurred during the 1950s and 1960s, it can be assumed that this water was not influenced by agricultural practices. Nitrogen-isotope speciation analyses for samples from three irrigation wells indicated that the source of nitrates in the ground water probably is synthetic fertilizer; however, the source at most irrigation wells probably is either naturally occurring or a mixture of water from various anthropogenic sources (such as synthetic fertilizer and animal waste).
Herbicides and nitrate in near-surface aquifers in the midcontinental United States, 1991
The occurrence and distribution of selected herbicides, atrazine metabolites, and nitrate were determined for near-surface aquifers (within 50 feet of land surface) in the corn- and soybean-producing region of the midcontinental United States. The study region included all or parts of Illinois, Indiana, Iowa, Kansas, Michigan, Minnesota, Missouri, Nebraska, North Dakota, Ohio, South Dakota, and Wisconsin. Water samples were collected during the spring and summer of 1991 from 303 wells completed in near-surface unconsolidated and near-surface bedrock aquifers. At least one herbicide or atrazine metabolite was detected in 24 percent of 579 water samples analyzed for herbicides, based on a reporting limit of 0.05 microgram per liter. However, no herbicide concentration exceeded the U.S. Environmental Protection Agency's maximum contaminant levels or health advisory levels for drinking water. The most frequently detected herbicide compound was desethylatrazine, an atrazine metabolite (18.1 percent), followed by atrazine (17.4 percent); deisopropylatrazine, an atrazine metabolite (5.7 percent); prometon (5.0 percent); metolachlor (2.7 percent); alachlor (1.7 percent); simazine (1.0 percent); metribuzin (1.0 percent); and cyanazine (0.7 percent). The herbicides ametryn, prometryn, propazine, and terbutryn were not detected during this study. Nitrate concentrations equal to or greater than 3.0 milligrams per liter (excess nitrate) were detected in 29 percent of the 599 nitrate analyses, and ammonium concentrations equal to or greater than 0.01 milligram per liter were detected in 78 percent of the 584 ammonium analyses. Nitrate concentrations equal to or greater than the U.S. Environmental Protection Agency's maximum contaminant level for drinking water of 10 milligrams per liter were found in 6 percent of the samples. The frequency of herbicide detection was, in part, affected by the analytical method's reporting limit. Results from this study show that the frequency of atrazine detection increases as the reporting limit decreases. Herbicide metabolite concentrations are critical to understanding the detection of herbicide residues. The frequency of detection of atrazine residue (atrazine + desethylatrazine + deisopropylatrazine) was 22.1 percent, which was more than the frequency of detection of atrazine alone (17.4 percent). Prometon was detected more frequently than every other herbicide except atrazine. The prometon appears to be derived from areas of nonagricultural land use, such as golf courses and residential areas. Herbicides and excess nitrate were both rarely detected in the eastern part of the study region, even though this is an area of intense herbicide and nitrogen-fertilizer use. Hydrogeologic factors, land use, agricultural practices, local features, and water chemistry were analyzed for possible relation to herbicide and excess-nitrate detections. Herbicides and excess nitrate were detected more frequently in near-surface unconsolidated aquifers than in nearsurface bedrock aquifers. The depth to the top of the aquifer was inversely related to the frequency of detection of herbicides and excess nitrate. The proximity of streams to sampled wells also affected the frequency of herbicide detection. Significant seasonal differences were determined for the frequency of herbicide detection, but not for the frequency of excess nitrate.
Baseline groundwater quality from 20 domestic wells in Sullivan County, Pennsylvania, 2012
Water samples were collected from 20 domestic wells during August and September 2012 and analyzed for 47 constituents and properties, including nutrients, major ions, metals and trace elements, radioactivity, and dissolved gases, including methane and radon-222. This study, done in cooperation with the Pennsylvania Department of Conservation and Natural Resources, Bureau of Topographic and Geologic Survey (Pennsylvania Geological Survey), provides a groundwater-quality baseline for central and southern Sullivan County prior to drilling for natural gas in the Marcellus Shale. The analytical results for the 20 groundwater samples collected during this study indicate that only one constituent (gross-alpha radioactivity) in one sample was found to exceed the U.S. Environmental Protection Agency (USEPA) primary drinking water maximum contaminant level (MCL). Water samples from 85 percent of the sampled wells exceeded the proposed USEPA MCL of 300 picocuries per liter (pCi/L) for radon-222; however, only two water samples (10 percent of sampled wells) exceeded the proposed USEPA alternate maximum contaminant level (AMCL) of 4,000 pCi/L for radon-222. In a few samples, the concentrations of total dissolved solids, iron, manganese, and chloride exceeded USEPA secondary maximum contaminant levels (SMCL). In addition, water samples from two wells contained methane concentrations greater than 1 milligram per liter (mg/L). In general, most of the water-quality problems involve aesthetic considerations, such as taste or odor from elevated concentrations of total dissolved solids, iron, manganese, and chloride that develop from natural interactions of water and rock minerals in the subsurface. The total dissolved solids concentration ranged from 31 to 664 mg/L; the median was 130 mg/L. The total dissolved solids concentration in one water sample exceeded the USEPA SMCL of 500 mg/L. Chloride concentrations ranged from 0.59 to 342 mg/L; the median was 12.9 mg/L. The concentration of chloride in one water sample exceeded the USEPA SMCL of 250 mg/L. Concentrations of dissolved iron ranged from less than 3.2 to 6,590 micrograms per liter (µg/L); the median was 11.5 µg/L. The iron concentration in samples from 20 percent of the sampled wells exceeded the USEPA SMCL of 300 µg/L. Concentrations of dissolved manganese ranged from less than 0.13 to 1,710 µg/L; the median was 38.5 µg/L. The manganese concentration in samples from 35 percent of the sampled wells exceeded the USEPA SMCL of 50 µg/L. Activities of radon-222 ranged from 169 to 15,300 picocuries per liter (pCi/L); the median was 990 pCi/L. The gross alpha-particle radioactivity ranged from below detection to 33 pCi/L; the median was 1.5 pCi/L. The gross alpha-particle radioactivity of one water sample exceeded the USEPA MCL of 15 pCi/L. Concentrations of dissolved methane ranged from less than 0.001 to 51.1 mg/L. Methane was not detected in water samples from 13 wells, and the methane concentration was less than 0.07 mg/L in samples from five wells. The highest dissolved methane concentrations were 4.1 and 51.1 mg/L, and the pH of the water from both wells was greater than 8. Water samples from these wells were analyzed for isotopes of carbon and hydrogen in the methane. The isotopic ratio values fell in the range for a thermogenic (natural gas) source. The water samples from these two wells had the highest concentrations of arsenic, boron, bromide, chloride, fluoride, lithium, molybdenum, and sodium of the 20 wells sampled.
Reconnaissance survey of sulfonamide, sulfonylurea, and imidazolinone herbicides in surface streams and groundwater of the Midwestern United States
The study objective was to conduct a small scale synoptic survey of representative water resources draining agricultural land for occurrence of several herbicide residues. These new classes of herbicides are commonly applied pre-emergence or post-emergence in conservation tillage systems to control grasses and broadleaf weeds in cropped and noncropped areas. Both surface water and groundwater samples were collected from 44 midwestern locations during the summer of 1997, and analyzed for herbicide residues of 15 sulfonylurea and imidazolinone chemicals, and one sulfonamide. Each site was sampled between mid-June and late-October with several stream sites sampled twice. The method, developed jointly by the chemical manufacturer's and the U.S. Environmental Protection Agency, provides a 100 ng/L limit of quantitation in surface water for all analytes. Analytes were detected and identity confirmed in surface water at six sites and in ground water at two sites. The most frequently detected herbicides were imazaquin, imazethapyr, and nicosulfuron. For field studies in which the source of surface and ground water associated with the farming system on the agricultural landscape is known, the sensitivity of the method can be improved with only minor modifications in detection criteria.
A Study of Natural and Restored Wetland Hydrology
The U.S. Geological Survey and the U.S. Environmental Protection Agency are jointly studying the hydrology of a long-existing natural wetland and a recently restored wetland in the Kankakee River Valley in northwestern Indiana. In characterizing the two wetlands, project investigators are testing innovative methods to identify the analytical tools best suited for evaluating the success of wetland restoration. Investigators also are examining and comparing the relations between hydrology and restored wetland vegetation.
Preliminary geologic framework developed for a proposed environmental monitoring study of a deep, unconventional Marcellus Shale drill site, Washington County, Pennsylvania
Background In the fall of 2011, the U.S. Geological Survey (USGS) was afforded an opportunity to participate in an environmental monitoring study of the potential impacts of a deep, unconventional Marcellus Shale hydraulic fracturing site. The drill site of the prospective case study is the “Range Resources MCC Partners L.P. Units 1-5H” location (also referred to as the “RR–MCC” drill site), located in Washington County, southwestern Pennsylvania. Specifically, the USGS was approached to provide a geologic framework that would (1) provide geologic parameters for the proposed area of a localized groundwater circulation model, and (2) provide potential information for the siting of both shallow and deep groundwater monitoring wells located near the drill pad and the deviated drill legs. The lead organization of the prospective case study of the RR–MCC drill site was the Groundwater and Ecosystems Restoration Division (GWERD) of the U.S. Environmental Protection Agency. Aside from the USGS, additional partners/participants were to include the Department of Energy, the Pennsylvania Geological Survey, the Pennsylvania Department of Environmental Protection, and the developer Range Resources LLC. During the initial cooperative phase, GWERD, with input from the participating agencies, drafted a Quality Assurance Project Plan (QAPP) that proposed much of the objectives, tasks, sampling and analytical procedures, and documentation of results. Later in 2012, the proposed cooperative agreement between the aforementioned partners and the associated land owners for a monitoring program at the drill site was not executed. Therefore, the prospective case study of the RR–MCC site was terminated and no installation of groundwater monitoring wells nor the collection of nearby soil, stream sediment, and surface-water samples were made. Prior to the completion of the QAPP and termination of the perspective case study the geologic framework was rapidly conducted and nearly completed. This was done for three principal reasons. First, there was an immediate need to know the distribution of the relatively undisturbed surface to near-surface bedrock geology and unconsolidated materials for the collection of baseline surface data prior to drill site development (drill pad access road, drill pad leveling) and later during monitoring associated with well drilling, well development, and well production. Second, it was necessary to know the bedrock geology to support the siting of: (1) multiple shallow groundwater monitoring wells (possibly as many as four) surrounding and located immediately adjacent to the drill pad, and (2) deep groundwater monitoring wells (possibly two) located at distance from the drill pad with one possibly being sited along one of the deviated production drill legs. Lastly, the framework geology would provide the lateral extent, thickness, lithology, and expected discontinuities of geologic units (to be parsed or grouped as hydrostratigraphic units) and regional structure trends as inputs into the groundwater model. This report provides the methodology of geologic data accumulation and aggregation, and its integration into a geographic information system (GIS) based program. The GIS program will allow multiple data to be exported in various formats (shapefiles [.shp], database files [.dbf], and Keyhole Markup Language files [.KML]) for use in surface and subsurface geologic site characterization, for sampling strategies, and for inputs for groundwater modeling.
Herbicides and their transformation products in source-water aquifers tapped by public-supply wells in Illinois, 2001-02
During 2001-02, ground-water samples were collected from 117 public-supply wells distributed throughout Illinois to evaluate the occurrence of herbicides and their transformation products in the State?s source-water aquifers. Wells were selected using a stratified-random method to ensure representation of the major types of source-water aquifers in the State. Samples were analyzed for 18 herbicides and 18 transformation products, including 3 triazine and 14 chloroacetanilide products. Herbicide compounds (field-applied parent herbicides and their transformation products) were detected in 34 percent of samples. A subset of samples was collected unfiltered to determine if analytical results for herbicides in unfiltered samples are similar to those in paired filtered samples and, thus, can be considered equally representative of herbicide concentrations in ground water supplied to the public. The study by the U.S. Geological Survey was done in cooperation with the Illinois Environmental Protection Agency. Parent herbicides were detected in only 4 percent of all samples. The six most frequently detected herbicide compounds (from 5 to 28 percent of samples) were chloroacetanilide transformation products. The frequent occurrence of transformation products and their higher concentrations relative to those of most parent herbicides confirm the importance of obtaining information on transformation products to understand the mobility and fate of herbicides in ground-water systems. No sample concentrations determined during this study exceeded current (2003) Federal or State drinking-water standards; however, standards are established for only seven parent herbicides. Factors related to the occurrence of herbicide compounds in the State?s source-water aquifers include unconsolidated and unconfined conditions, various hydrogeologic characteristics and well-construction aspects at shallow depths, and proximity to streams. Generally, the closer an aquifer (or well location) is to a recharge area and (or) the stronger the hydraulic connection between an aquifer and a recharge area, the younger the ground water and the more vulnerable the aquifer will be to contamination by herbicide compounds. The weak relation between current (2001) statewide application rates of herbicides and current (2001-02) occurrence of herbicide compounds in source-water aquifers indicates that additional factors must be considered when relating herbicide-application rates to occurrence. These factors include historical application rates and the mobility and persistence of the various herbicide compounds in ground-water systems. Frequency of detection and concentrations of herbicides compounds in the State?s source-water aquifers are indicated to be highest during the spring, when crops are planted and herbicides primarily are applied. Excess nitrate (concentrations of nitrate, as nitrogen, higher than 3 milligrams per liter) in ground water strongly indicates the co-occurrence of herbicide compounds. However, nitrate concentrations are not a reliable indicator of herbicide-compound concentrations. The inverse relation found between current use of land for corn and soybean production and current occurrence of herbicide compounds in underlying aquifers indicates that various factors, along with current agricultural land use, contribute to herbicide occurrence. These factors include, among others, land-use history, ground-water age, ground-water-flow patterns, geology, soil microbiology, and chemistry and persistence of the herbicide compounds. Detection of agriculture-specific herbicide compounds in 71 percent of samples from urban areas with no current or recent agricultural land use near the sampled wells indicates that recharge to certain high-capacity supply wells may originate at considerable distances (up to about 10 miles) from the wells. Essentially no difference was found between the analytical results for herbicides in paired unfiltered and filtered samples,
Microphotographs of cyanobacteria documenting the effects of various cell-lysis techniques
Cyanotoxins are a group of organic compounds biosynthesized intracellularly by many species of cyanobacteria found in surface water. The United States Environmental Protection Agency has listed cyanotoxins on the Safe Drinking Water Act's Contaminant Candidate List 3 for consideration for future regulation to protect public health. Cyanotoxins also pose a risk to humans and other organisms in a variety of other exposure scenarios. Accurate and precise analytical measurements of cyanotoxins are critical to the evaluation of concentrations in surface water to address the human health and ecosystem effects. A common approach to total cyanotoxin measurement involves cell membrane disruption to release the cyanotoxins to the dissolved phase followed by filtration to remove cellular debris. Several methods have been used historically, however no standard protocols exist to ensure this process is consistent between laboratories before the dissolved phase is measured by an analytical technique for cyanotoxin identification and quantitation. No systematic evaluation has been conducted comparing the multiple laboratory sample processing techniques for physical disruption of cell membrane or cyanotoxins recovery. Surface water samples collected from lakes, reservoirs, and rivers containing mixed assemblages of organisms dominated by cyanobacteria, as well as laboratory cultures of species-specific cyanobacteria, were used as part of this study evaluating multiple laboratory cell-lysis techniques in partnership with the U.S. Environmental Protection Agency. Evaluated extraction techniques included boiling, autoclaving, sonication, chemical treatment, and freeze-thaw. Both treated and untreated samples were evaluated for cell membrane integrity microscopically via light, epifluorescence, and epifluorescence in the presence of a DNA stain. The DNA stain, which does not permeate live cells with intact membrane structures, was used as an indicator for cyanotoxin release into the dissolved phase. Of the five techniques, sonication (at 70 percent) was most effective at complete cell destruction while QuikLyse (Trademarked) was least effective. Autoclaving, boiling, and sequential freeze-thaw were moderately effective in physical destruction of colonies and filaments.
Analytical results for As species and related elements in interstitial porewater and sediment from the Maurice River and Union Lake in Vineland, New Jersey
Union Lake, the Maurice River, and the Blackwater Branch , a tributary of the Maurice River, all parts of a small watershed near Vineland, New Jersey, are contaminated by arsenic (As) from a local chemical factory (fig. l)(Faust and others, 1987). An indepth study to be used for the design of the remedial action at the Vineland Chemical Co. Superfund site was initiated by the U.S. Environmental Protection Agency to determine the extent and severity of the contamination. The Vineland Chemical Co. site is located in Cumberland County, New Jersey. Organic As herbicides were manufactured there from approximately 1949 to the late 1980's. As part of the effort, core samples were collected in the Maurice River close to the chemical factory and from Union Lake, a reservoir approximately seven miles from the factory. This report summarizes the analytical results for As speciation and various constituents in the interstitial porewater and associated sediment from these cores. Because the U.S. Geological Survey has the analytical expertise and necessary equipment, the samples were analyzed in USGS laboratories in Denver, Colorado and Seattle, Washington.
Concentration data for anthropogenic organic compounds in groundwater, surface water, and finished water of selected community water systems in the United States, 2002-10
The National Water-Quality Assessment Program of the U.S. Geological Survey began implementing Source Water-Quality Assessments (SWQAs) in 2001 that focus on characterizing the quality of source water and finished water of aquifers and major rivers used by some of the larger community water systems in the United States. As used in SWQA studies, source water is the raw (ambient) water collected at the supply well before water treatment (for groundwater) or the raw (ambient) water collected from the river near the intake (for surface water), and finished water is the water that has been treated and is ready to be delivered to consumers. Finished-water samples are collected before the water enters the distribution system. The primary objective of SWQAs is to determine the occurrence of more than 250 anthropogenic organic compounds in source water used by community water systems, many of which currently are unregulated in drinking water by the U.S. Environmental Protection Agency. A secondary objective is to understand recurrence patterns in source water and determine if these patterns also occur in finished water before distribution. SWQA studies were conducted in two phases for most studies completed by 2005, and in one phase for most studies completed since 2005. Analytical results are reported for a total of 295 different anthropogenic organic compounds monitored in source-water and finished-water samples collected during 2002-10. The 295 compounds were classified according to the following 13 primary use or source groups: (1) disinfection by-products; (2) fumigant-related compounds; (3) fungicides; (4) gasoline hydrocarbons, oxygenates, and oxygenate degradates; (5) herbicides and herbicide degradates; (6) insecticides and insecticide degradates; (7) manufacturing additives; (8) organic synthesis compounds; (9) pavement- and combustion-derived compounds; (10) personal-care and domestic-use products; (11) plant- or animal-derived biochemicals; (12) refrigerants and propellants; and (13) solvents. This report presents the analytical results of source- water samples from 448 community water system wells and 21 surface-water sites. This report also presents the analytical results of finished-water samples from 285 wells and 20 surface-water sites from community water systems. Results of quality-assurance/quality-control samples also are presented including data for equipment blanks, field blanks, source solution blanks, and replicate samples.
Summary of urban stormwater quality in Albuquerque, New Mexico, 2003-12
Urban stormwater in the Albuquerque metropolitan area was sampled by the U.S. Geological Survey in cooperation with the City of Albuquerque, the Albuquerque Metropolitan Arroyo Flood Control Authority, the New Mexico Department of Transportation, and the University of New Mexico. Stormwater was sampled from a network of monitoring stations from 2003 to 2012 by following regulatory requirements for the National Pollutant Discharge Elimination System stormwater permit. During this period, stormwater was sampled in the Albuquerque metropolitan area at outfalls from nine drainage basins with residential, industrial, commercial, agricultural, and undeveloped land uses. Stormwater samples were analyzed for selected physical and chemical characteristics, nutrients, major ions, metals, organic compounds, and bacteria. General quality of stormwater samples, as measured by dissolved solids, nutrient (with the exception of phosphorus), major ion, and dissolved metal concentrations, was similar to that in samples from the Rio Grande. Of the nearly 200 organic compounds that were analyzed for this study, less than one-third (58 constituents) were positively identified at or above the analytical detection limit in stormwater. Concentrations for volatile organic compounds, semivolatile organic compounds, polychlorinated biphenyls, and pesticides were generally low in the stormwater samples. Fifteen of the 16 polycyclic aromatic hydrocarbons listed on the U.S. Environmental Protection Agency Priority Chemicals list were detected in at least one stormwater sample from each outfall. Maximum concentrations for some polycyclic aromatic hydrocarbons in stormwater did exceed a water-quality criterion. Median concentrations for Escherichia coli ( E. coli ) bacteria in the stormwater samples, including those from the background location (Embudo Arroyo), were above the New Mexico water-quality standard. Concentrations for E. coli in stormwater often exceeded the water-quality criterion. The stormwater quality in Albuquerque was compared with that of six other Western U.S. cities (Phoenix, Arizona; Tucson, Arizona; Las Vegas, Nevada; Denver, Colorado; Salt Lake City, Utah; and Boise, Idaho) for selected constituents. In general, water-quality data for stormwater samples from these six other Western U.S. cities were similar to water-quality data for the stormwater samples from the Albuquerque outfalls. Median concentrations for suspended solids, total phosphorus, and bacteria ( E. coli and fecal coliform) in stormwater samples from the Albuquerque outfalls, as a whole, were higher than those in samples from the other Western U.S. cities except for Las Vegas.
Ground-water sampling, analytical results, and water-level measurements at sites FT03, LF13, and WP14/LF15, East Management Unit, Dover Air Force Base, Delaware, January-October 2000
The U.S. Geological Survey, in cooperation with the U.S. Air Force, collected ground-water samples and made water-level measurements from January through October 2000 to monitor natural attenuation at four sites in the East Management Unit of Dover Air Force Base in Kent County, Delaware. The information in this report is based on data from ground-water samples collected during two sampling events, which occurred from January through March 2000 and September through October 2000. Ground-water samples and water-level measurements were collected from 36 monitor wells during the first sampling event. During the second sampling event, groundwater samples were collected from 34 monitor wells and water-level measurements were made in 29 monitor wells. Water-level measurements were also made in 103 wells during a synoptic in March 2000. The analytical results from the groundwater samples, the water-level measurements, and data-collection techniques are presented in this report. Analytical results indicate that the U.S. Environmental Protection Agency's maximum contaminant levels for constituents analyzed were exceeded in 10 samples collected during the first sampling event and 11 samples collected during the second sampling event. An independent quality-assurance data validation indicated that the water-quality data collected during this study were of good quality, reproducible, and unbiased.
Quality of groundwater and surface water, Wood River Valley, south-central Idaho, July and August 2012
Residents and resource managers of the Wood River Valley of south-central Idaho are concerned about the effects that population growth might have on the quality of groundwater and surface water. As part of a multi-phase assessment of the groundwater resources in the study area, the U.S. Geological Survey evaluated the quality of water at 45 groundwater and 5 surface-water sites throughout the Wood River Valley during July and August 2012. Water samples were analyzed for field parameters (temperature, pH, specific conductance, dissolved oxygen, and alkalinity), major ions, boron, iron, manganese, nutrients, and Escherichia coli (E.coli) and total coliform bacteria. This study was conducted to determine baseline water quality throughout the Wood River Valley, with special emphasis on nutrient concentrations. Water quality in most samples collected did not exceed U.S. Environmental Protection Agency standards for drinking water. E. coli bacteria, used as indicators of water quality, were detected in all five surface-water samples and in two groundwater samples collected. Some analytes have aesthetic-based recommended drinking water standards; one groundwater sample exceeded recommended iron concentrations. Nitrate plus nitrite concentrations varied, but tended to be higher near population centers and in agricultural areas than in tributaries and less populated areas. These higher nitrate plus nitrite concentrations were not correlated with boron concentrations or the presence of bacteria, common indicators of sources of nutrients to water. None of the samples collected exceeded drinking-water standards for nitrate or nitrite. The concentration of total dissolved solids varied considerably in the waters sampled; however a calcium-magnesium-bicarbonate water type was dominant (43 out of 50 samples) in both the groundwater and surface water. Three constituents that may be influenced by anthropogenic activity (chloride, boron, and nitrate plus nitrite) deviate from this pattern and show a wide distribution of concentrations in the unconfined aquifer, indicating possible anthropogenic influence. Time-series plots of historical water-quality data indicated that nitrate does not seem to be increasing or decreasing in groundwater over time; however, time-series plots of chloride concentrations indicate that chloride may be increasing in some wells. The small amount of temporal variability in nitrate concentrations indicates a lack of major temporal changes to groundwater inputs.