Search USGS⌕ Search

Geology topics

Karl B. Haase

Publications and source records attributed to Karl B. Haase.

18 recordsLinked to original sources

Continuous measurements reveal wind and temperature affect orphan well methane emissions on the Kevin-Sunburst Dome, Montana

Fifteen leaking orphan wells on the Kevin-Sunburst Dome in northern Montana had emission rates that were affected by surface winds and diurnal temperature swings based on continuous monitoring data. Some wells showed correlating spikes in emissions when temperatures changed or wind speed increased while others demonstrated independent flow behavior despite being drilled into the same reservoir and located only a few hundred meters apart. Time-weighted mean methane emission rates ranged from non-detectable levels up to 2.7 kg/h in their as-discovered conditions, with leaking wells averaging 211 g/h. Emissions were measured continuously for up to 452 h per well during monitoring, revealing that leak rates can fluctuate by an order of magnitude within hours. Fluctuations in emission rates often synchronized between wells with overlapping emission measurement intervals, suggesting weather conditions, such as temperature and wind, affect emission rates (up to a factor of 4) with the most relevant factor being the effect of wind on wells with open holes. Additionally, this study presents the first methane emissions measured from an orphan well in two distinct conditions: as initially discovered (closed leaking valve, 2.7 kg/h) and again under unrestricted flow conditions (open valve, 11.8 kg/h), illustrating the maximum unobstructed leak rate and quantifying the constraints restricted leaking wells can have on emissions compared to open holes.

Montana↗

Geothermal potential of orphan oil and gas wells

The United States is estimated to have hundreds of thousands of orphan oil and gas wells. Orphan wells are abandoned wells that are both unremediated and have no responsible operator. While traditionally considered environmental and economic liabilities, orphan oil and gas wells may offer new opportunities in sustainable geothermal energy development. This study evaluates the potential of repurposing orphan wells for geothermal energy production. We analyzed more than 1.4 million bottom-hole temperature (BHT) records from oil and gas well logs to create corrected temperature-depth profiles in a grid across the United States. Total depth values, where available, in documented orphan wells from a U.S. Geological Survey (USGS) database were then correlated to these temperature-depth profiles to estimate a corrected BHT for each orphan well. The orphan wells were then categorized as having low (<90°C), moderate (90–150°C), and high (>150°C) geothermal potential, identifying them as wells in the U.S. that could be used to access geothermal resources. In addition, repurposing these wells could contribute to broader environmental and economic goals, including well remediation, rogue methane emissions reduction, and energy production. This study provides a framework for integrating inactive well inventories with geothermal resource assessments and further highlights the potential for orphan wells to play a transformative role in expanding geothermal energy capacity in the United States.

contiguous United States↗

Evaluating mass flow meter measurements from chambers for greenhouse gas emissions from orphan wells and other point sources

This study evaluates the performance of a rigid gas flux chamber equipped with a mass flow meter (MFM) for measuring gas emissions from leaking orphan wells and similar pressure-driven gas point sources. We conducted a series of laboratory and field experiments to evaluate the sensitivity, stability, and dynamic range of an MFM chamber system and found an optimal method for sealing the chamber to the ground to isolate the emission source. From these results, we estimate the effects of different soil gas permeabilities on measurements and identify the uncertainty of environmental processes that can impact measurements. Simulations of an MFM chamber are compared to those of a dynamic flux chamber to contrast the data derived with both methodologies and illustrate the potential for measuring high variability leaks with the MFM chamber. Using a low flow resistance MFM and a chamber well-sealed to the ground, it is possible to measure leaks down to 1.08 x 10 -3 cubic meters per hour (m 3 h −1 ) (refenced to 25°/1 atm), corresponding to 0.77 grams per hour (g h −1 ) methane or 2.11 g h −1 carbon dioxide, with a mean uncertainty of 0.89 % relative standard deviation. Environmental processes such as heated gas inside the chamber from solar gain, wind blowing across the chamber vent, and changing humidity in the chamber, can cause variation in MFM measurements. Over 11 d of continuous monitoring under varying weather conditions, the standard deviation of the environmentally sourced signals was found to be 7.40 x 10 -3 m 3 h −1 (equivalent to or 5.27 g h −1 methane or 14.45 g h −1 carbon dioxide). Strategies to obtain the highest quality data from MFM chambers include burying the edges of the chamber below the surface sufficiently deep to seal the chamber edges against gas flow and soaking the dirt with water to lower the chances of escaping gases, while monitoring the gas flow and adjusting the chamber seal to achieve a maximum flow rate.

Atmospheric Measurement Techniques↗

A geospatial analysis of water-quality threats from orphan wells in principal and secondary aquifers of the United States

Throughout the history of oil and gas production in the United States, millions of wells have been drilled for exploration and energy production. Hundreds of thousands of unplugged wells are no longer actively producing and are currently under orphan status, with no responsible party obligated for plugging. Orphan wells can pose threats to water resources by providing pathways for contaminants such as hydrocarbons and brines to migrate into water-supply aquifers. In this study, we investigate the potential threats to groundwater resources posed by orphan wells at the national scale. Water-quality data is extremely sparse in relation to orphan wells nationally and may not be suitable for identifying contamination from oil and gas development. We used geospatial and statistical methods to evaluate which principal and secondary aquifer systems may be most susceptible to contamination from orphan wells. Analysis involved three sets of susceptibility factors including: 1) factors related to the number and density of orphan wells; 2) factors that can threaten well integrity and contribute to transport of contaminants; and 3) factors related to groundwater withdrawal rates and the affected populations/communities in the event of water quality disturbances. From a dataset of 117,672 documented orphan wells, 64,203 fall within a principal aquifer system, while the remainder fall within a secondary aquifer system. By assessing the combination of well integrity and hydrogeologic factors within these aquifer systems, five groupings of principal aquifers were identified, where groups ranged from aquifer systems with high numbers of orphan wells, multiple well integrity threats and high withdrawals, to aquifers with a relatively low number of orphan wells, limited well integrity threats and minimal water use. Three regions of the country emerge containing aquifers with higher susceptibility to contamination from orphan oil and gas wells. These regions include 1) The Appalachian Basin (including the Pennsylvanian Aquifer System), 2) The Gulf Coast Aquifers (including the Coastal Lowlands Aquifer system) and 3) The California Aquifers (including the California Coastal Basin Aquifer system). This work is the first multivariate geospatial investigation of orphan wells and groundwater resources on a national scale, and sheds light on which aquifers are most susceptible to groundwater contamination from orphan wells.

Science of the Total Environment↗

Geologic sources and well integrity impact methane emissions from orphaned and abandoned oil and gas wells

The 160-year history of oil and gas drilling in the United States has left a legacy of unplugged orphaned and abandoned wells, some of which are leaking methane and other hazardous chemicals into the environment. The locations of around 120,000 documented orphaned wells are currently known with the number of undocumented orphaned wells possibly ranging towards a million. The bulk of methane emissions originate from only 10 % of orphaned and abandoned wells, while the remaining wells have undetectable emissions. Understanding the sources of methane emissions from orphaned wells is key to estimating emission rates and prioritizing plugging. In this article, we identify key studies reporting methane emission measurements from orphaned and abandoned wells in the published literature and analyze previously published isotopic methane data to categorize the sources of methane emissions. Three primary geologic sources provide methane to a leaking well that can migrate from geologic formations into or along the wellbore to contaminate groundwater, the surface environment, and the atmosphere. These geologic sources of methane are petroleum (oil and gas) sourced reservoirs, coal seams, and methanogenesis occurring in and around the wellbore. Thermogenic petroleum gas reservoirs are associated with the highest emission rates measured to date. The next highest rates are from coalbed methane sources, while biogenic sources are the lowest based on the publicly available measured emissions data. Well conditions that could potentially enable methane transport include decay of the wellhead and surface infrastructure, wellbore deterioration from corrosive fluids in the subsurface, delamination of the casing and cement, damage from seismicity, and new fracture networks created by hydraulic fracturing of newly drilled neighboring wells. With an understanding of these geologic sources and well conditions, we can (1) better identify areas where high-emitting wells are likely to be present, (2) improve emission rate estimates from orphaned and abandoned wells, and (3) better prioritize wells for plugging.

Science of the Total Environment↗

Groundwater quality and geochemistry of the western wet gas part of the Marcellus Shale Oil and Gas Play in West Virginia

Thirty rural residential water wells in the wet gas region of the Marcellus Shale oil and gas play in northwestern West Virginia were sampled by the U.S. Geological Survey (USGS) in 2018, in cooperation with West Virginia State agencies, to analyze for a range of water-quality constituents, including major ions, trace metals, radionuclides, bacteria, and methane and other dissolved hydrocarbon gases. The groundwater-quality data collected for this study were used to assess the overall quality of groundwater in the study area in relation to public drinking-water standards. The groundwater-quality data were also evaluated with respect to geology, well depth, topographic setting, and proximity to oil and gas wells to identify possible relations to these factors. The presence of total coliform bacteria in groundwater is a potential indicator of surface contamination. The presence of Escherichia coli bacteria is indicative of fecal contamination of groundwater from either human or animal sources and may be considered an indicator of other related pathogens such as viruses. Total coliforms were detected in 26 of the 30 (87 percent) wells sampled. Eleven of the 30 (37 percent) wells sampled had detections of Escherichia coli bacteria. Sodium concentrations in 24 of 30 (80 percent) samples exceeded the U.S. Environmental Protection Agency (EPA) 20-milligram per Liter (mg/L) health-based value (HBV). Manganese, aluminum, and iron concentrations exceeded the EPA 50, 2.0, and 300 micrograms per liter (μg/L) secondary maximum contaminant level (SMCL) drinking-water standards at 14 (47 percent), 7 (23 percent), and 5 (17 percent) of the 30 wells sampled. Two of the 30 (7 percent) wells sampled had concentrations of manganese that exceeded the 300-μg/L USGS health-based screening level (HBSL). Arsenic concentrations at 7 of 30 (23 percent) wells sampled exceeded the 10-μg/L EPA maximum contaminant level (MCL) health-based drinking water standard. The EPA maximum contaminant level goal (MCLG) for arsenic is 0 μg/L and 29 of 30 wells sampled contained detectable concentrations of arsenic. None of the 30 wells sampled exceeded the U.S. Office of Surface Mining Reclamation and Enforcement (OSMRE) 28-mg/L immediate action level (IAL) for methane in groundwater and only 1 of 30 (3 percent) sites exceeded the 10-mg/L OSMRE level of concern (LOC) for methane in groundwater. Of the 28 wells sampled for radon-222 all 28 (100 percent) exceeded the EPA proposed 300-picocuries per liter (pCi/L) MCL for radon. None of the samples exceeded the 4,000-pCi/L alternate maximum contaminant level (AMCL) which is applicable to public drinking water systems that have adopted radon mitigation programs. Wilcoxon Signed Rank Tests indicated statistically significant differences at a 95 percent confidence interval (p less than 0.05) in radium-226, barium, and ethane groundwater concentrations with respect to the density of oil and gas wells present within a 500-meter (m) radius around the rural residential wells sampled for the study. Samples from residential wells that had four or fewer oil and gas wells in the surrounding 500-m radius had statistically lower concentrations of radium-226, bromide, and ethane than samples from residential wells sampled that had five or more oil and gas wells in the surrounding 500-m radius. Given the available data, the relationship between concentrations of radium-226, bromide, and ethane for wells sampled in this study and oil and gas development or natural geochemical processes is not clear. Groundwater-age tracers (chlorofluorocarbons, tritium, and sulfur hexafluoride) were sampled at 17 of the 30 wells. All 17 samples contained a fraction of young, post-1950s groundwater. Many of the groundwater samples collected for this study have high calcium to sodium ratios and low total dissolved solids concentrations, indicating they are dominated by recently recharged water. A subset of samples had chloride to bromide mass ratios between 70 and 200, indicating that deep Appalachian basin brines mixed with the shallow groundwater. For most of the samples in this study, the C 1 through C 6 hydrocarbons have characteristics that reflect a biogenic gas signature that has, to varying degrees, undergone oxidation processes during transport. None of the samples show a characteristic thermogenic cracking pattern among the hydrocarbon ratios.

West Virginia↗

DGMETA (version 1)—Dissolved gas modeling and environmental tracer analysis computer program

DGMETA (Dissolved Gas Modeling and Environmental Tracer Analysis) is a Microsoft Excel-based computer program that is used for modeling air-water equilibrium conditions from measurements of dissolved gases and for computing concentrations of environmental tracers that rely on air-water equilibrium model results. DGMETA can solve for the temperature, salinity, excess air, fractionation of gases, or pressure/elevation of water when it is equilibrated with the atmosphere. Models are calibrated inversely using one or more measurements of dissolved gases such as helium, neon, argon, krypton, xenon, and nitrogen. Excess nitrogen gas, originating from denitrification or other sources, also can be included as a fitted parameter or as a separate calculation from the dissolved gas modeling results. DGMETA uses the air-water equilibrium models to separate measured concentrations of gases and isotopes of gases into components that are used for tracing water in the environment. DGMETA calculates atmospheric dry-air mole fractions (mixing ratios) for transient atmospheric gas tracers such as chlorofluorocarbons, sulfur hexafluoride, and bromotrifluoromethane (Halon-1301); and concentrations of tritiogenic helium-3 and radiogenic helium-4, which accumulate from the decay of tritium in water and the decay of uranium and thorium in rocks, respectively. Sample data can be graphed to identify applicable models of excess air, samples that contain excess nitrogen gas, or samples that have partially degassed, for example. Monte Carlo analysis of errors associated with dissolved gas equilibrium model results can be carried through computations of environmental tracer concentrations to provide robust estimates of error. In addition, graphical routines for separating helium sources using helium isotopes are included to refine estimates of tritiogenic helium-3 when terrigenic helium from mantle or crustal sources is present in samples. Environmental tracer concentrations and their errors computed from DGMETA can be used with other programs, such as TracerLPM (Jurgens and others, 2012), to determine groundwater ages and biogeochemical reaction rates. DGMETA also produces output files in a format that meets the U.S. Geological Survey open data requirements for documentation of model inputs and outputs. DGMETA is a versatile and adaptable program that allows users to add solubility data for new gases, modify the existing set of gas solubility data, modify the default set of gases used for modeling, choose calculations based on real (non-ideal) gas behavior, and select various concentration units for data entry and results to match laboratory reports and study objectives. DGMETA comes with a set of gases widely used in hydrology and oceanography and many gases include multiple solubilities from previous work. Seventeen dissolved gases are included in the default version of the program: noble gases (helium, neon, argon, krypton, and xenon), reactive gases (nitrogen, oxygen, methane, carbon dioxide, carbon monoxide, hydrogen, and nitrous oxide), and environmental tracers (chlorofluorocarbon-11, chlorofluorocarbon-12, chlorofluorocarbon-113, sulfur hexafluoride, and Halon-1301).

Techniques and Methods↗

Groundwater quality and geochemistry of West Virginia’s southern coal fields

Coal mining has been the dominant industry and land use in West Virginia’s southern coal fields since the mid-1800s. Mortality rates for a variety of serious chronic conditions, such as diabetes, heart disease, and some forms of cancer in Appalachian coal mining regions, are higher than in areas lacking substantial coal mining activity within the Appalachian Region or elsewhere in the United States. Causes of the increased mortality and morbidity are not clear, but poor diet, high rates of smoking, socioeconomic factors, and the quality of groundwater used by area residents are all possible contributing factors. This study was conducted by the U.S. Geological Survey in cooperation with the West Virginia Department of Health and Human Resources and the West Virginia Department of Environmental Protection, with grant support from the Centers for Disease Control and Prevention (CDC) to assess the quality of groundwater in southern West Virginia. The data from this assessment of groundwater quality may be used by the CDC and other agencies to potentially investigate the role or lack thereof of groundwater quality with respect to mortality and morbidity rates in the region. The study was conducted in a region where a high density of current or past coal mining combined with a lack of advanced sewage treatment could affect concentrations of commonly occurring constituents plus contaminants, including nitrate, trace metals, major ions, indicator bacteria, radon, hydrogen sulfide, and dissolved hydrocarbons. Because rural residential wells and mine outfalls are considered private sources of water in the region, and are therefore unregulated and unmonitored, water-quality data are sparse. To fill the data gap and assess the groundwater quality in the region, water-quality samples were collected from 60 sites in a 10-county area. The 60 sites sampled included 46 rural residential homeowner wells and 14 mine outfall discharges used for residential supply. For this study, all samples were collected prior to any filtration or other treatments, typically at the pressure tank, and are indicative of total and dissolved constituents in the untreated water. Generally, data for the 60 sites indicate that most waters sampled do not exceed thresholds for most U.S. Environmental Protection Agency (EPA) drinking-water standards and U.S. Geological Survey (USGS) drinking-water screening criteria. However, there were several notable exceptions. Turbidity exceeded the 5-Nephelometric Turbidity Unit (NTU) EPA treatment technique (TT) drinking-water standard in 14 of 60 (23 percent) sites sampled and exceeded the 1-NTU TT standard in 51 of 60 (85 percent) sites sampled. Turbidity is common in many wells in southern West Virginia and may be attributed to iron oxyhydroxide precipitates, sediment carried into the aquifers from the shallow soil zone due to improperly constructed or cased wells or transported to the aquifer in shallow stress-relief fracture zones or through permeable bedding-plane partings. For the sites sampled, 31 of 60 (52 percent) had pH values at, above, or below the upper and lower range of the EPA Secondary Maximum Contaminant Level (SMCL, 6.5–8.5 standard units). Of those 31 sites, 28 (90 percent) were indicative of acidic corrosive water and 3 (10 percent) were indicative of alkaline water. The Langelier Saturation Index (LSI), which is a measure of the corrosivity of the water, was computed for all sites sampled for the study. Eighty-two percent of the sites sampled had waters that were classified as corrosive, based on a LSI less than −0.5. Corrosive water has the potential to leach lead, copper, and other metals from lead, copper, galvanized, or lead-tin soldered connections in water lines. The chloride to sulfate mass ratio also was assessed with the alkalinity to indicate the potential to promote galvanic corrosion (PPGC) of water lines and plumbing fixtures. Only one of the sites (1.7 percent) classified as a corrosive water site, had a PPGC considered high; the remaining sites were classified as having either a moderate (53.3 percent) or low (45 percent) PPGC. Therefore, the type of plumbing systems sampled for this study may be affected by corrosive water, but the potential for leaching trace metals and other constituents from residential plumbing systems containing older galvanized pipes or lead-tin soldered copper pipes is moderate to low. The indicator bacteria total coliform and Escherichia coli ( E. coli ) also were detected in groundwater samples to varying degrees. Total coliforms, which are a broad class of indicator bacteria, are common in groundwater in southern West Virginia and were detected in 39 of the 60 sites (65 percent) sampled. The presence of total coliform bacteria is a potential indicator of surface contamination, due to improperly constructed or cased wells, or infiltration of soil or other surface contaminants into the aquifer or well bore. E. coli bacteria, however, are much more indicative of fecal contamination of groundwater from either human or animal sources, and 14 of the 60 (23 percent) sites sampled had detections of E. coli . Although only a few strains of E. coli are known pathogens, their presence in groundwater may be an indicator of other related pathogens such as viruses and should be regarded as a serious potential issue. Water treatment such as chlorination, ozonation, or ultraviolet light may be appropriate to kill potential pathogenic bacteria or viruses in the source water. Manganese and iron were prevalent contaminants in the groundwater samples collected for this study, with 30 of 60 (50 percent) sites analyzed for manganese and 25 of 60 (42 percent) sites analyzed for iron exceeding the proposed 50- and 300-micrograms per liter (µg/L) SMCL drinking-water standards, respectively, for aesthetic criteria such as taste, odor, or staining of plumbing fixtures. Fourteen of the 60 sites sampled (23 percent) had concentrations of manganese that exceeded the 300-µg/L USGS health-based screening level, and 1 site exceeded the 1,600-µg/L EPA drinking-water equivalent level, which is based on a lifetime exposure level. Sodium is another common constituent in groundwater within the study area. Sodium has an EPA health-based value (HBV) of 20 milligrams per liter (mg/L) for individuals who are on a sodium-restricted diet for blood pressure or other health reasons. Sodium concentrations exceeded the 20-mg/L EPA HBV in 27 of 60 (45 percent) samples. Radon, a naturally occurring carcinogenic radioactive gas known to cause lung cancer, was detected at concentrations at or exceeding the proposed 300-picocuries per liter (pCi/L) EPA Maximum Contaminant Level (MCL) in 12 of the 60 (20 percent) sites sampled. Sites with radon gas concentrations exceeding the 300-pCi/L proposed MCL have the potential for airborne concentrations of radon to exceed the 4-pCi/L indoor air standard. Inhalation of radon can cause lung cancer, and the 4-pCi/L indoor air standard is based on an inhalation standard. Therefore, homeowners whose wells have radon gas concentrations exceeding 300 pCi/L may be advised to have their indoor air tested to determine if indoor air concentrations exceed the 4-pCi/L indoor air standard established by the EPA. Various factors were analyzed statistically and graphically to determine whether they have an influence on groundwater quality within the study area, including topographic setting, well depth, type of mining (surface or underground), type of site (well or mine outfall), and geologic formation. Only geologic formation and the type of site sampled had strong statistical correlations with one or more of the constituents of concern for this study. The overall chemistry of outfalls (mine outfalls) and wells was significantly different, with a much higher dissolved oxygen content in outfalls than in wells. The dissolved oxygen content is the primary component driving the oxidation and reduction of minerals, and the precipitation of minerals that are saturated or super saturated with respect to various cations and anions. Median dissolved oxygen concentrations for the outfalls sampled was 8.75 mg/L, and only 0.4 mg/L for the wells sampled. Median concentrations of sulfate and selenium were much higher in waters from the outfalls sampled, with median concentrations of 73.75 mg/L and 2.35 µg/L, respectively, compared to the wells sampled, which had median concentrations of 18.3 mg/L and less than (<) the 0.05-µg/L method detection limit, respectively. The maximum selenium concentration was for a well, with a concentration of 16.6 µg/L. The geochemical processes that control sulfate and selenium concentrations in groundwater are similar and are the result of the oxidation of sulfide minerals such as pyrite and ferroselite. Iron and manganese concentrations were elevated in most of the wells sampled, with median concentrations of 269.5 and 124.5 µg/L, respectively, but were rarely detected in the outfalls sampled, with median concentrations of < 4.0 and < 0.4 µg/L, respectively. The difference in iron and manganese between wells and outfalls is indicative of the role of dissolved oxygen on processes controlling groundwater chemistry in the region. Three principal geologic formations were assessed for the study, and the overall chemistry for the Pocahontas, New River, and Kanawha Formations varied substantially with respect to several constituents. Concentrations of calcium, magnesium, and total dissolved solids were highest for sites sampled in the Pocahontas Formation, with median concentrations of 41.9, 18.6, and 312 mg/L, respectively. For constituents that are commonly associated with mining activity, the highest concentrations were for sites sampled in the New River Formation, with median concentrations of iron and manganese of 2,450 µg/L and 482 µg/L, respectively, and a median pH of 6.35 standard units. Concentrations of barium also were elevated in samples collected from sites in the New River Formation, with a median barium concentration of 184 µg/L. The source of the barium is not fully known but may be associated with commingling of shallow groundwater with deeper brines or dissolution of the mineral barite. The highest median sulfate concentrations were from sites sampled in the Pocahontas Formation, with a median concentration of 64.0 mg/L. Of the 12 sites at or exceeding the 300-pCi/L proposed drinking-water standard for radon, 8 (67 percent of MCL exceedances) were for sites deriving water from the Kanawha Formation, 3 (25 percent of MCL exceedances) were for sites deriving water from the New River Formation, and only 1 site was for water from the Pocahontas Formation (8 percent of proposed MCL exceedances). Dissolved hydrocarbons, including methane, ethane, propane, propene, n - and i -butane, 1-butene, n - and i -pentane, pentane, 2- and 3-ethyl pentane, hexane, and benzene were analyzed in samples collected from 59 of the 60 sites to assess the potential occurrence and sources of these trace gases in groundwater within the study area. Results of the analysis indicate that most of the gas is of shallow biogenic origin, possibly associated with coal-bed methane, but a subset of samples has a gas signature and a chloride to bromide ratio indicative of potential mixing with deeper thermogenic gases. Only 2 of the 59 (3.3 percent) sites sampled had concentrations of methane gas, which is a highly combustible and explosive gas, exceeding the 10 milligrams per kilogram level of concern established by the U.S. Office of Surface Mining Reclamation and Enforcement. Principal components analysis was used to assess the primary geochemical processes occurring in the aquifers sampled. The first principal component had significant positive loadings for bromide, chloride, silica, ammonia, barium, iron, manganese, and arsenic, and significant negative loadings for dissolved oxygen, potassium, nitrate, and uranium, and reflects reduction and oxidation (redox) processes occurring in deeper anoxic groundwater or shallow oxic groundwater. The strong positive loadings for iron, manganese, barium, and arsenic are correlated with reducing conditions often found deeper in the aquifer. More oxic water is correlated with oxidation of nitrogen species to nitrate and environmental mobilization of uranium and sulfate in shallow wells and mine outfalls.

West Virginia↗

Organic geochemistry and toxicology of a stream impacted by unconventional oil and gas wastewater disposal operations

Water and sediment extracts samples were analyzed for extractable hydrocarbons by gas chromatography/mass spectrometry (GC/MS) using an Agilent (Agilent Technologies, Palo Alto, CA, USA) 7890 series GC and 5975 electron ionization (EI) mass selective detector (MSD) operated in scan mode. Agilent ChemStation software was used for data acquisition and analysis (version E.02.00.493 on GC/MS computer and version F.01.03.2357 on laptop for data workup). A 30 m x 250 m x 0.25 m HP-5MS column (95% dimethyl 5% diphenyl polydimethylsiloxane) was used for GC/MS under the following conditions: 1.0 L splitless injection, constant flow of 0.7 mL/min, solvent delay of 7.5 min, injector temperature of 280C, interface at 300C, temperature program of 50-150C at 7C/min, 150-230C at 6C/min, and 230-300C at 3C/min with mass scanned from 35-500 Da.

West Virginia↗

Spatial fingerprinting of biogenic and anthropogenic volatile organic compounds in an arid unsaturated zone

Subsurface volatile organic compounds (VOCs) can pose risks to human and environmental health and mediate biological processes. VOCs have both anthropogenic and biogenic origins, but the relative importance of these sources has not been explored in subsurface environments. This study synthesizes 17 years of VOC data from the Amargosa Desert Research Site (ADRS) with the goal of improving understanding of spatial and temporal variations that distinguish sources of VOCs from a landfill and surrounding ambient sources including biogenic VOCs (bVOCs). Gas samples were collected from 1999 to 2016 from an array of shallow sample points (0.5 m and 1.5 m depth) and from vertical profiles at three deep boreholes, two (109 m deep) near the border of a waste facility (33 and 100 m distant), and one (29 m deep) in a remote area 3 km to the south. Samples were analyzed for target VOCs and a subset was analyzed for non-target VOCs to enumerate a greater variety of potential bVOCs. Principal components analysis of the target and non-target VOCs provided an assessment of spatial variability of VOCs originating from the landfill site and from ambient sources. Ambient VOCs occurred at all sample sites over a range of depths and most were consistent with biogenic origins, indicating, for the first time, presence of bVOCs in the deep unsaturated zone. Because some VOCs have both anthropogenic and biogenic sources, discrimination of sources can be important for estimating the extent and migration of anthropogenic plumes in arid unsaturated zones.

Nevada↗

Acetylenotrophy: A hidden but ubiquitous microbial metabolism?

Acetylene (IUPAC name: ethyne) is a colorless, gaseous hydrocarbon, composed of two triple bonded carbon atoms attached to hydrogens (C 2 H 2 ). When microbiologists and biogeochemists think of acetylene, they immediately think of its use as an inhibitory compound of certain microbial processes and a tracer for nitrogen fixation. However, what is less widely known is that anaerobic and aerobic microorganisms can degrade acetylene, using it as a sole carbon and energy source and providing the basis of a microbial food web. Here, we review what is known about acetylene degrading organisms and introduce the term 'acetylenotrophs' to refer to the microorganisms that carry out this metabolic pathway. In addition, we review the known environmental sources of acetylene and postulate the presence of an hidden acetylene cycle. The abundance of bacteria capable of using acetylene and other alkynes as an energy and carbon source suggests that there are energy cycles present in the environment that are driven by acetylene and alkyne production and consumption that are isolated from atmospheric exchange. Acetylenotrophs may have developed to leverage the relatively high concentrations of acetylene in the pre-Cambrian atmosphere, evolving later to survive in specialized niches where acetylene and other alkynes were produced.

FEMS Microbiology Ecology↗

Environmental signatures and effects of an oil and gas wastewater spill in the Williston Basin, North Dakota

Wastewaters from oil and gas development pose largely unknown risks to environmental resources. In January 2015, 11.4 M L (million liters) of wastewater (300 g/L TDS) from oil production in the Williston Basin was reported to have leaked from a pipeline, spilling into Blacktail Creek, North Dakota. Geochemical and biological samples were collected in February and June 2015 to identify geochemical signatures of spilled wastewaters as well as biological responses along a 44-km river reach. February water samples had elevated chloride (1030 mg/L) and bromide (7.8 mg/L) downstream from the spill, compared to upstream levels (11 mg/L and < 0.4 mg/L, respectively). Lithium (0.25 mg/L), boron (1.75 mg/L) and strontium (7.1 mg/L) were present downstream at 5–10 times upstream concentrations. Light hydrocarbon measurements indicated a persistent thermogenic source of methane in the stream. Semi-volatile hydrocarbons indicative of oil were not detected in filtered samples but low levels, including tetramethylbenzenes and di-methylnaphthalenes, were detected in unfiltered water samples downstream from the spill. Labile sediment-bound barium and strontium concentrations (June 2015) were higher downstream from the Spill Site. Radium activities in sediment downstream from the Spill Site were up to 15 times the upstream activities and, combined with Sr isotope ratios, suggest contributions from the pipeline fluid and support the conclusion that elevated concentrations in Blacktail Creek water are from the leaking pipeline. Results from June 2015 demonstrate the persistence of wastewater effects in Blacktail Creek several months after remediation efforts started. Aquatic health effects were observed in June 2015; fish bioassays showed only 2.5% survival at 7.1 km downstream from the spill compared to 89% at the upstream reference site. Additional potential biological impacts were indicated by estrogenic inhibition in downstream waters. Our findings demonstrate that environmental signatures from wastewater spills are persistent and create the potential for long-term environmental health effects.

North Dakota↗

Detection of diazotrophy in the acetylene-fermenting anaerobe Pelobacter sp. strain SFB93

Acetylene (C2H2) is a trace constituent of the present Earth's oxidizing atmosphere, reflecting a mixture of terrestrial and marine emissions from anthropogenic, biomass-burning, and unidentified biogenic sources. Fermentation of acetylene was serendipitously discovered during C2H2 block assays of N2O reductase, and Pelobacter acetylenicus was shown to grow on C2H2 via acetylene hydratase (AH). AH is a W-containing, catabolic, low-redox-potential enzyme that, unlike nitrogenase (N2ase), is specific for acetylene. Acetylene fermentation is a rare metabolic process that is well characterized only in P. acetylenicus DSM3246 and DSM3247 and Pelobacter sp. strain SFB93. To better understand the genetic controls for AH activity, we sequenced the genomes of the three acetylene-fermenting Pelobacter strains. Genome assembly and annotation produced three novel genomes containing gene sequences for AH, with two copies being present in SFB93. In addition, gene sequences for all five compulsory genes for iron-molybdenum N2ase were also present in the three genomes, indicating the cooccurrence of two acetylene transformation pathways. Nitrogen fixation growth assays showed that DSM3426 could ferment acetylene in the absence of ammonium, but no ethylene was produced. However, SFB93 degraded acetylene and, in the absence of ammonium, produced ethylene, indicating an active N2ase. Diazotrophic growth was observed under N2 but not in experimental controls incubated under argon. SFB93 exhibits acetylene fermentation and nitrogen fixation, the only known biochemical mechanisms for acetylene transformation. Our results indicate complex interactions between N2ase and AH and suggest novel evolutionary pathways for these relic enzymes from early Earth to modern days.

Applied and Environmental Microbiology↗

Dating base flow in streams using dissolved gases and diurnal temperature changes

A method is presented for using dissolved CFCs or SF 6 to estimate the apparent age of stream base flow by indirectly estimating the mean concentration of the tracer in the inflowing groundwater. The mean value is estimated simultaneously with the mean residence times of the gas and water in the stream by sampling the stream for one or both age tracers, along with dissolved nitrogen and argon at a single location over a period of approximately 12–14 h. The data are fitted to an equation representing the temporal in-stream gas exchange as it responds to the diurnal temperature fluctuation. The efficacy of the method is demonstrated by collecting and analyzing samples at six different stream locations across parts of northern Virginia, USA. The studied streams drain watersheds with areas of between 2 and 122 km 2 during periods when the diurnal stream temperature ranged between 2 and 5°C. The method has the advantage of estimating the mean groundwater residence time of discharge from the watershed to the stream without the need for the collection of groundwater infiltrating to streambeds or local groundwater sampled from shallow observation wells near the stream.

Virginia↗

Groundwater Dating with Atmospheric Halogenated Compounds

"Atmospheric environmental releases refer to the emission of stable, long-lived compounds of solely anthropogenic origin into the atmosphere and the use of the compounds to estimate dates of their incorporation into groundwater."

Book chapter↗

Measurements of HFC-134a and HCFC-22 in groundwater and unsaturated-zone air: implications for HFCs and HCFCs as dating tracers

A new analytical method using gas chromatography with an atomic emission detector (GC–AED) was developed for measurement of ambient concentrations of hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) in soil, air, and groundwater, with the goal of determining their utility as groundwater age tracers. The analytical detection limits of HCFC-22 (difluorochloromethane, CHClF 2 ) and HFC-134a (1,2,2,2-tetrafluoroethane, C 2 H 2 F 4 ) in 1 L groundwater samples are 4.3 × 10 − 1 and 2.1 × 10 − 1 pmol kg − 1 , respectively, corresponding to equilibrium gas-phase mixing ratios of approximately 5–6 parts per trillion by volume (pptv). Under optimal conditions, post-1960 (HCFC-22) and post-1995 (HFC-134a) recharge could be identified using these tracers in stable, unmixed groundwater samples. Ambient concentrations of HCFC-22 and HFC-134a were measured in 50 groundwater samples from 27 locations in northern and western parts of Virginia, Tennessee, and North Carolina (USA), and 3 unsaturated-zone profiles were collected in northern Virginia. Mixing ratios of both HCFC-22 and HFC-134a decrease with depth in unsaturated-zone gas profiles with an accompanying increase in CO 2 and loss of O 2 . Apparently, ambient concentrations of HCFC-22 and HFC-134a are readily consumed by methanotrophic bacteria under aerobic conditions in the unsaturated zone. The results of this study indicate that soils are a sink for these two greenhouse gases. These observations contradict the previously reported results from microcosm experiments that found that degradation was limited above-ambient HFC-134a. The groundwater HFC and HCFC concentrations were compared with concentrations of chlorofluorocarbons (CFCs, CFC-11, CFC-12, CFC-113) and sulfur hexafluoride (SF 6 ). Nearly all samples had measured HCFC-22 or HFC-134a that were below concentrations predicted by the CFCs and SF6, with many samples showing a complete loss of HCFC-22 and HFC-134a. This study indicates that HCFC-22 and HFC-134a are not conservative as environmental tracers and leaves in question the usefulness of other HCFCs and HFCs as candidate age tracers.

North Carolina, Tennessee, Virginia↗

Changes in monoterpene mixing ratios during summer storms in rural New Hampshire (USA)

Monoterpenes are an important class of biogenic hydrocarbons that influence ambient air quality and are a principle source of secondary organic aerosol (SOA). Emitted from vegetation, monoterpenes are a product of photosynthesis and act as a response to a variety of environmental factors. Most parameterizations of monoterpene emissions are based on clear weather models that do not take into account episodic conditions that can drastically change production and release rates into the atmosphere. Here, the monoterpene dataset from the rural Thompson Farm measurement site in Durham, New Hampshire is examined in the context of a set of known severe storm events. While some storm systems had a negligible influence on ambient monoterpene mixing ratios, the average storm event increased mixing ratios by 0.59 ± 0.21 ppbv, a factor of 93% above pre-storm levels. In some events, mixing ratios reached the 10's of ppbv range and persisted overnight. These mixing ratios correspond to increases in the monoterpene emission rate, ranging from 120 to 1240 g km −2 h −1 compared to an estimated clear weather rate of 116 to 193 g km −2 h −1 . Considering the regularity of storm events over most forested areas, this could be an important factor to consider when modeling global monoterpene emissions and their resulting influence on the formation of organic aerosols.

New Hampshire↗

Changes in monoterpene mixing ratios during summer storms in rural New Hampshire (USA)

Monoterpenes are an important class of biogenic hydrocarbons that influence ambient air quality and are a principle source of secondary organic aerosol (SOA). Emitted from vegetation, monoterpenes are a product of photosynthesis and act as a response to a variety of environmental factors. Most parameterizations of monoterpene emissions are based on clear weather models that do not take into account episodic conditions that can drastically change production and release rates into the atmosphere. Here, the monoterpene dataset from the rural Thompson Farm measurement site in Durham, New Hampshire is examined in the context of a set of known severe storm events. While some storm systems had a negligible influence on ambient monoterpene mixing ratios, the average storm event increased mixing ratios by 0.59 ± 0.21 ppbv, a factor of 93 % above pre-storm levels. In some events, mixing ratios reached the 10’s of ppbv range and persisted overnight. These mixing ratios correspond to increases in the monoterpene emission rate, ranging from 120 to 1240 g km−2 h −1 compared to an estimated clear weather rate of 116 to 193 g km−2 h −1 . Considering the regularity of storm events over most forested areas, this could be an important factor to consider when modeling global monoterpene emissions and their resulting influence on the formation of organic aerosols.

New Hampshire↗