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USGS2020

Hydrogeologic characterization, groundwater chemistry, and vulnerability assessment, Ute Mountain Ute Reservation, Colorado and Utah

The U.S. Geological Survey, in cooperation with the Ute Mountain Ute Tribe (UMUT), initiated a study in 2016 to increase understanding of the hydrogeology and chemistry of groundwater within select areas of the Ute Mountain Ute Reservation (UMUR) in Colorado and Utah, identify vulnerabilities to the system and other natural resources, and outline information needs to aid in the understanding and protection of groundwater resources. The results presented for this study can be used to support the UMUT’s goal of protecting their vital groundwater resources on the UMUR. Hydrogeologic conditions were characterized for the surficial aquifer contained in Quaternary-age unconsolidated surficial deposits and the Dakota aquifer contained in the Cretaceous-age Dakota Sandstone. In the surficial aquifer, median depth to water ranges from about 5.4 to 17.2 feet below land surface in the Farm and Ranch Enterprise area and 11 to 34 feet below land surface in the Towaoc area, and the water table slopes generally southwest or south. A map of depth to the top of the Dakota Sandstone was constructed from existing well data. Depths range from zero in outcrop areas to more than 3,000 feet below land surface on mesas in the southeastern part of the UMUR. Groundwater-chemistry data were collected by the UMUT from 13 springs and 31 wells from 1996 through 2017. Specific conductance was much lower for samples from springs than from wells; median values were 512 and 6,024 microsiemens per centimeter at 25 degrees Celsius, respectively. Spring samples were well oxygenated. A few well samples were anoxic (dissolved oxygen concentrations less than 0.5 milligrams per liter [mg/L]), indicating reducing conditions in the aquifer. About 75 percent of spring samples had fresh water (total dissolved solids concentrations less than 1,000 mg/L), and about 85 percent of well samples had brackish or highly saline water (total dissolved solids concentrations greater than 1,000 mg/L). Water type for springs on the Ute Mountains was calcium bicarbonate. Lower-altitude springs had a calcium-sulfate water type. Most well samples had sodium as the dominant cation, and sulfate, bicarbonate, and chloride as the dominant anions. Fluoride concentrations in about 45 percent of well samples were greater than an agricultural-use standard of 2 mg/L. Nitrate plus nitrite concentrations in most spring and well samples were less than about 1.6 mg/L per liter. Concentrations in samples from wells in the irrigated agricultural area were elevated; the maximum concentration was 78.5 mg/L. About one-half of the trace-element samples had concentrations that were less than laboratory reporting limits. Only aluminum, arsenic, and selenium in spring samples, and boron and selenium in well samples, were detected at concentrations greater than surface-water standards or water-quality standards for agricultural use of groundwater. Only three organic compounds, the pesticides alachlor and atrazine and the volatile organic compound di(2-ethylhexyl) phthalate, were detected in well samples. The Escherichia coli bacteria was detected in 47 and 23 percent of samples from wells and springs, respectively. The E. coli detections included samples from three culturally significant springs, which did not meet the UMUT cultural-use standard of total absence of E. coli. Tritium and carbon-14 were the primary environmental tracers used for interpreting groundwater ages for Lopez 2 Spring and five wells (AP–1, 5000 Block, Cottonwood Spring, Goodknight, and SE Toe). Water from the AP–1 well contained a mixture of pre- and post-1950s recharge. Tritium and carbon-14 recharge ages for Lopez 2 Spring (post-1950s in age), Goodknight and SE Toe wells (pre-1950s in age), and Cottonwood Spring well (primarily pre-1950s in age) are supported by helium-4 data. The helium-4 data for the 5000 Block well are inconsistent with the tritium and carbon-14 age of pre-1950s recharge because of interference caused by high methane concentrations in the water. Springs and surficial deposits are more vulnerable to contamination from anthropogenic chemicals than deeper bedrock wells. Bedrock aquifers are vulnerable in areas where the geologic formations containing the aquifers are exposed at the land surface. Groundwater in deep bedrock aquifers is likely thousands of years old and is not currently affected by present-day land uses. Both shallow and deep groundwater are vulnerable to naturally occurring salts and minerals, such as of total dissolved solids, major ions, nitrate, and trace elements. Effects of a changing climate on water resources and other ecological characteristics of the UMUR could include changes in evapotranspiration, a decrease in snowpack, decreased aquifer recharge and flow of springs, a decrease in soil moisture, and increased occurrence of wildfires and forest mortality. Of particular interest for the UMUT are possible effects of a changing climate on medicinal and culturally important plants and springs Several information needs were identified during this study that would aid in the understanding and protection of groundwater resources on the UMUR. These include well-completion information for bedrock wells, the collection of environmental tracer data at additional wells, the addition of methane and hydrocarbon analysis to well sampling plans, and the resampling of springs and wells that were last sampled in 2002 or earlier.

Colorado↗

USGS1999

Ground-water system, estimation of aquifer hydraulic properties, and effects of pumping on ground-water flow in Triassic sedimentary rocks in and near Lansdale, Pennsylvania

Ground water in Triassic-age sedimentary fractured-rock aquifers in the area of Lansdale, Pa., is used as drinking water and for industrial supply. In 1979, ground water in the Lansdale area was found to be contaminated with trichloroethylene, tetrachloroethylene, and other man-made organic compounds, and in 1989, the area was placed on the U.S. Environmental Protection Agency's (USEPA) National Priority List as the North Penn Area 6 site. To assist the USEPA in the hydrogeological assessment of the site, the U.S. Geological Survey began a study in 1995 to describe the ground-water system and to determine the effects of changes in the well pumping patterns on the direction of ground-water flow in the Lansdale area. This determination is based on hydrologic and geophysical data collected from 1995-98 and on results of the simulation of the regional ground-water-flow system by use of a numerical model. Correlation of natural-gamma logs indicate that the sedimentary rock beds strike generally northeast and dip at angles less than 30 degrees to the northwest. The ground-water system is confined or semi-confined, even at shallow depths; depth to bedrock commonly is less than 20 feet (6 meters); and depth to water commonly is about 15 to 60 feet (5 to 18 meters) below land surface. Single-well, aquifer-interval-isolation (packer) tests indicate that vertical permeability of the sedimentary rocks is low. Multiple-well aquifer tests indicate that the system is heterogeneous and that flow appears primarily in discrete zones parallel to bedding. Preferred horizontal flow along strike was not observed in the aquifer tests for wells open to the pumped interval. Water levels in wells that are open to the pumped interval, as projected along the dipping stratigraphy, are drawn down more than water levels in wells that do not intersect the pumped interval. A regional potentiometric map based on measured water levels indicates that ground water flows from Lansdale towards discharge areas in three drainages, the Wissahickon, Towamencin, and Neshaminy Creeks. Ground-water flow was simulated for different pumping patterns representing past and current conditions. The three-dimensional numerical flow model (MODFLOW) was automatically calibrated by use of a parameter estimation program (MODFLOWP). Steady-state conditions were assumed for the calibration period of 1996. Model calibration indicates that estimated recharge is 8.2 inches (208 millimeters) and the regional anisotropy ratio for the sedimentary-rock aquifer is about 11 to 1, with permeability greatest along strike. The regional anisotropy is caused by up- and down-dip termination of high-permeability bed-oriented features, which were not explicitly simulated in the regional-scale model. The calibrated flow model was used to compare flow directions and capture zones in Lansdale for conditions corresponding to relatively high pumping rates in 1994 and to lower pumping rates in 1997. Comparison of the 1994 and 1997 simulations indicates that wells pumped at the lower 1997 rates captured less ground water from known sites of contamination than wells pumped at the 1994 rates. Ground-water flow rates away from Lansdale increased as pumpage decreased in 1997. A preliminary evaluation of the relation between ground-water chemistry and conditions favorable for the degradation of chlorinated solvents was based on measurements of dissolved-oxygen concentration and other chemical constituents in water samples from 92 wells. About 18 percent of the samples contained less than or equal to 5 milligrams per liter dissolved oxygen, a concentration that indicates reducing conditions favorable for degradation of chlorinated solvents.

Water-Resources Investigations Report↗

USGS2006

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↗

USGS2023

Modeling, mapping, and measuring the risk of freshwater invasive species across Alaska

Freshwater ecosystems of the Alaskan Arctic and Subarctic provide resources that are culturally, ecologically, and economically invaluable. Presently, these regions are relatively free of the impacts from invasive species compared to southern latitudes. To date, there have been relatively few verified introductions of aquatic invasive species (AIS) to freshwater ecosystems in Alaska. The expanding list and distribution of AIS has led to significant negative ecological and economic impacts (e.g., waterweed Elodea nuttalli ; E. canadensis and northern pike Esox Lucius introduced outside its native range in Alaska). Escalating human activity across Alaskan lands and waters, coupled with rapidly shifting environmental conditions, increases the potential for new species introductions and subsequent establishment. Creating a proactive framework for well-informed decision-making and action can improve the effectiveness of prevention efforts and bolster decision support tools that help resource managers direct limited resources. Prioritizing AIS that may be introduced and become established, as well as the locations at highest risk of invasion, is foundational to building a proactive invasive species management framework in Alaska. This project sought to identify and prioritize AIS known to be invasive in the contiguous United States, evaluate current and future habitat suitability for AIS in Alaska, and assess potential for AIS to be transported to habitats across Alaska, utilizing similar assessment methods as implemented for Bering Sea marine invasive species and non-native plants in Alaska. To accomplish this goal, the objectives of the project were to: 1) develop a formal ranked list of potential AIS to freshwater systems of Alaska; 2) assess the level of establishment risk for potential AIS by developing habitat suitability models for waterbodies across Alaska; and 3), identify potential pathways and specific vectors for high-risk AIS to invade Alaska and develop a framework for how vector analysis will be completed to understand transport risk. Overall, our goal is horizon scanning which is defined by Roy et al. (2019) as “a systematic examination of potential threats and opportunities, within a given context, and likely future developments, which are at the margin of current thinking and planning.” The scans include pathway analyses and risk screening of species present at pathway origin points, with a focus on identifying species at high risk of being introduced, becoming established, spreading, and causing harm. We refined a list of 28 AIS from a list of hundreds based on characterizations of species’ invasiveness and species’ proximity to Alaska (USGS 2020; GBIF 2022). Next, we evaluated the relative invasiveness of individual species to create an initial AIS ranking. We sought to characterize habitat suitability of AIS by selecting variables that were continental in scale, covering North America to include Alaska as well as the lower 48 states comparing natural discharge, sub-basin average terrain slope (degrees), average silt fraction, average organic carbon, lithological class, and human footprint in sub-basin in 2009. We estimated AIS habitat suitability across the entire state of Alaska using the physiological tolerances of the AIS (Appendix 2). We also evaluated pathways and vectors for the introduction of AIS (Appendix 2). Many pathways and vectors considered did not meet the criteria for Alaska or freshwater systems. Of the 28 ranked species that we categorized as very high, high, and moderate levels of invasiveness; all three risk groups included fish and mollusks (Appendix 2). One commonality of the very high-invasiveness-ranked species was the availability of Ecological Risk Screening Summary documents (USFWS, 2022) produced by U.S. Fish and Wildlife Service (USFWS), except for the goldfish ( Carassius auratus ) and the New Zealand mudsnail ( Potamopyrgus antipodarum ). The Ecological Risk Screening Summary is now available for New Zealand mudsnails. In general, fish species often ranked very high or high in invasiveness and included sportfish and aquarium fish, suggesting the importance of pathways such as aquarium trade, fishing industry, intentional (but illegal) introductions of sportfishes and aquarium fishes for establishment. The technique we used for habitat suitability models necessitated aquatic environmental datasets that were continental in scale, which was often interpolated from very coarse resolution source data layers, particularly in Alaska. Better spatial data representing aquatic environments would likely improve this approach. While the lack of introductions in Alaska and nearby provinces and states is encouraging, the lack of occurrence data for the focal species also created complications for habitat suitability modeling. Despite the challenges, the habitat suitability models indicated limited suitability for warmwater species while some species, such as Brook trout (S alvelinus fontinalis ), have high habitat suitability across Alaska no matter what threshold approach is taken. Some environmental predictors were more important than others. Specifically, the most important predictor variable, ‘frost free days,’ was critical for 15 out of 28 species as expected due to harsh winter conditions in Arctic and Subarctic regions. The second most important predictor was ‘subbasin land surface runoff’, a variable that indicates the amount of discharge and runoff, while the third most important predictor was ‘snow cover’ another indication of winter conditions. Overall, the ability to understand the effect of future climate scenarios on the establishment of AIS was challenging. A detailed dataset of freshwater temperatures and water chemistry (e.g., pH, calcium) would greatly improve the ability to predict invasiveness of freshwater species to Alaska’s ecosystems on a regional basis. Future studies may benefit from a more focused geographic scope examining a group of subbasins or a regional basin rather than the entire state. These drainages could be selected based upon the mostly likely locations of introduction pathways. The two most prevalent pathway risks for AIS are in-state transfer and stowaways/contaminants. Although there are examples of introductions from other pathways, the risk is somewhat mitigated by Alaska’s climate and regulations. However, variable application of protocols for inspection and cleaning of fishing gear, watercraft, and other similar items while traveling into Alaska as well as transferring from waterbody to waterbody within the state creates a substantial risk in introducing invasive species. We plot cumulative invasive vulnerability for all subbasins and for the top 10% of subbasins (Appendix 3).

Alaska↗

USGS2018

Baseline water quality of an area undergoing shale-gas development in the Muskingum River watershed, Ohio, 2015–16

In 2015–16, the U.S. Geological Survey, in cooperation with the Muskingum Watershed Conservancy District, led a study to assess baseline (2015–16) surface-water quality in six lake drainage basins within the Muskingum River watershed that are in the early years of shale-gas development. In 2015, 9 of the 10 most active counties in Ohio for oil and gas development were wholly or partially within the Muskingum River watershed. In addition to shale gas development, the area has a history of conventional oil and gas development and coal mining. In all, 30 surface-water sites were sampled: 20 in tributaries flowing to the lakes, 4 in lakes themselves, and 6 downstream of the lakes. At each of the 30 sites, 6 samples were collected to characterize surface-water chemistry throughout a range of hydrologic conditions. The sampling generally occurred during low flows (periods of greater groundwater contribution) rather than during runoff events (periods of high stream stage). Trilinear diagrams of major ion chemistry revealed three main types of water in the study area―sulfate-dominated waters, bicarbonate-dominated waters, and waters with mixed bicarbonate and chloride anions. Most sites produced samples of bicarbonate-dominated water, and 11 sites produced samples with sulfate-type waters. Mixed bicarbonate and chloride waters were found in samples from two of the six lake drainage basins studied. The baseline (2015–16) assessment of surface-water quality in the study area indicated that few water-chemistry constituents and properties occurred at concentrations or levels that would adversely affect aquatic organisms. Chemical-specific, aquatic life use criteria were not met in only three instances: two were for total dissolved solids at sites likely impacted by coal mining in their drainage basins (hereafter referred to as “mine-impacted sites”), and one was for dissolved oxygen. Mine drainage from historical coal mining in the region likely affected the quality of about one-third of the streams sampled. To simplify interpretation of water-chemistry results, 11 sites with sulfate-type water were identified as mine-impacted sites based on water-quality criteria established by Ohio Department of Natural Resources, Division of Mineral Resources Management, and separated out for subsequent statistical analysis. Concentrations or levels of bicarbonate, boron, calcium, carbonate, total dissolved solids, fluoride, magnesium, lithium, pH, potassium, sodium, specific conductance, strontium, sulfate, and suspended sediment in water were higher (significance level of 0.05) at mine-impacted stream sites than at non-mine-impacted stream sites. An accidental release of oil- and gas-related brines could increase salinity (sodium and chloride), the concentration of total dissolved solids in shallow groundwater and streams, and specific conductance. For this study, chloride concentrations in the study area ranged from 2.12 to 76.1 milligrams per liter. Sources of chloride in water samples were evaluated using binary mixing curves and ratios of chloride to bromide. These ratios indicated that 13 samples from 3 sites in the drainage basin that contained the highest density of conventional oil and gas wells in the study, as well as 4 samples collected from other drainage basins, likely contained a component of brine. Concentrations or levels of barium, bromide, chloride, iron, lithium, manganese, and sodium were significantly higher (alpha = 0.05) in samples with a component of brine than in samples without a component of brine. Benzene, toluene, ethylbenzene and xylene (BTEX), compounds that occur naturally in crude oil, made up 24 of the 45 detections (53 percent) of volatile organic compounds in the study area. The BTEX detections were not associated with sites containing a component of brine. The only volatile organic compound detected in any of the 17 samples that contained a component of brine was acetone, detected in 3 (18 percent) of these samples and in 11 percent of samples not containing a component of brine. Considering that BTEX are gasoline hydrocarbons and that most of the detections occurred during warmer months in and around the lakes, the BTEX detections likely are associated with increases in outdoor activities such as automobile and boating traffic. Radium-226 and radium-228 were included in the list of analytes for this study because production water from shale-gas drilling can contain these naturally occurring radioactive materials. Concentrations of radium-226 exceeded background levels in only two surface-water samples. Concentrations of radium-228 exceeded background levels in one surface-water sample. A brine signature potentially indicative of oil and gas contamination was detected in samples collected at two sites that contained active or plugged waste injection wells, or both. Results from the study indicated significant differences in the median concentrations of bromide, chloride, lithium, manganese, sodium, and total dissolved nitrogen between sites with and without injection wells in their drainage areas. Median concentrations of bromide, chloride, lithium, and sodium, which are common oil- and gas-related contaminants, were higher at sites with injection wells in their drainage areas compared to sites without injection wells. Historical (1960s, 1970s, and 1980s) chloride concentrations and streamflow data at or near five of the six sampling sites downstream from each lake dam were compared to current (2015–16) values. An analysis of covariance was done to test the effects of streamflow, time (decade), and the combined effects (cross product) of streamflow and time on chloride concentrations. Those analyses indicated that streamflow was not significant in explaining the variation in chloride concentration, likely because streamflow in those locations is controlled by dam operations; therefore, association between runoff-generating events and streamflow is less direct than in unregulated streams. From the 1980s to the study period (2015–16), data for three of the five lakes indicated an increase in chloride concentrations. The comparison of historical and current (2015–16) study data from samples collected at another lake indicated that chloride concentrations increased from the 1960s to the 1970s, but concentrations in the 1970s and 2015–16 were similar even though 13 samples from this lake drainage basin were classified as having a component of brine. Median chloride concentrations for the fifth lake, however, seemed to decrease from the 1980s to 2015–16.

Ohio↗

USGS2008

Environmental presence and persistence of pharmaceuticals: An overview

Emerging contaminants (ECs) in the environment – that is, chemicals with domestic, municipal, industrial, or agricultural sources that are not commonly monitored but may have the potential for adverse environmental effects – is a rapidly growing field of research. The use of “emerging” is not intended to infer that the presence of these compounds in the environment is new. These chemicals have been released into the environment as long as they have been in production or, in the case of hormones and other endogenous compounds, since the rise of animal life. What is emerging is the interest by the scientific and lay communities in the presence of these chemicals in the environment, the analytical capabilities required for detection, and the subtle effects that very small concentrations of these chemicals appear to have on aquatic biota. In December 2006, Environmental Science & Technology devoted an entire special issue (volume 40, number 23) to the topic of ECs, illustrating the increased interest in the subject. Within the EGs, one particular class that has seen a substantial increase in research over the past 10 years is pharmaceuticals and personal-care products (PPCPs). This increased research interest can be demonstrated by several means, including requests for proposals from funding agencies, but the clearest indication of a focused effort to understand the introduction, transformation, and potential health and environmental effects of PPCPs and ECs, in general, is the number of published reports. This increase can be shown by examining six environmental journals that regularly publish PPCP-related papers – Chemosphere , Environmental Science & Technology , Environmental Toxicology and Chemistry , Science of the Total Environment , Water Research , and Water Science and Technology . In 1998 there were 22 papers published on pharmaceuticals, antibiotics, or drugs in these 6 journals; by 2006, this number increased sixfold to 132 papers (Figure 1.1). This growth can be attributed to a number of factors. The presence of pharmaceuticals in surface-water samples from Europe and the United States was documented in several sentinel papers. These ground-breaking works encouraged other scientists to examine the rivers, streams, lakes, and reservoirs in their regions for such chemicals. In addition, the intense public attention paid to news reports on the environmental detections of these chemicals and possible effects of aquatic life has made this issue visible to the wastewater-treatment, drinking-water treatment, and regulatory communities. This has driven the funding bodies associated with these communities to fund studies or request proposals that address the presence, fate, and effects of PPCPs in aquatic systems. The release of the first comprehensive reconnaissance of pharmaceuticals and other wastewater contaminants in the United States provides an example of the intense media interest in this topic. Within 6 days on online publication of this study, 72 newspapers across the United States had published articles describing the results, either locally written or based on international media syndicate reports. There also was substantial concurrent coverage by local and national radio and television outlets, including the Cable News Network, ABC World News Tonight , and National Public Radio. A substantial fraction of these news stories may be attributable to press releases and media briefings prior to publication. However, the interest by television and print journalists in reporting the results of a peer-reviewed journal article to the general public was motivated by the recognition that describing the presence of PPCPs in water supplies would be of interest to the public. To better convey the results of the study published by Koplin et al. to the public, a separate general-interest fact sheet was published to summarize the important points of the study. Because PPCPs are commonly and widely used by individuals, there is likely a preexisting, personal identification with these compounds that does not occur for the wide range of other organic and inorganic contaminants whose presence in the environment has previously been described. This greater public “name recognition” makes itself known through the media to the regulatory and technical community and has prompted interest in sponsoring research that defines the composition and concentrations of PPCPs in potential sources and their fate and effects following relase into the environment. Independent of the drivers that potentially fuel the interest in studies of PPCPs, it is clear that PPCP research has grown beyond surface-water studies to examine issues such as: • Presence in other matrices, such as groundwater, landfill leachates, sediments, and biosolids. • Environmental transport and fate in surface water, groundwater, and soils amended with reclaimed water or biosolids. • PPCP source elucidation, such as wastewater treatment plant (WWTP) effluents, confined animal feeding operations (CAFOs), and aquaculture. • Removal during wastewater and drinking-water treatment. • Effects on aquatic ecosystems, terrestrial ecosystems, and human health. The chapters in this book provide an extensive examination of current environmental pharmaceutical research and are divided into three sections: “Occurrence and Analysis of Pharmaceuticals in the Environment,” “Environment Fate and Transformations of Veterinary Pharmaceuticals,” and “treatment of Pharmaceuticals in Drinking Water and Wastewater.” The purpose of this introductory overview chapter is to outline current (2004-2006) knowledge about the presence and concentration of PPCPs as described in the published literature. Previous reviews should be consulted for discussions on pre-2004 publications. Those reviews will provide the reader with a comprehensive introduction to the topic of PPCPs in the environment. This chapter describes the sources of PPCPs and other organic contaminants often associated with human wastewater into the environment, the range of concentrations present in various environmental compartments, and the potential routes of removal/sequestration. An overview of the sources and fate of veterinary pharmaceuticals will be discussed in Chapter 5, “Fate and Transport of Veterinary Medicines in the Soil Environment.”

Book chapter↗

USGS2000

Diagenetic fate of organic contaminants on the Palos Verdes Shelf, California

Municipal wastes discharged through deepwater submarine outfalls since 1937 have contaminated sediments of the Palos Verdes Shelf. A site approximately 6–8 km downcurrent from the outfall system was chosen for a study of the diagenetic fate of organic contaminants in the waste-impacted sediments. Concentrations of three classes of hydrophobic organic contaminants (DDT+metabolites, polychlorinated biphenyls (PCBs), and the long-chain alkylbenzenes) were determined in sediment cores collected at the study site in 1981 and 1992. Differences between the composition of effluent from the major source of DDT (Montrose Chemical) and that found in sediments suggests that parent DDT was transformed by hydrolytic dehydrochlorination during the earliest stages of diagenesis. As a result, p , p ′-DDE is the dominant DDT metabolite found in shelf sediments, comprising 60–70% of ΣDDT. The p , p -DDE/ p , p ′-DDMU concentration ratio decreases with increasing sub-bottom depth in sediment cores, indicating that reductive dechlorination of p , p ′-DDE is occurring. Approximately 9–23% of the DDE inventory in the sediments may have been converted to DDMU since DDT discharges began ca. 1953. At most, this is less than half of the decline in p , p ′-DDE inventory that has been observed at the study site for the period 1981–1995. Most of the observed decrease is attributable to remobilization by processes such as sediment mixing coupled to resuspension, contaminant desorption, and current advection. Existing field data suggest that the in situ rate of DDE transformation is 10 2 –10 3 times slower than rates determined in recent laboratory microcosm experiments (Quensen, J.F., Mueller, S.A., Jain, M.K., Tiedje, J.M., 1998. Reductive dechlorination of DDE to DDMU in marine sediment microcosms. Science, 280, 722–724.). This explains why the DDT composition (i.e. o , p ′-, p , p ′-isomers of DDE, DDD, DDT) of sediments from this site have not changed significantly since at least 1972. Congener-specific PCB compositions in shelf sediments are highly uniform and show no evidence of diagenetic transformation. Apparently, the agents/factors responsible for reductive dechlorination of DDE are not also effecting alteration of the PCBs. Two types of long-chain alkylbenzenes were found in the contaminated sediments. Comparison of chain length and isomer distributions of the linear alkylbenzenes in wastewater effluent and surficial sediment samples indicate that these compounds undergo biodegradation during sedimentation. Further degradation of the linear alkylbenzenes occurs after burial despite relatively invariant isomer compositions. The branched alkylbenzenes are much more persistent than the linear alkylbenzenes, presumably due to extensive branching of the alkyl side chain. Based on these results, p , p ′-DDE, PCBs, and selected branched alkylbenzenes are sufficiently persistent for use in molecular stratigraphy. The linear alkylbenzenes may also provide information on depositional processes. However, their application as quantitative molecular tracers should be approached with caution.

California↗

USGS2015

Status and understanding of groundwater quality in the Northern Coast Ranges study unit, 2009: California GAMA Priority Basin Project

Groundwater quality in the 633-square-mile (1,639-square-kilometer) Northern Coast Ranges (NOCO) study unit was investigated as part of the Priority Basin Project (PBP) of the Groundwater Ambient Monitoring and Assessment (GAMA) Program and the U.S. Geological Survey (USGS) National Water-Quality Assessment Program. The study unit is composed of two study areas (Interior Basins and Coastal Basins) and is located in northern California in Napa, Sonoma, Lake, Colusa, Mendocino, Glenn, Humboldt, and Del Norte Counties. The GAMA-PBP is being conducted by the California State Water Resources Control Board in collaboration with the USGS and the Lawrence Livermore National Laboratory. The GAMA NOCO study was designed to provide a spatially unbiased assessment of the quality of untreated (ambient) groundwater in the primary aquifer system within the study unit. The assessment is based on water-quality and ancillary data collected in 2009 by the USGS from 58 sites and on water-quality data from the California Department of Public Health (CDPH) database. The primary aquifer system is defined by the perforation intervals of sites listed in the CDPH water-quality database for the NOCO study unit. Groundwater quality in the primary aquifer system may differ from the quality in the shallow or deep water-bearing zones. The first component of this study, the status assessment of the current quality of the groundwater resource, was performed by using data from samples analyzed for inorganic constituents (such as trace elements and major and minor ions), organic constituents (volatile organic compounds and pesticides and pesticide degradates), the special-interest constituent perchlorate, and microbial indicators. This status assessment is intended to characterize the quality of groundwater resources in the primary aquifer system of the NOCO study unit, not the quality of treated drinking water delivered to consumers by water purveyors. Relative-concentrations (sample concentration divided by the health- or aesthetic-based benchmark concentration) were used for evaluating groundwater quality for those constituents that have Federal or California regulatory or nonregulatory benchmarks for drinking-water quality. A relative-concentration greater than (>) 1.0 indicates a concentration greater than a benchmark, and a relative-concentration less than or equal to (≤) 1.0 indicates a concentration less than or equal to a benchmark. Relative-concentrations of organic constituents and perchlorate were classified as “high” (relative-concentration >1.0), “moderate” (0.1 < relative-concentration ≤1.0), or “low” (relative-concentration ≤0.1). Relative-concentrations of inorganic constituents were classified as “high” (relative-concentration >1.0), “moderate” (0.5 < relative-concentration ≤1.0), or “low” (relative-concentration ≤0.5). Aquifer-scale proportion was used as the primary metric in the status assessment for evaluating regional-scale groundwater quality. High aquifer-scale proportion was defined as the percentage of the area of the primary aquifer system with a relative-concentration >1.0 for a particular constituent or class of constituents; the percentage is based on an aerial rather than a volumetric basis. Moderate and low aquifer-scale proportions were defined as the percentage of the primary aquifer system with moderate and low relative-concentrations, respectively. Two statistical approaches—grid-based and spatially weighted—were used to evaluate aquifer-scale proportions for individual constituents and classes of constituents. Grid-based and spatially weighted estimates were comparable in the NOCO study unit (within 90 percent confidence intervals). Inorganic constituents (one or more) with health-based benchmarks were detected at high relative-concentrations in 10.3 percent and at moderate relative-concentrations in 13.8 percent of the primary aquifer system. The high aquifer-scale proportion of inorganic constituents primarily reflected high aquifer-scale proportions of boron (in 8.6 percent of the primary aquifer system), arsenic (in 3.4 percent), and barium (in 1.7 percent). Inorganic constituents with aesthetic-based benchmarks were detected at high relative-concentrations in 39.7 percent and at moderate relative-concentrations in 10.3 percent of the primary aquifer system. The constituents present at high relative-concentrations were iron (25.9 percent) and manganese (39.7 percent). Relative-concentrations of organic constituents with health-based benchmarks (one or more) were high in 0.2 percent, moderate in 1.7 percent, and low in 39.7 percent of the primary aquifer system. Organic constituents were not detected in 58.4 percent of the primary aquifer system. Of the 168 organic constituents analyzed, 11 constituents were detected. Two organic constituents had detection frequencies >10 percent: the trihalomethane chloroform and the herbicide simazine. For the 10 detected organic constituents that had health-based benchmarks, nearly all detections had low relative-concentrations. The special-interest constituent perchlorate was detected at moderate relative-concentrations in 1.7 percent and at low relative-concentrations in 22.4 percent of the primary aquifer system. Perchlorate was not detected in 75.9 percent of the primary aquifer system. The second component of this study, the understanding assessment , evaluated relations between constituent concentrations and values of selected potential explanatory factors to identify the factors potentially affecting the concentrations and occurrences of constituents found at high relative-concentrations or, for organic constituents, with detection frequencies >10 percent. The potential explanatory factors evaluated were land use (including density of septic tanks and leaking or formerly leaking underground fuel tanks), well construction (well depth and depth to the top of the perforated interval in the well), hydrologic conditions (aridity index, field water temperature, and distance to nearest hot spring and geothermal well), pH, dissolved oxygen concentration, study area, groundwater age distribution, and geochemical conditions. High and moderate relative-concentrations of boron primarily occurred in the Interior Basins study area and may be attributed to groundwater interacting with hydrothermal systems. High and moderate relative-concentrations of boron were associated with elevated groundwater temperatures, groundwater chemistry characteristics similar to those of geothermal waters, and distance to known geothermal areas. Boron concentrations generally were higher where low dissolved oxygen concentrations or anoxic conditions exist. High and moderate relative-concentrations of arsenic predominantly occur in the Interior Basins study area under reducing conditions. Arsenic concentrations also may be influenced by hydrothermal systems (when present). Chloroform, simazine, and perchlorate were observed in the Interior Basins and Coastal Basins study areas, predominantly at shallow sites with top-of-perforation depths ≤70 feet below land surface, with modern water (post-1950s), and with oxic groundwater conditions.

California↗

USGS2017

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↗

USGS2022

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↗

USGS2017

Fluorine

Fluorine compounds are essential in numerous chemical and manufacturing processes. Fluorspar is the commercial name for fluorite (isometric CaF 2 ), which is the only fluorine mineral that is mined on a large scale. Fluorspar is used directly as a fluxing material and as an additive in different manufacturing processes. It is the source of fluorine in the production of hydrogen fluoride or hydrofluoric acid, which is used as the feedstock for numerous organic and inorganic chemical compounds. The United States was the world’s leading producer of fluorspar until the mid-1950s. In the mid-1970s, the U.S. fluorspar mining industry began to decline because of foreign competition. By 1982, there was essentially only a single U.S. producer left, and that company ceased mining in 1996. Consumption of fluorspar in the United States peaked in the early 1970s, which was also the peak period of U.S. steel production. Since then, U.S. fluorspar consumption has decreased substantially; the United States has nonetheless increased its imports of downstream fluorine compounds, such as, in order of tonnage imported, hydrofluoric acid, aluminum fluoride, and cryolite. This combination of no U.S. production (until recently) and high levels of consumption has made the United States the world’s leading fluorspar-importing country, in all its various forms. The number of fluorspar-exporting countries has decreased substantially in recent decades, and, as a result, the United States has become dependent on just a few countries to supply its needs. In 2013, the United States imported the majority of its fluorspar from three countries, which were, in descending order of the amount imported, Mexico, China, and South Africa. Geologically, in igneous systems, fluorine is one of a number of elements that are “incompatible.” These incompatible elements become concentrated in the residual magma while the common silicates crystallize upon magma ascent and cooling, leading to relatively high fluorine concentrations in the more evolved or differentiated igneous rocks and in hydrothermal deposits associated with those evolved igneous rocks. In sedimentary rocks, fluorine’s highest concentrations are found in phosphorites because fluorine substitutes for hydroxyl ions in apatite, which leads to fluorine concentrations of, typically, from 2 to 4 weight percent in phosphorites. Because of the presence of fluorine, phosphate fertilizer manufacturers can produce a fluorosilicic acid byproduct. Most deposits mined for fluorine are hydrothermal, however, and consist of fluorine minerals that precipitated from hot water. Magmatic brines and brines from deep within sedimentary basins that have high concentrations of dissolved fluoride are the mineralizing fluids for various types of hydrothermal fluorspar deposits. Relatively dilute hydrothermal fluids that formed in some volcanic rocks can also transport sufficient fluoride to form a high-grade fluorspar deposit. Fluorite has low solubility in a common range of hydrothermal temperatures, particularly from about 160 degrees Celsius (°C) down to 60 °C. The increasing fluorite solubility below 60 °C partly explains why some water with exceptionally high levels of dissolved fluorine are found even at ambient temperatures in evaporitic lake basins in some East African Rift valleys in Kenya and Tanzania. The geologic conditions that led to the high concentrations there are known to exist in a number of other places in the world as well, including, perhaps, places in the Basin and Range province of the United States. Eight minerals or mineral groups have sufficient fluorine in their structures to be considered as possible ores of the element; they are bastnaesite (also spelled bastnäsite; and other fluorocarbonates), cryolite, sellaite, villiaumite, fluorite, fluorapatite (in phosphorites), various phyllosilicates, and topaz. Fluorite is currently the only mineral that is mined for fluorine, and nomineral except fluorite is likely to become a source of commercially produced fluorine as a primary product as long as supplies from relatively thick and high-grade fluorite deposits continue to be available. At least seven classes (which include one subclass) of hydrothermal fluorite deposits are recognized; they are classified according to their tectonic and (or) magmatic settings, as follows: (1) carbonatite-related fluorspar deposits; (2) alkaline-intrusion-related fluorspar deposits; (3) alkaline-volcanic-related epithermal fluorspar deposits; (4) Mississippi Valley-type fluorspar deposits (and a subclass of salt-related carbonate-hosted fluorspar deposits); (5) fluorspar deposits related to strongly differentiated granites; (6) subalkaline-volcanic-related epithermal fluospar deposits; and (7) fluorspar deposits that appear to be conformable within tuffaceous limy lacustrine sediments. An eighth class (not hydrothermal) is that of fluorspar deposits concentrated in soils and weathered zones; that is, residual fluorspar deposits. Generally, fluorspar deposits related to strongly differentiated granites have larger tonnages and lower grades than carbonatite-related fluorspar deposits, which, in turn, have larger tonnages and lower grades than fluorspar vein deposits from various other classes. The United States has a few identified resources of fluorspar, most notably the Klondike II property in the Illinois- Kentucky fluorspar district located about 8 kilometers southwest of Salem, Kentucky, which has a large vein that contains at least 1.6 million metric tons at a grade of 60 percent CaF 2 (Feytis, 2009). Additional fluorspar resources of lower grade but larger tonnage have been identified at Hicks Dome in the Illinois-Kentucky fluorspar district and at Lost River near the western tip of the Seward Peninsula in Alaska, along with a couple of dozen smaller, higher grade resources. Internationally, new mines that either opened before the beginning of 2013 or were scheduled to open soon after that time include the Nui Phao tungsten-fluorspar-bismuth-copper-gold deposit in northern Vietnam; the St. Lawrence project in Newfoundland, Canada, which is located in a well-known fluorspar district; the Bamianshan deposit, which is related to a strongly differentiated granite in northwestern Zhejiang Province, China, near some of that Province’s large, subalkaline-volcanic-related epithermal veins; and the Nokeng project in South Africa, which is also related to a strongly differentiated granite. Other deposits in northwestern Australia, Nevada (United States), Norway, South Africa, and Sweden have been identified and could be put into production within just a few years. Among undiscovered resources, an interesting possibility might be to produce a fluorine product from evaporitic, high-fluorine, high-pH sodium-carbonate brines like Lake Magadi (Kenya) and Lake Natron (Tanzania) in Africa’s Eastern Rift Valley. In addition, apparently conformable fluorspar deposits in tuffaceous limy lacustrine sediments, such as those in Italy, are likely to occur in similar young alkalic volcanic settings elsewhere in the world. Modern geophysical and geochemical exploration techniques have typically not been brought to bear in exploration for new fluorspar deposits, although such techniques are likely to be used in future exploration. The tendency for fluorine to dissolve in significant concentrations in water at low temperature allows both surface water and groundwater to be used as sampling media in geochemical exploration. Evolved granite-related fluorspar deposits may be particularly susceptible to geophysical exploration methods because crystalline rocks that form a basement to sedimentary sections can be approximately defined with gravity and magnetic methods, and magnetite-bearing skarns can be directly detected with magnetic surveys. Environmental considerations of fluorine mining focus especially on drinking water, where high fluorine concentrations can lead to tooth decay; dental and skeletal fluorosis; and bone and cartilage conditions, including genu valgum, which is the crippling bone deformity more commonly known as knock knee. Trace amounts of other elements in fluorspar ores are a concern at some deposits; for example, high beryllium concentrations in alkaline-volcanic-related epithermal deposits or high cadmium concentrations associated with Mississippi Valley-type and salt-related carbonate-hosted fluorspar deposits. Future research might include testing whether fluorine can be extracted economically from high-pH, sodium-carbonate brines and exploring for new occurrences of apparently conformable fluorspar deposits in tuffaceous limy lacustrine sediments outside of the Latium Region of Italy. Other promising new areas of research could be studies of fluorspar deposit fluid inclusion compositions by quadrupole mass spectrometry, by noble gas mass spectrometry on irradiated fluid inclusions, or by chlorine isotopes, while also measuring the chemistry of the same fluid inclusions either by bulk crush-and-leach methods or by laser ablation-inductively coupled plasma mass spectrometry. Advanced studies of fluid inclusion chemistry could be applied beneficially to some of the enigmatic large epithermal fluorspar veins at various places in the world, where they might determine those deposits’ possible relationships to igneous intrusions, or to dissolved salt, or to heated meteoric water in volcanic sections, or perhaps to all three. This knowledge could help focus new exploration.

Professional Paper↗