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Reductive dechlorination rates of 4,4′-DDE (1-chloro-4-[2,2-dichloro-1-(4-chlorophenyl)ethenyl]benzene) in sediments of the Palos Verdes Shelf, CA

Wastes from the world's largest manufacturer of DDT (1-chloro-4-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene) were released into the Los Angeles County municipal sewer system from 1947 to 1971. Following primary treatment, the effluent was discharged through a submarine outfall system whereupon a portion of the DDT and associated degradation products were deposited in sediments of the Palos Verdes Shelf (PVS). Parent DDT is present only in trace amounts in the sediments today, the vast majority having been transformed to DDE (1-chloro-4-[2,2-dichloro-1-(4-chlorophenyl)ethenyl]benzene) shortly following deposition. Previously believed to be inert, DDE is slowly being converted to DDMU (1-chloro-4-[2-chloro-1-(4-chlorophenyl)ethenyl]benzene) and DDMU to DDNU (1-chloro-4-[1-(4-chlorophenyl)ethenyl]benzene) via microbially-mediated reductive dechlorination (RDC). Kinetic and compositional data suggest that this process began sometime in the mid- to late 1970s. Rates of DDE RDC in shelf sediments are spatially variable and have proven difficult to determine accurately. This limits our ability to understand the factors controlling RDC rates and to predict the course of natural recovery. In the present study, concentrations of ten DDT compounds and twelve PCB (polychlorinated biphenyl) congeners were determined in cores collected at two locations on the PVS (stations 3C, 6C, ~7km and ~2km downcurrent from the outfalls, respectively). DDE inventories, normalized to those of non-degrading PCB congeners having similar physico-chemical properties, were modeled to yield first-order RDC rates for the period 1981–2010. Average rates at stations 3C and 6C were 0.044±0.004 and 0.008±0.002yr −1 , respectively, with depth-dependent RDC rates at station 3C (1992–2003) ranging from 0.0025 to 0.102yr −1 . Comparison of RDC and total loss (i.e., RDC+physical loss) rates suggests that the average per cent loss of DDE due to RDC is ~90% at station 3C (1981–2010) and ~57% at station 6C (1992–2010). Trajectories of adjusted molar inventories of DDE, DDMU, and DDNU were forecast using a first-order multi-step reaction series (M-SRS) model. The results for DDE are consistent with the normalization procedure; RDC rates at stations 3C and 6C were 0.036±0.002yr −1 and 0.010±0.001yr −1 , respectively. At station 6C, the DDE to DDMU transformation appears to be the rate limiting step in the reaction sequence, DDE k 1 → DDMU k 2 → DDNU k3 → unidentified compound(s), whereas at station 3C RDC rates for DDE and DDMU are roughly equivalent. At both locations the transformation rate of DDNU is 7–20 times that of the other steps. Estimated half-lives of DDE at stations 3C and 6C based on the M-SRS model results are ~19 and 72 years, respectively.

California

Factors related to occurrence and distribution of selected bacterial and protozoan pathogens in Pennsylvania streams

The occurrence and distribution of fecal indicator bacteria (FIB) and bacterial and protozoan pathogens are controlled by diverse factors. To investigate these factors in Pennsylvania streams, 217 samples were collected quarterly from a 27-station water-quality monitoring network from July 2007 through August 2009. Samples were analyzed for concentrations of Escherichia coli (EC) and enterococci (ENT) indicator bacteria, concentrations of Cryptosporidium oocysts and Giardia cysts, and the presence of four genes related to pathogenic types of EC ( eae A, stx 2, stx 1, rfb O157 ) plus three microbial source tracking (MST) gene markers that are also associated with pathogenic ENT and EC ( esp , LTIIa, STII). Water samples were concurrently analyzed for basic water chemistry, physical measures of water quality, nutrients, metals, and a suite of 79 organic compounds that included hormones, pharmaceuticals, and antibiotics. For each sample location, stream discharge was measured by using standardized methods at the time of sample collection, and ancillary sample site information, such as land use and geological characteristics, was compiled. Samples exceeding recreational water quality criteria were more likely to contain all measured pathogen genes but not Cryptosporidium or Giardia (oo)cysts. FIB and Giardia density and frequency of eae A gene occurrence were significantly related to season. When discharge at a sampling location was high (>75th percentile of daily mean discharge), there were greater densities of FIB and Giardia , and the stx2 , rfb O157 , STII, and esp genes were found more frequently than at other discharge conditions. Giardia occurrence was likely related to nonpoint sources, which are highly influential during seasonal overland transport resulting from snowmelt and elevated precipitation in late winter and spring in Pennsylvania. When MST markers of human, swine, or bovine origin were present, samples more frequently carried the eae A, stx 2, stx 1, and rfb O157 genes, but no genes were related exclusively to an individual MST marker. The human source pharmaceuticals (HSPs) acetaminophen and caffeine were correlated with Giardia , and the presence of HSPs proved to be more useful than MST markers in distinguishing the occurrence of Giardia . The HSPs caffeine and carbamazepine were correlated with the sum total of pathogen genes detected in a sample, demonstrating the value of using HSPs as an indicator of fecally derived pathogens. Sites influenced by urban land use with less forest were more likely to have greater FIB and Giardia densities and sum of the array of pathogen genes. Sites dominated by shallow carbonate bedrock in the upstream catchment were likely to have greater FIB densities and higher sum totals of pathogen genes but no correlation with Giardia detection. Our study provides a range of specific environmental, chemical, geologic, and land-use variables related to occurrence and distribution of FIB and selected bacterial and protozoan pathogens in Pennsylvania streams. The information presented could be useful for resource managers in understanding bacterial and protozoan pathogen occurrence and their relation to fecal indicator bacteria in similar settings.

Pennsylvania

Use of dissolved oxygen monitoring to evaluate phosphorus loading in Connecticut streams, 2015–18

The Connecticut Department of Energy and Environmental Protection (CT DEEP) has developed an interim phosphorus reduction strategy to establish water-quality-based phosphorus limits in nontidal freshwaters for industrial and municipal water pollution control facilities. A recommendation in the strategy included the addition of diurnal dissolved oxygen (DO) sampling to the sampling of diatom communities collected by CT DEEP. The chemistry data coupled with biological data will help to examine the effects of phosphorus loading in streams. The U.S. Geological Survey (USGS), in cooperation with the CT DEEP and New England Interstate Water Pollution Control Commission, implemented a summer DO monitoring program from 2015 to 2018 to examine the effects of phosphorus loading in streams. Continuous DO data were collected at 18 sites in streams with varying concentrations of phosphorus throughout the State of Connecticut. Discrete water-quality nutrient data were collected by the USGS at 11 of the 18 sites. All continuous and discrete data collected from June to September for the 4 years were examined for all sites. This report documents a pattern of diurnal DO for monitoring sites across 4 years and presents estimated daily gross primary productivity (GPP), ecosystem respiration (ER), and a standardized rate coefficient for gas exchange for selected streams. Relations of phosphorus concentrations to the diurnal DO response and stream metabolism are described. Interannual variability in average annual total phosphorus (TP) concentrations and maximum daily DO concentrations were evaluated among sites in years of the study. Streams identified as impaired by CT DEEP such as Naugatuck River at Beacon Falls (USGS station 01208500), Still River at Route 7 at Brookfield Center (USGS station 01201487), and Quinnipiac River at Wallingford (USGS station 01196500) had higher TP concentrations (greater than 0.10 milligram per liter [mg/L]) throughout the study. Reference streams considered unimpaired had lower concentrations of TP (less than 0.10 mg/L). The range in daily DO concentrations remained less than 4 mg/L for most of the sites during the study except for Naugatuck River at Beacon Falls and Still River at Route 7 at Brookfield Center. Daily GPP and ER were summarized for 11 sites using the maximum likelihood estimation model of the streamMetabolizer package in the R statistical program. The models indicated that most sites had an estimated negative net primary productivity, based on the daily estimates of GPP and ER, which indicates the systems are heterotrophic and dominated by respiration. The high variation of GPP and ER reported for several sites can be affected by many physical, chemical, and biological factors, including the abundance and community composition of phytoplankton, periphyton, and macrophyte algae present. The variability in mean GPP was similar to the variability in maximum DO concentrations when plotted against annual average TP concentrations for the maximum likelihood estimation model in streamMetabolizer. The concept that phosphorus loading can affect the stream metabolism requires more detailed knowledge of stream geomorphic variables (canopy cover, stream velocity, water depth) and algal communities to help improve the scientific basis for managing phosphorus loading.

Connecticut

Hydrostratigraphy, soil/sediment chemistry, and water quality, Potomac-Raritan-Magothy aquifer system, Puchack Well Field Superfund site and vicinity, Pennsauken Township, Camden County, New Jersey, 1997-2001

Drinking-water supplies from the Potomac-Raritan-Magothy aquifer system at the Puchack well field in Pennsauken Township, Camden County, New Jersey, have been contaminated by hexavalent chromium-the most toxic and mobile form-at concentrations exceeding the New Jersey maximum contaminant level of 100 micrograms per liter. Also, scattered but widespread instances of volatile organic compounds (primarily trichloroethylene) at concentrations that exceed their respective maximum contaminant levels in the area's ground water have been reported. Because inorganic and organic contaminants are present in the ground water underlying the Puchack well field, no water from there has been withdrawn for public supply since 1998, when the U.S. Environmental Protection Agency (USEPA) added the area that contains the Puchack well field to the National Priorities List. As part of the USEPA's investigation of the Puchack Well Field Superfund site, the U.S. Geological Survey (USGS) conducted a study during 1997-2001 to (1) refine previous interpretations of the hydrostratigraphic framework, hydraulic gradients, and local directions of ground-water flow; (2) describe the chemistry of soils and saturated aquifer sediments; and (3) document the quality of ground water in the Potomac-Raritan-Magothy aquifer system in the area. The four major water-bearing units of the Potomac-Raritan-Magothy aquifer system-the Upper aquifer (mostly unsaturated in the study area), the Middle aquifer, the Intermediate Sand (a local but important unit), and the Lower aquifer-are separated by confining units. The confining units contain areas of cut and fill, resulting in permeable zones that permit water to pass through them. Pumping from the Puchack well field during the past 3 decades resulted in downward hydraulic gradients that moved contaminants into the Lower aquifer, in which the production wells are finished, and caused ground water to flow northeast, locally. A comparison of current (1997-2001) water levels near the site of the former pumping center with data from previous investigations indicates that, since pumping at the Puchack well field ceased, the dominant local ground-water flow direction is to the southeast, aligned with regional flow. Chromium concentrations were highest (8,010 micrograms per liter in 2000-01) in water from the Middle aquifer immediately downgradient from a possible source; the extent of this chromium plume is unknown but appears to be small. A second, unrelated, localized chromium plume also was identified in the Middle aquifer. The Intermediate Sand was found to contain an areally extensive plume of chromium-contaminated water, with concentrations up to 6,310 micrograms per liter in 2000-01, and another plume of about the same size, with concentrations up to 4,810 micrograms per liter in 2000-01, was identified in the Lower aquifer. The previous USGS investigation indicated the approximate extent of the combined plumes; the current delineation indicates that their locations have shifted slightly to the southeast since 1998. Concentrations of chromium in ground water decreased at some well locations by as much as 60 percent between sampling rounds in 1997-98 and 1999-2001. The decrease in chromium concentration at a given well could be the result of the chemical reduction of hexavalent chromium and precipitation of the resulting trivalent chromium, the sorption of hexavalent chromium to aquifer materials, or the physical movement of the plumes. Available data indicate that all three processes likely have affected concentrations. The distribution of hexavalent and total chromium in the soils and sediments of a possible source area indicates that some hexavalent chromium has undergone chemical reduction in the soils, but the degree to which this process takes place in the aquifer currently is not known. Nor is it known whether contaminated soils continue to contribute chromium to the aquifer system. Contamination by vola

Scientific Investigations Report

Pesticide concentrations in multiple physical and biological stream matrices are impacted by a bioenergy production facility receiving pesticide coated corn seeds

Insecticide and fungicide seed coatings have become prevalent in conventional agriculture in recent decades. From 2015 to 2021, the AltEn bioenergy plant (Mead, Nebraska, USA) generated ethanol from almost 100% unused/expired treated corn seeds. This use of these seeds for ethanol production resulted in the accumulation of large amounts of contaminated wastewater and solid residue, a portion of which was applied to surrounding farmland. To better understand the potential long-term environmental effects from the processing of treated seeds at this facility, five nearby stream sites were sampled in 2022 after the closure of the plant; these included two sites directly impacted by AltEn, one upstream, and two downstream of the impacted sites. Water and sediment were collected in March through July, and algae and fish samples were collected in July for chemical analysis. Overall, 60 pesticide compounds (parents and transformation products) were detected in one or more matrices, including 23 fungicides, 20 insecticides, 16 herbicides, and 1 bacterial growth inhibitor. Pesticide results (maximum detection frequency, maximum concentration) varied substantially by environmental compartment: water (100% multiple pesticides; 4,600 ng L −1 thiamethoxam transformation product (NOA-407475)), algae (100% multiple pesticides, 190 ng g −1 atrazine), sediment (60% dithiopyr, 2.3 ng g −1 acetochlor) and fish (20% pyraclostrobin, 2.2 ng g −1 atrazine). Pesticides associated with treated corn seeds (e.g., insecticides clothianidin, thiamethoxam; fungicides fluoxastrobin, thiabendazole) were detected at significantly higher concentrations ( p < 0.05) in stream water from sites impacted by the AltEn facility compared to non-impacted sites. Study results indicate that pesticides associated with the AltEn facility continue to be a source of contaminants to aquatic systems after the plant’s closure in 2021.

Environmental Toxicology and Chemistry

Physical and hydrochemical evidence of lake leakage near Jim Woodruff Lock and Dam and of ground-water inflow to Lake Seminole, and an assessment of karst features in and near the lake, southwestern Georgia and northwestern Florida

Hydrogeologic data and water-chemistry analyses indicate that Lake Seminole leaks into the Upper Floridan aquifer near Jim Woodruff Lock and Dam, southwestern Georgia and northwestern Florida, and that ground water enters Lake Seminole along upstream reaches of the lake’s four impoundment arms (Chattahoochee and Flint Rivers, Spring Creek, and Fishpond Drain). Written accounts by U.S. Army Corps of Engineers geologists during dam construction in the late 1940s and early 1950s, and construction-era photographs, document karst-solution features in the limestone that comprise the lake bottom and foundation rock to the dam, and confirm the hydraulic connection of the lake and aquifer. More than 250 karst features having the potential to connect the lake and aquifer were identified from preimpoundment aerial photographs taken during construction. An interactive map containing a photomosaic of 53 photographic negatives was orthorectfied to digital images of 1:24,000-scale topographic maps to aid in identifying karst features that function or have the potential to function as locations of water exchange between Lake Seminole and the Upper Floridan aquifer. Some identified karst features coincide with locations of mapped springs, spring runs, and depressions that are consistent with sinkholes and sinkhole ponds. Hydrographic surveys using a multibeam echosounder (sonar) with sidescan sonar identified sinkholes in the lake bottom along the western lakeshore and in front of the dam. Dye-tracing experiments indicate that lake water enters these sinkholes and is transported through the Upper Floridan aquifer around the west side of the dam at velocities of about 500 feet per hour to locations where water "boils up" on land (at Polk Lake Spring) and in the channel bottom of the Apalachicola River (at the "River Boil"). Water discharging from Polk Lake Spring joins flow from a spring-fed ground-water discharge zone located downstream of the dam; the combined flow disappears into a sinkhole located on the western floodplain of the river and is transmitted through the Upper Floridan aquifer, eventually discharging to the Apalachicola River at the River Boil. Acoustic Doppler current profiling yielded flow estimates from the River Boil in the range from about 140 to 220 cubic feet per second, which represents from about 1 to 3 percent of the average daily flow in the river. Binary mixing-model analysis using naturally occurring isotopes of oxygen and hydrogen (oxygen-18 and deuterium) indicates that discharge from the River Boil consists of a 13-to-1 ratio of lake water to ground water and that other sources of lake leakage and discharge to the boil probably exist. Analyses of major ions, nutrients, radon-222, and stable isotopes of hydrogen and oxygen contained in water samples collected from 29 wells, 7 lake locations, and 5 springs in the Lake Seminole area during 2000 indicate distinct chemical signatures for ground water and surface water. Ground-water samples contained higher concentrations of calcium and magnesium, and higher alkalinity and specific conductance than surface-water samples, which contained relatively high concentrations of total organic carbon and sulfate. Solute and isotopic tracers indicate that, from May to October 2000, springflow exhibited more ground-water qualities (high specific conductance, low dissolved oxygen, and low temperature) than surface water; however, the ratio of ground water to surface water of the springs was difficult to quantify from November to April because of reduced springflow and rapid mixing of springflow and lake water during sampling. The saturation index of calcite in surface-water samples indicates that while surface water is predominately undersaturated with regard to calcite year-round, a higher potential for dissolution of the limestone matrix exists from late fall through early spring than during summer. The relatively short residence time (5–7 hours) and rapid flow velocity (nearly 500 feet per hour) of lake water leaking into the Upper Floridan aquifer and exiting at the River Boil in the Apalachicola River implies that calcite-undersaturated water is in constant contact with the limestone, increasing the potential for limestone dissolution and enlargement of flow pathways by erosion. A relatively low potential exists, however, for limestone dissolution to cause sudden sinkhole collapse followed by catastrophic lake drainage because ground-water levels close to the lake, except near the dam, are nearly the same as lake stage, resulting in low vertical and lateral hydraulic gradients and low flow between the lake and aquifer. An increased potential for lake leakage and sinkhole formation and collapse exists near some in-lake springs during colder months of the year, as density differences and the hydraulic potential between lake water and ground water establish the conditions for calcite-undersaturated lake water to enter nonflowing springs and contact limestone.

Florida, Georgia

National water summary 1990-91: Hydrologic events and stream water quality

National Water Summary 1990-91 Hydrologic Events and Stream Water Quality was planned to complement existing Federal-State water-quality reporting to the U.S. Congress that is required by the Clean Water Act of 1972. This act, formally known as the Federal Water Pollution Control Act Amendments of 1972 (Public Law 92-500), and its amendments in 1977,1979,1980,1981,1983, and 1987, is the principal basis for Federal-State cooperation on maintaining and reporting on water quality in the United States. Under section 305(b) of the Clean Water Act, the States must designate uses for waterbodies, biennially assess whether the waterbodies meet designated uses, and report to the U.S. Environmental Protection Agency (EPA), which in turn summarizes the findings of the State assessments in a biennial National Water Quality Inventory report to the Congress. This volume of the National Water Summary uses a nationally consistent data base and methods of statistical analysis to document stream water quality in the United States, Puerto Rico, and the Western Pacific Islands. As a basis for preparation of this report, the U.S. Geological Survey (uses) created a data base of waterquality data from about 2,900 stream water-quality monitoring stations in the United States (Lanfear, 1993). These data, which were extracted primarily from the uses National Water Information System (NWIS) and supplemented with data from the EPA national data base known as STORET, consisted mostly of water-chemistry and physical-sediment data. About 1,400 of these stations met a criterion, used in this volume for trends analysis of data, of having a period of record that began before water year 1980. (A water year is the period from October 1 through September 30 and is identified by the calendar year at the end of the period.) Inasmuch as the determination of trends requires about 10 years of data, few biological data were suitable for trends analysis because biological indicators of water quality were not being collected extensively by water year 1980. Also, because of the lack of long-term data, an assessment of the water quality of lakes and reservoirs is not included in this National Water Summary . Constituent and waterproperty data were selected from this data base and analyzed with statistical techniques that have been used extensively by the uses to summarize conditions and trends in water quality. (Throughout the remainder of this article, the term "constituent" is used also to represent water properties, such as pH and alkalinity.) Selected results from this analysis are presented graphically, both by State and nationally, in this volume. The data base created for preparation of this volume and the resulting nationally consistent statistical analysis of these data provide a unique opportunity to compare and contrast stream water-quality conditions and trends nationally and State by State. Because of the complexity of water quality and the natural seasonal and diurnal variations in the concentrations of waterquality constituents, the determination of trends in water quality requires a relatively long period of record. Trends in constituent concentrations in the State summaries in this volume were calculated for one or more of four periods water years 1970-89,1975-89,1980- 89, and 1982-89. Unfortunately, few water-quality monitoring stations have periods of record of more than 10 or 15 years, and therefore most analyses in the State summaries were done for 8- or 10-year periods. Although interest in water quality has continued to heighten since passage of the Clean Water Act, funds for support of data-collection programs are limited and data records of many of the constituents now of current concern, especially organic constituents, do not exist or are less than 10-years long; consequently only a modest number of organic constituents are presented in this volume. Discussion of conditions and trends in water quality in this National Water Summary also draw upon information about land use, population, water use, application of agricultural chemicals in rural areas, the siting of industrial facilities, and other ancillary information. Because the results of analysis of a restricted number of constituents are presented in this volume, State 305(b) reports also are cited in the discussion of water quality in each State. The following discussion is an overview of the three parts of this 1990-91 National Water Summary - "Hydrologic Conditions and Water-Related Events, Water Years 1990-91," "Hydrologic Perspectives on Water Issues," and "State Summaries of Stream Water Quality."

Water Supply Paper

Cascadia Margin cold seeps: Subduction zone fluids, gas hydrates, and chemosynthetic habitats

Priority Geographic Area: The outer continental shelf and upper continental slope from Canada/U.S. border offshore Washington State to the Mendocino Fracture Zone (Northern California), entirely within the U.S. Exclusive Economic Zone (EEZ), from the outermost shelf to at least 2000 m water depth (Figure 1). Description of Priority Area: Since 2015, over a thousand water column gas plumes originating at seafloor gas seeps have been discovered landward of the Cascadia deformation front (e.g., Embley et al., 2016; Johnson et al., 2015, 2019; Merle and Embley, 2016; NA-95 Cruise Report, 2018; Riedel et al., 2018), adding to those that had long been known on Hydrate Ridge (e.g., Heeschen et al., 2003; Tréhu et al., 2004). The recently-discovered seeps stretch from offshore Vancouver Island to the Mendocino Fracture Zone and from the outer shelf to ~2000 m water depth, occurring both landward and seaward of the nominal limit for gas hydrate stability zone on the upper continental slope (Figure 1). Hundreds of seeps likely remain undiscovered. Water column imaging is incomplete both within the target geographic area and farther seaward, between the 2000 m isobath and the deformation front, which is the subject of an imaging study described in a white paper by Watt et al. The recently-discovered Cascadia Margin cold seeps partially overlap an important active margin gas hydrate province (Spence et al., 2001; Tréhu et al., 2003, 2004), as well as an area where sediments on the North American plate are folded and faulted and affected by fluids generated in the subduction complex beneath the Cascadia forearc (e.g., Saffer and Tobin, 2011). Several Ocean Drilling Program expeditions have focused on hydrate systems offshore Vancouver and Oregon (e.g., Riedel et al., 2009; Tréhu et al., 2004) and on the connection between the shallow and deep hydrogeologic systems. Cabled observatories now continuously monitor physical, chemical, and venting processes on south Hydrate Ridge (OOI; e.g., Philip et al., 2016a) and offshore Vancouver Island (NEPTUNE; e.g. Römer et al., 2016). Outside of these well-studied gas hydrate areas, a subset of the recently-discovered Cascadia seeps, including some that we visited with R/V Falkor in 2019 (e.g., https://schmidtocean.org/cruise/methane-seeps-at-edge-of-hydrate-stability/), also likely emit methane associated with shallow subseafloor gas hydrate systems. Other seeps are delivering not only methane, but also deep-derived gases (Baumberger et al., 2018, 2020) to the seafloor. Many Cascadia Margin seeps have also been recognized at water depths too shallow (e.g., 175 m) to be connected to gas hydrate dynamics. These seeps are postulated to be emitting gas and fluids that originated deep in accretionary wedge before migrating up normal faults generated during forearc extension associated with large earthquakes (Johnson et al., 2019). Only a small fraction of the recently discovered U.S. Cascadia Margin water column gas plumes has so far been verified by ROVs (Hercules from E/V Nautilus in 2016 and 2018; SuBastian from R/V Falkor in 2018 and 2019) to correspond to seafloor seeps. Careful scientific mapping, investigation, and sampling at the seeps have also been limited (e.g., Baumberger et al., 2018, 2020; Merle and Embley, 2016; Seabrook et al., 2018; Greinert et al. 2019). This white paper focuses on expanding exploration of already-identified U.S. Cascadia Margin cold seeps through a multipronged and multidisciplinary discovery program that could be accomplished with a variety of NOAA assets. The goals of the proposed exploration activities are to develop high-resolution maps of seep fields from deep ocean vehicles; to verify (and sample) seafloor gas emissions at the locations of water column plumes for compositional and isotopic studies; to map, sample, and conduct analyses on chemosynthetic communities and deep-sea coral habitats near seep sites to document species distributions and habitats as a function of depth and latitude along the margin; to collect seep geologic samples that can constrain the timing of methane emissions through geochronology; and to record environmental data (e.g., CTD) near the seafloor and in the water column above the seeps. Seafloor mapping using shipboard systems (multibeam/backscatter) would be needed to characterize seafloor features near seep sites. Water column imaging (EK60/80 and/or multibeam WCD data) conducted before and after seafloor explorations would capture active methane plumes and constrain temporal variations in seep emissions (e.g., Kannberg et al., 2013; Philip et al., 2016a, 2016b), which are known to vary on time scales as rapid as tidal cycles on this margin (e.g., Römer et al., 2016). What are the characterization and data needs in this area? Check all that apply: __x_ Biology, Geology, Physical Oceanography, Chemistry ___ Marine Archaeology ___ Other Provide a list or brief description of the data needed within this area, from your perspective: 1. Water column backscatter to image active gas plumes 2. High-resolution multibeam bathymetry, seafloor backscatter, and shallow sub-bottom imaging 3. Visual characterization and ground truthing of potential seeps, including high-resolution mapping and photography from near-seafloor vehicles; collection of seep-associated species, corals, sediments, authigenic carbonates, gases, and seawater Describe relevance to national security, conservation, and/or the economy: The Cascadia margin seeps provide significant ecosystem services, including habitat for commercially important fishes and support for diversity along the continental margin. Methane seeps are also biological hotspots for krill, plankton, and crustaceans, which in turn sustain higher trophic levels (e.g., whales). Methane-derived authigenic carbonates serve as a hard substrate for deep-sea corals and sponges on millennial time scales. The studies proposed here will elucidate the relationship among seep environments, deep-sea corals, sponges, fisheries, and other organisms and provide new insight into subduction zone and hydrate-associated fluids in this important seismogenic zone. The studies address fishery management concerns and inform future conservation of sensitive species (e.g., deep-sea corals) and benthic habitats. From your perspective, what makes this area unique? The Cascadia Margin seeps are a critical component of the leaky margin that stretches from Baja California to the Aleutian Arc along the Pacific coastline of North America. Cold seeps have been intensely studied on the Gulf of Mexico and U.S. Atlantic passive margins with a focus on chemosynthetic communities, deep-sea corals, and leakage of microbially-generated and/or thermogenic hydrocarbons; however, the recently-discovered Cascadia Margin seeps, as well as active margin seep systems in general, remain more poorly characterized. Such seeps not only contribute to the ocean carbon cycle (e.g., Pohlman et al., 2011), thereby fueling the base of the food chain in these settings, but also emit subduction zone fluids that provide clues about processes within the seismogenic zone and the accretionary complex. The Cascadia seeps area allows both biological (e.g., benthic habitats, coral distributions) and physical processes (e.g., generation of subduction zone fluids) to be studied along both depth (perpendicular to the deformation front) and latitudinal gradients.

California, Oregon, Washington

A preliminary survey of marine contamination from mining-related activities on Marinduque Island, Philippines: porewater toxicity and chemistry results from a field trip, October 14-19, 2000

As a follow-up of an initial overview of environmental problems caused by mining activities on Marinduque Island, Philippines, USGS and TAMU-CC scientists went to Marinduque in October 2000 to do a preliminary assessment of potential impacts of mining-related activities on the marine environment. Like the previous visit in May 2000, the marine assessment was conducted at the invitation of Philippine Congressman Edmund O. Reyes. In this report we present the results of sediment porewater toxicity tests and chemical analyses. Toxicity tests consist of laboratory analyses for the assessment of adverse effects caused by environmental contaminants to animals or plants. Sediments (sand or mud) are known to accumulate contaminants (e.g., copper and other heavy metals). Therefore, it is common to perform toxicity tests using different phases of the sedimentary environment in order to analyze adverse effects of contaminants accumulated in the sediment. Sediment pore water (or interstitial water, i.e., the water distributed among the sediment grains) is a sedimentary phase which controls the bioavailability of contaminants to bottom dwelling aquatic organisms (both plants and animals). There are several different kinds of organisms with which toxicity tests can be performed. Among those, tests with sea urchin early life stages (gametes and embryos) are very common due to their high sensitivity to contaminants, ease of maintenance under laboratory conditions, and ecological importance, particularly in coral reefs. The basis of these tests is the exposure of gametes or embryos to the pore water to be analyzed for toxicity. If the pore water contains contaminants in levels that can adversely affect a number of marine species, fertilization and/or embryological development of sea urchins is inhibited. Chemical analyses provide additional information and aid in the interpretation of the toxicity test results. For the current study, chemical analyses were performed for the measurement of porewater concentrations of several heavy metals associated with copper mining activities. Pore waters for toxicological and chemical analyses were collected at several stations on the coast of Marinduque, near the mouths of the Boac and Mogpog rivers, and near the causeways formed by mine tailings disposal. Porewater samples were also collected at the Tres Reyes Marine Reserve, so that these non-contaminated samples could serve as a reference for test performance. Sea urchin embryological development and fertilization were only significantly impaired by two porewater samples, suggesting the presence of contaminants in toxic amounts at those stations. The toxic samples were collected near the up current side of the Calancan (Marcopper) mine tailings causeway (stations 2 and 3 – see figure 10). The pore water from station 2 also had the highest levels of heavy metals, particularly cadmium, cobalt, copper, nickel, lead and zinc (Table 5). The concentrations of cobalt, nickel and zinc were also elevated 2 at station 3. Copper concentrations were also elevated at the two river mouth stations (8 and 9) and near the CMI tailings causeway (station 7). Visual observations also indicated biological degradation due to heavy siltation and smothered coral at a gradient off the Calancan causeway, suggesting that siltation might also be causing a physical impact. This preliminary survey suggests that effects related to past mining activities are still evident and warrant a more comprehensive study to assess their severity and areal extent.

Open-File Report

Baseline groundwater quality from 34 wells in Wayne County, Pennsylvania, 2011 and 2013

Wayne County, Pennsylvania, is underlain by the Marcellus Shale, which currently (2014) is being developed elsewhere in Pennsylvania for natural gas. All residents of largely rural Wayne County rely on groundwater for water supply, primarily from bedrock aquifers (shales and sandstones). This study, conducted by the U.S. Geological Survey 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 Wayne County prior to development of the natural gas resource in the Marcellus Shale. Selected wells completed in the Devonian-age Catskill Formation, undifferentiated; the Poplar Gap and Packerton Members of the Catskill Formation, undivided; and the Long Run and Walcksville Members of the Catskill Formation, undivided, were sampled. Water samples were collected once from 34 domestic wells during August 2011 and August and September 2013 and analyzed to characterize their physical and chemical quality. Samples were analyzed for 45 constituents and properties, including nutrients, major ions, metals and trace elements, radioactivity, and dissolved gases, including methane and radon-222. The quality of the sampled groundwater was generally within U.S. Environmental Protection Agency (USEPA) drinking-water standards, although in some samples, the concentrations of a few constituents exceeded USEPA drinking-water standards and health advisories. The pH of water samples ranged from 5.5 to 9.3 with a median of 7.0. The pH was outside the USEPA secondary maximum contaminant level (SMCL) range of 6.5 to 8.5 in water samples from 14 of the 34 wells (41 percent). Eleven samples had a pH less than 6.5, and three samples had a pH greater than 8.5. Dissolved oxygen concentrations ranged from 0.2 to 11.5 milligrams per liter (mg/L) with a median of 4.7 mg/L. The dissolved oxygen concentration was less than 1 mg/L in water samples from 6 wells; 5 of these 6 water samples had a pH greater than 7.7. Concentrations of dissolved methane ranged from less than 0.00006 to 3.3 mg/L. Methane was detectable in 22 of the 34 wells sampled (65 percent). Methane concentrations were greatest in the 5 samples with pH of 7.8 or higher, ranging from 0.040 to 3.3 mg/L. These samples also had among the lowest concentrations of dissolved oxygen. Three water samples, which had sufficient dissolved methane concentrations (greater than 0.9 mg/L), were analyzed for isotopes of carbon and hydrogen in the methane. The isotopic ratio values fell within (two samples) or close to (one sample) the range for a thermogenic natural gas source. The total dissolved solids concentration ranged from 33 to 346 mg/L; the median concentration was 126 mg/L. Sodium concentrations ranged from 1.07 to 116 mg/L; the median concentration was 9.42 mg/L. The sodium concentration exceeded the USEPA health advisory for sodium of 20 mg/L in water samples from 7 of the 34 wells (21 percent). Concentrations of dissolved arsenic ranged from less than 0.06 to 21.8 micrograms per liter (&micro;g/L); the median concentration was 0.59 &micro;g/L. Water samples from 2 of the 34 wells (6 percent) exceeded the USEPA maximum contaminant level (MCL) of 10 &micro;g/L for arsenic. Concentrations of dissolved manganese ranged from less than 0.15 to 61.5 &micro;g/L; the median concentration was 0.42 &micro;g/L. A water sample from 1 of the 34 wells (3 percent) exceeded the USEPA SMCL of 50 &micro;g/L for manganese; the concentration was less than the USEPA lifetime health advisory of 300 &micro;g/L for manganese. Activities of radon-222 in water from the 34 sampled wells ranged from 110 to 7,180 picocuries per liter (pCi/L); the median activity was 2,105 pCi/L. Water samples from 33 of the 34 wells (97 percent) exceeded the proposed USEPA MCL of 300 pCi/L, and 4 water samples (12 percent) exceeded the USEPA proposed alternative MCL of 4,000 pCi/L for radon-222. Differences in groundwater chemistry were related to pH. Water with a pH greater than 7.6 generally had low dissolved oxygen concentrations, indicating reducing conditions in the aquifer. These high pH waters also had relatively elevated concentrations of methane, arsenic, boron, bromide, fluoride, lithium, and sodium but low concentrations of copper, nickel, and zinc. Water samples with a pH greater than 7.8 had methane concentrations equal to or greater than 0.04 mg/L.

Pennsylvania

Mercury and methylmercury in reservoirs in Indiana

Mercury (Hg) is an element that occurs naturally, but evidence suggests that human activities have resulted in increased amounts being released to the atmosphere and land surface. When Hg is converted to methylmercury (MeHg) in aquatic ecosystems, MeHg accumulates and increases in the food web so that some fish contain levels which pose a health risk to humans and wildlife that consume these fish. Reservoirs unlike natural lakes, are a part of river systems that are managed for flood control. Data compiled and interpreted for six flood-control reservoirs in Indiana showed a relation between Hg transport, MeHg formation in water, and MeHg in fish that was influenced by physical, chemical, and biological differences among the reservoirs. Existing information precludes a uniform comparison of Hg and MeHg in all reservoirs in the State, but factors and conditions were identified that can indicate where and when Hg and MeHg levels in reservoirs could be highest. As part of a statewide monitoring network for Hg and MeHg in Indiana streams, 66 water samples were collected from four reservoir tailwater sites (downstream near the dams) on a quarterly schedule for 5 years. The reservoirs were Brookville Lake, Cagles Mill Lake, J. Edward Roush Lake, and Mississinewa Lake. Particulate-bound Hg concentrations were significantly lower in tailwater samples than in samples from free-flowing streams in the statewide network. (Free-flowing streams were not affected by dams and were not upstream from these reservoirs.) These data indicated the reduced flow velocity of water upstream from dams was allowing particulate-bound Hg to settle out of the water in the reservoir pools. The concentration ratios of MeHg to Hg were significantly higher in the tailwater samples than in samples from free-flowing streams, and the MeHg to Hg ratios were significantly higher in summer than in other seasons. To evaluate the conditions related to MeHg formation, pools of three reservoirs (Brookville Lake, Monroe Lake, and Patoka Lake) were investigated during summer hydrologic conditions. Water temperature and dissolved oxygen were measured from the water surface to the lake bottom at 10 to 17 transects across each reservoir to identify three thermal strata, defined by water temperature, dissolved oxygen concentration, and depth. Depth-specific water samples were collected from these thermal strata throughout each reservoir, from the headwaters to the dam and from the tailwater. Mercury concentrations higher than 0.04 nanogram per liter (ng/L) were detected in all 53 samples, and MeHg concentrations higher than 0.04 ng/L were detected in 53 percent of the samples. The investigation found a zone of water below 8 or 9 meters, with temperatures less than 18 degrees Celsius and dissolved oxygen less than 3.5 milligrams per liter, extending through nearly half the reservoir area in Monroe Lake and Patoka Lake. This zone had abundant dissolved MeHg and concentration ratios of dissolved MeHg to Hg that ranged from 25 to 82 percent. This zone also had water with pH less than 7 and decreased dissolved sulfate, conditions indicating sulfate reduction by microorganisms that promoted a high potential for the conversion of Hg to MeHg. Reservoir outflow came from this zone at Monroe Lake and contributed to a tailwater concentration ratio for dissolved MeHg to Hg of 56 percent. Reservoir outflow at Patoka Lake was not from this zone, and dissolved MeHg was not detected in the tailwater. In contrast, samples from the summer pool at Brookville Lake had no MeHg detections even though Hg was detected, probably because the water pH higher than 7 inhibited sulfate reduction and did not promote the conversion of Hg to MeHg. Mercury and MeHg concentrations and the concentration ratios of MeHg to Hg in water varied among the six reservoirs in Indiana, and the differences were related to a combination of factors that could apply to other reservoirs. In areas with moderate to high rates of atmospheric Hg wet and dry deposition, Hg runoff and transport to streams and reservoirs was potentially highest for reservoirs with heavily forested watersheds in steep terrains of near-surface bedrock. Methylmercury concentrations and concentration ratios of MeHg to Hg were highest for reservoirs with the longest summer pools and highest inflow-to-outflow retention times, where water-chemistry conditions favoring sulfate reduction promoted conversion of Hg to MeHg. Methylmercury (reported as Hg) in fish-tissue samples collected for the State fish consumption advisory program was used to describe MeHg food-web accumulation and magnification in the reservoirs. The highest percentages of fish-tissue samples with Hg concentrations that exceeded the criterion of 0.30 milligram per kilogram for protection of human health were from Monroe Lake (38 percent) and Patoka Lake (33 percent). A review of the number and size of fish species caught from these two reservoirs resulted in two implications for fish consumption by humans. First, the highest numbers of fish harvested for potential human consumption were species more likely to have MeHg concentrations lower than the human-health criterion (crappie, bluegill, and catfish). Second, although largemouth bass were likely to have MeHg concentrations higher than the human-health criterion, they were caught and released more often than they were harvested. However, the average size largemouth bass (in both reservoirs) and above-average size walleye (in Monroe Lake) that were harvested for potential human consumption were likely to have MeHg concentrations higher than the human-health criterion.

Indiana

Potential effects of energy development on environmental resources of the Williston Basin in Montana, North Dakota, and South Dakota—Water resources

The Williston Basin has been a leading oil and gas producing area for more than 50 years. While oil production initially peaked within the Williston Basin in the mid-1980s, production rapidly increased in the mid-2000s, largely because of improved horizontal (directional) drilling and hydraulic fracturing methods. In 2012, energy development associated with the Bakken Formation was identified as a priority requiring collaboration toward improved timeliness of issuing permits for new wells combined with reasonable measures to maintain environmental quality. Shortly thereafter, the Bakken Federal Executive Group was created to address common challenges associated with energy development. The Bakken Federal Executive Group partner agencies identified a gap in current understanding of the cumulative environmental challenges attributed to energy development throughout the area, resulting in an effort to aggregate scientific data and identify additional research and information needs related to natural resources within areas of energy development in the Williston Basin. As part of this effort, water resources in the area (including groundwater; streams and rivers; and lakes, reservoirs, and wetlands) were characterized and described in terms of physical occurrence, flow characteristics, recharge, water quality, and water use. Similarly, waters produced during energy-development activities also were characterized even though these waters are not considered usable resources within the area. Groundwater resources were characterized by the major hydrogeologic units, or aquifers, identifying the units that supply most groundwater used for domestic, stock, agricultural, and industrial purposes. The groundwater characterization included other deeper hydrogeologic units in the Williston Basin that may be a useable source of water with treatment, have utility as a reservoir for reinjection of produced waters, or be a source of minerals and energy resources. A generalized groundwater budget and flow system identifying the sources of recharge (stream infiltration, precipitation, and movement [leakage] from other aquifers) and the general groundwater flow direction is included for each of the major hydrogeologic units. Rivers and streams within the Williston Basin with 10 or more years of continuous streamflow data were identified. For a subset of these sites, streamflow characteristics, including the monthly and annual mean flow, were generated to identify seasonal and interannual changes in streamflow and thus provide information on the drivers and reliability of streamflow at the seasonal or multiyear scale. Daily streamflow and annual extreme flows (peak and low flow) also were estimated for the subset of sites. The daily streamflow and annual extreme flow values provide information on short-term or extreme events that are relevant to infrastructure design and evaluating spills, leaks, or accidental discharges of water or petroleum products. Surface-water features (lakes, ponds, and wetlands) were classified using the Cowardin system and identified on the National Wetlands Inventory maps generated by the U.S. Fish and Wildlife Service. The spatial distribution of the surface-water features was analyzed by State, county, and specifically in comparison to the Prairie Pothole Region. The proximity of the surface-water features to energy development infrastructure (specifically oil or gas well pads) was evaluated. It was determined that, although oil or gas wells are often near a surface-water feature, most surface-water features do not have wells nearby, with the exception of wells in the Prairie Pothole Region. Water-quality data were aggregated from two data sources: (1) the Water-Quality Portal, sponsored by the U.S. Geological Survey (USGS), U.S. Environmental Protection Agency (EPA), and National Water Quality Monitoring Council; and (2) a data compilation completed as part of the USGS National Water-Quality Assessment project. The Water-Quality Portal integrates publicly available water-quality data from databases maintained by the USGS, EPA, and U.S. Department of Agriculture, including water-quality data from Tribal, State, and local databases. Water-quality data for 15 commonly measured water-quality constituents were aggregated for groundwater, rivers and streams, and lakes and reservoirs. For each aggregated dataset (groundwater, rivers and streams, and lakes and reservoirs), analyses of the water-quality data included summary statistics, maps of spatial distribution of constituent values, boxplots of constituent values by timeframe or hydrogeologic unit, spatial comparisons of site locations and constituent values to petroleum well density, and comparisons of the constituent values measured to EPA drinking-water standards/guidelines. Produced water includes all fluids brought to the surface along with the targeted hydrocarbons as part of the oil and gas exploration and extraction processes. These fluids may include formation water (waters that co-exist with rock/oil/gas), hydraulic fracturing fluids, and other combinations of water and chemicals used during oil and gas well drilling, development, treatments, recompletions, and workovers. Produced water datasets were aggregated from two sources: the USGS National Produced Waters Geochemical database (ver. 2.1) and a series of projects focused specifically on sampling produced water in the Williston Basin from 2010 to 2014. The National Produced Waters Geochemical database was useful for a general understanding of produced-water chemistry. Produced waters are characterized by extreme salinity and contain elevated concentrations of other constituents (including arsenic, barium, cadmium, lead, zinc, radium-226/radium-228, and ammonium) that could negatively affect water and aquatic resources if released. Produced waters also have a generally unique chemical (isotopic) signature that may be useful in tracking water from different geologic units; for example, the oxygen/deuterium and strontium ratio values measured in brine waters from the Bakken Formation are distinct from brines collected from other geologic units in the Williston Basin. Water-use information related to energy production in the area also was aggregated and summarized. The summary of water use is not limited to oil and gas production but includes water used to produce all types of energy resources in the Williston Basin, including coal/lignite, thermoelectric power, oil and gas, hydropower, biomass and biofuels, wind, geothermal, and solar. Each State has its own methods for regulating and reporting water usage within its jurisdiction. These methods can introduce problems when examining water use from sources, such as the Missouri River or Fox Hills aquifer, that are shared across political boundaries. Without the one-to-one match for usage types and amounts used from a water source, it is difficult to develop a comprehensive water budget for the water source being evaluated. A large amount of freshwater is required to prepare a well for oil and gas well production; in some cases, 3 to 7 million gallons of water are needed per well. The EPA estimates that hydraulic fracturing in the Williston Basin uses between 70 to 140 billion gallons per year. Water also is used for myriad other purposes related to ancillary oil and gas extraction. In addition to water used for immediate energy development, the expanded human workforce migrating into the area and other support staff who have moved into the area during the development also use water. Research and information needs were identified that could be relevant in the evaluation of the effects of energy development on water resources. Information needs related to the evaluation of groundwater resources include the following: improved potentiometric-surface maps for glacial units; availability of a uniform stream network digital geographic coverage that spans the international boundary with Canada; enhanced surface-water use information with regards to the gain and loss of streamflow to shallow groundwater, which would increase understanding groundwater and surface-water interactions; and expanded geophysical assessments. Gaps in the availability of streamflow data include the lack of information on ice-jam flooding despite potential for effects to infrastructure (pipelines, roads, and facilities) and an understanding of the cumulative effects of largely undocumented stock and diversion dams. Although this study resulted in the aggregation of a large quantity of water-quality data, the availability of consistently collected, systematically processed and reported data over large parts of the Williston Basin is sparse. Few samples have been analyzed for constituents that may indicate the effect of energy development on water resources. Constituents that could be considered include boron, chloride, bromide, iodine, fluoride, manganese, lithium, radium, strontium isotopes, volatile organic compounds, and isotopes of inorganic ions (such as hydrogen and carbon). Collaboration between Tribal, Federal, State, and local entities to identify a common study design, common monitoring constituents, and consistent sampling locations would generate datasets with broad utility and would likely result in overall cost savings for monitoring over time. Similarly, there is a need for standardized sample collection, processing, laboratory analytical methods, and the collection of ancillary data for produced waters sampling. Additional characterization of the range of chemical, microbial, and isotopic compositions and quantities of “end-member” produced waters, and the collection of time-series datasets to document the changes in produced waters during and after well development also were needs identified during this study. Water-use estimates would be improved through the implementation of comprehensive studies of water use from groundwater and surface-water sources using consistent methodologies across the Williston Basin. The submission of chemical and water data related to hydraulic fracturing collected by the oil and gas industry would add to the quantity of available data. Consistent implementation of regulations and monitoring controls across political boundaries (State, county, and international) would further improve the consistency of data available for the estimates of water use.

Montana, North Dakota, South Dakota

Groundwater quality for 75 domestic wells in Lycoming County, Pennsylvania, 2014

Groundwater is a major source of drinking water in Lycoming County and adjacent counties in north-central and northeastern Pennsylvania, which are largely forested and rural and are currently undergoing development for hydrocarbon gases. Water-quality data are needed for assessing the natural characteristics of the groundwater resource and the potential effects from energy and mineral extraction, timber harvesting, agriculture, sewage and septic systems, and other human influences. This report, prepared in cooperation with Lycoming County, presents analytical data for groundwater samples from 75 domestic wells sampled throughout Lycoming County in June, July, and August 2014. The samples were collected using existing pumps and plumbing prior to any treatment and analyzed for physical and chemical characteristics, including nutrients, major ions, metals and trace elements, volatile organic compounds, gross-alpha particle and gross beta-particle activity, uranium, and dissolved gases, including methane and radon-222. Results indicate groundwater quality generally met most drinking-water standards, but that some samples exceeded primary or secondary maximum contaminant levels (MCLs) for arsenic, iron, manganese, total dissolved solids (TDS), chloride, pH, bacteria, or radon-222. Arsenic concentrations were higher than the MCL of 10 micrograms per liter (µg/L) in 9 of the 75 (12 percent) well-water samples, with concentrations as high as 23.6 μg/L; arsenic concentrations were higher than the health advisory level (HAL) of 2 μg/L in 23 samples (31 percent). Total iron concentrations exceeded the secondary maximum contaminant level (SMCL) of 300 μg/L in 20 of the 75 samples. Total manganese concentrations exceeded the SMCL of 50 μg/L in 20 samples and the HAL of 300 μg/L in 2 of those samples. Three samples had chloride concentrations that exceeded the SMCL of 250 milligrams per liter (mg/L); two of those samples exceeded the SMCL of 500 mg/L for TDS. The pH ranged from 5.3 to 9.15 and did not meet the SMCL range of 6.5 to 8.5 in 22 samples, with 17 samples having a pH less than 6.5 and 8 samples having pH greater than 8.5. Generally, the samples that had elevated TDS, chloride, or arsenic concentrations had high pH. Total coliform bacteria were detected in 39 of 75 samples (52 percent), with Escherichia coli detected in 10 of those 39 samples. Radon-222 activities ranged from non-detect to 7,420 picocuries per liter (pCi/L), with a median of 863 pCi/L, and exceeded the proposed drinking-water standard of 300 pCi/L in 50 (67 percent) of the 75 samples; radon-222 activities were higher than the alternative proposed standard of 4,000 pCi/L in 3 samples. Water from 15 of 75 (20 percent) wells had concentrations of methane greater than the reporting level of 0.01 mg/L; detectable methane concentrations ranged from 0.04 to 16.8 mg/L. Two samples had methane concentrations (13.1 and 16.8 mg/L) exceeding the action level of 7 mg/L. Low levels of ethane (up to 0.12 mg/L) were present in the five samples with the highest methane concentrations (near or above 1 mg/L) that were analyzed for hydrocarbon compounds and isotopic composition. The isotopic composition of methane in four of these groundwater samples, from the Catskill and Lock Haven Formations and the Hamilton Group, have sample carbon isotopic ratio delta values (carbon-13/carbon-12) ranging from –42.36 to –36.08 parts per thousand (‰) and hydrogen isotopic ratio delta values (deuterium/protium) ranging from –212.0 to –188.4 ‰, which are consistent with the isotopic compositions reported for mud-gas logging samples from these geologic units and a thermogenic source of the methane. However, the isotopic composition and ratios of methane to ethane in a fifth sample indicate the methane in that sample may be of microbial origin that subsequently underwent oxidation. The fifth sample had the highest concentration of methane, 16.8 mg/L, with an carbon isotopic ratio delta values of -50.59 ‰ and a hydrogen isotopic ratio delta values of -209.7 ‰. The six well-water samples with the highest methane concentrations also had among the highest pH values (8.25 to 9.15) and elevated concentrations of sodium, lithium, boron, fluoride, arsenic, and bromide. Relatively elevated concentrations of some other constituents, such as barium, strontium, and chloride, commonly were present in, but not limited to, those well-water samples with elevated methane. Three of the six groundwater samples with the highest methane concentrations had chloride/bromide ratios that indicate mixing with a small amount of brine (0.02 percent or less) similar in composition to those reported at undetermined depth below the freshwater aquifer and for gas and oil well brines in Pennsylvania. The sample with the highest methane concentration and most other samples with low methane concentrations (less than about 1 mg/L) have chloride/bromide ratios that indicate predominantly anthropogenic sources of chloride, such as road-deicing salt, septic systems, and (or) animal waste. Brines that are naturally present may originate from deeper parts of the aquifer system, while anthropogenic sources are more likely to affect shallow groundwater because they occur on or near the land-surface. The spatial distribution of groundwater compositions generally indicate that (1) uplands along the western border of Lycoming County usually have dilute, slightly acidic oxygenated, calcium-bicarbonate type waters; (2) intermediate altitudes or areas of carbonate bedrock usually have water of near neutral pH, with highest amounts of hardness (calcium and magnesium); (3) stream valleys, low elevations where groundwater may be discharging, and deep wells in uplands usually have water with pH values greater than 8 and highest arsenic, sodium, lithium, bromide concentrations. Geochemical modeling indicated that for samples with elevated pH, sodium, lithium, bromide, and alkalinity, the water chemistry could have resulted by dissolution of calcite (calcium carbonate) combined with cation-exchange and mixing with a small amount of brine. Through cation-exchange reactions between water and bedrock, which are equivalent to processes in a water softener, calcium ions released by calcite dissolution are exchanged for sodium ions on clay minerals. Thus, the assessment of groundwater quality in Lycoming County indicates groundwater is generally of good quality, but various parts of Lycoming County can have groundwater with low to moderate concentrations of methane and other constituents that appear in naturally present brine and produced waters from gas and oil wells at high concentrations."

Pennsylvania