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USGS2012

Nutrient concentrations and loads in the northeastern United States - Status and trends, 1975-2003

The U.S. Geological Survey (USGS) National Water-Quality Assessment Program (NAWQA) began regional studies in 2003 to synthesize information on nutrient concentrations, trends, stream loads, and sources. In the northeastern United States, a study area that extends from Maine to central Virginia, nutrient data were evaluated for 130 USGS water-quality monitoring stations. Nutrient data were analyzed for trends in flow-adjusted concentrations, modeled instream (non-flow-adjusted) concentrations, and stream loads for 32 stations with 22 to 29 years of water-quality and daily mean streamflow record during 1975-2003 (termed the long-term period), and for 46 stations during 1993-2003 (termed the recent period), by using a coupled statistical model of streamflow and water quality developed by the USGS. Recent trends in flow-adjusted concentrations of one or more nutrients also were analyzed for 90 stations by using Tobit regression. Annual stream nutrient loads were estimated, and annual nutrient yields were calculated, for 47 stations for the long-term and recent periods, and for 37 additional stations that did not have a complete streamflow and water-quality record for 1993-2003. Nutrient yield information was incorporated for 9 drainage basins evaluated in a national NAWQA study, for a total of 93 stations evaluated for nutrient yields. Long-term downward trends in flow-adjusted concentrations of total nitrogen and total phosphorus (18 and 19 of 32 stations, respectively) indicate regional improvements in nutrient-related water-quality conditions. Most of the recent trends detected for total phosphorus were upward (17 of 83 stations), indicating possible reversals to the long-term improvements. Concentrations of nutrients in many streams persist at levels that are likely to affect aquatic habitat adversely and promote freshwater or coastal eutrophication. Recent trends for modeled instream concentrations, and modeled reference concentrations, were evaluated relative to ecoregion-based nutrient criteria proposed by the U.S. Environmental Protection Agency. Instream concentrations of total nitrogen and total phosphorus persist at levels higher than proposed criteria at more than one-third and about one-half, respectively, of the 46 stations analyzed. Long-term trends in nutrient loads were primarily downward, with downward trends in total nitrogen and total phosphorus loads detected at 12 and 17 of 32 stations, respectively. Upward trends were rare, with one upward trend for total nitrogen loads and none for total phosphorus. Trends in loads of nitrite-plus-nitrate nitrogen included 7 upward and 8 downward trends among 32 stations. Downward trends in loads of ammonia nitrogen and total Kjeldahl nitrogen were detected at all six stations evaluated. Long-term downward trends detected in four of the five largest drainage basins evaluated include: total nitrogen loads for the Connecticut, Delaware, and James Rivers; total Kjeldahl nitrogen and ammonia nitrogen loads for the Susquehanna River; ammonia nitrogen and nitrite-plus-nitrate nitrogen loads for the James River; and total phosphorus loads for the Connecticut and Delaware Rivers. No trends in load were detected for the Potomac River. Nutrient yields were evaluated relative to the extent of land development in 93 drainage basins. The undeveloped land-use category included forested drainage basins with undeveloped land ranging from 75 to 100 percent of basin area. Median total nitrogen yields for the 27 undeveloped drainage basins evaluated, including 9 basins evaluated in a national NAWQA study, ranged from 290 to 4,800 pounds per square mile per year (lb/mi 2 /yr). Total nitrogen yields even in the most pristine drainage basins may be elevated relative to natural conditions, because of high rates of atmospheric deposition of nitrogen in parts of the northeastern United States. Median total phosphorus yields ranged from 12 to 330 lb/mi 2 /yr for the 26 undeveloped basins evaluated. The undeveloped category includes some large drainage basins with point-source discharges and small percentages of developed land; in these basins, streamflow from undeveloped headwater areas dilutes streamflow in more urbanized reaches, and dampens but does not eliminate the point-source "signal" of higher nutrient loads. Median total nitrogen yields generally do not exceed 1,700 lb/mi 2 /yr, and median total phosphorus yields generally do not exceed 100 lb/mi 2 /yr, in the drainage basins that are least affected by human land-use and waste-disposal practices. Agricultural and urban land use has increased nutrient yields substantially relative to undeveloped drainage basins. Median total nitrogen yields for 24 agricultural basins ranged from 1,700 to 26,000 lb/mi 2 /yr, and median total phosphorus yields ranged from 94 to 1,000 lb/mi 2 /yr. The maximum estimated total nitrogen and total phosphorus yields, 32,000 and 16,000 lb/mi 2 /yr, respectively, for all stations in the region were in small (less than 50 square miles (mi 2 )) agricultural drainage basins. Median total nitrogen yields ranged from 1,400 to 17,000 lb/mi 2 /yr in 26 urbanized drainage basins, and median total phosphorus yields ranged from 43 to 1,900 lb/mi 2 /yr. Urbanized drainage basins with the highest nutrient yields are generally small (less than 300 mi2) and are drained by streams that receive major point-source discharges. Instream nutrient loads were evaluated relative to loads from point-source discharges in four drainage basins: the Quinebaug River Basin in Connecticut, Massachusetts, and Rhode Island; the Raritan River Basin in New Jersey; the Patuxent River Basin in Maryland; and the James River Basin in Virginia. Long-term downward trends in nutrient loads, coupled with similar trends in flow-adjusted nutrient concentrations, indicate long-term reductions in the delivery of most nutrients to these streams. However, the absence of recent downward trends in load for most nutrients, coupled with instream concentrations that exceed proposed nutrient criteria in several of these waste-receiving streams, indicates that challenges remain in reducing delivery of nutrients to streams from point sources. During dry years, the total nutrient load from point sources in some of the drainage basins approached or equaled the nutrient load transported by the stream.

Connecticut;Delaware;Maine;Maryl;Massachusetts;New↗

USGS2015

Geochemical conditions and the occurrence of selected trace elements in groundwater basins used for public drinking-water supply, Desert and Basin and Range hydrogeologic provinces, 2006-11: California GAMA Priority Basin Project

The geochemical conditions, occurrence of selected trace elements, and processes controlling the occurrence of selected trace elements in groundwater were investigated in groundwater basins of the Desert and Basin and Range (DBR) hydrogeologic provinces in southeastern California as part of the Priority Basin Project (PBP) of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA PBP is designed to provide an assessment of the quality of untreated (raw) groundwater in the aquifer systems that are used for public drinking-water supply. The GAMA PBP is being conducted by the California State Water Resources Control Board in collaboration with the U.S. Geological Survey and the Lawrence Livermore National Laboratory. The DBR hydrogeologic provinces consist of 141 defined groundwater basins separated by mountain ranges, faults, and other features. This report presents analyses of data collected from nine study areas within the DBR hydrogeologic provinces: Antelope Valley, Borrego Valley, the Central Desert area, Coachella Valley, Colorado River, Indian Wells Valley, Low-Use Basins of the Mojave and Sonoran Deserts, the Mojave, and Owens Valley. Collectively, these nine study areas are referred to as the DBR study unit. The study unit covers approximately 7,000 square miles and includes the 63 groundwater basins in the DBR hydrogeologic provinces in which groundwater is used for public drinking-water supply. The vast majority of the 223 wells sampled for this study were long-screened production wells used primarily for public supply. Uncorrected carbon-14 ( 14 C) groundwater ages for samples collected in the DBR study unit ranged from less than (<) 100 to 33,700 years before present (BP). Sixty-six percent of sample ages were greater than (>) 100 years BP, and 40 percent were >3,800 years BP. Samples collected from wells located adjacent to mountain-front recharge areas or major surface-water features generally had younger groundwater ages than did samples collected from wells located away from mountain fronts or towards the distal ends of basin groundwater flow paths. Most groundwater sampled in the DBR study unit had alkaline pH: 89 percent of sample pH values ranged from 7.1 to 9.8, with 37 percent greater than or equal to (≥) 7.9. Groundwater age was significantly correlated (positively) with pH, likely because silicate weathering is a primary control on groundwater pH and is a slow process. The oxidation-reduction (redox) condition of the groundwater sampled in the DBR study unit was predominantly oxic (71 percent), except in the Colorado River study area where organic-rich fluvial aquifers provide the electron donors necessary to support iron-reducing (anoxic-Fe) redox processes. The cation type of 78 percent of the samples was either sodium- or mixed-type, and the anion type of 83 percent of the samples was either bicarbonate- or mixed-type. Sodium-type groundwaters generally were older and more alkaline than calcium-type groundwaters, consistent with the change in water chemistry expected from cation exchange between groundwater and aquifer sediments over long periods of time. Because of the correlation with young groundwater, calcium-type groundwater was predominantly from wells located adjacent to mountain-front recharge areas. Arsenic (As), boron (B), fluoride (F), molybdenum (Mo), strontium (Sr), uranium (U), and vanadium (V) were selected for assessment in this study because they occurred at concentrations greater than California Department of Public Health or U.S. Environmental Protection Agency regulatory or non-regulatory drinking-water-quality benchmarks in more than 2 percent of the 223 samples collected in the DBR study unit. As and F were detected most commonly (18 and 13 percent, respectively) at concentrations above associated water-quality benchmarks and Sr and V least frequently (both at 3 percent). Given that 14 C groundwater ages are predominantly >100 years BP, land use in the study unit is primarily undeveloped, and chemicals derived from anthropogenic sources, such as volatile organic compounds, were infrequently detected, high concentrations of these trace elements in groundwater were most likely the result of natural factors and not anthropogenic factors. As, F, Mo, and V concentrations showed significant positive correlations to groundwater age and to pH. This relation is partly due to the sources of trace elements likely being the weathering of primary minerals, such as silicate minerals, which is a slow process that takes place over hundreds to thousands of years. This relation also reflects the positive correlation between groundwater age and pH. Geochemical modeling predicted that the dominant species of As, Mo, and V in solution were oxyanions (HAsO 4 2– , MoO 4 2– , and H 2 VO 4– ), which are likely to be mobile in alkaline groundwater because mineral surfaces composing aquifer matrices have a predominantly negative surface charge under alkaline conditions. F also exists predominantly as a negatively charged ion (F – ). At pH values >7.5, saturation indices generated by the geochemical modeling program PHREEQC indicated that F solubility may be somewhat limited by the precipitation of the mineral fluorapatite [Ca 5 (PO 4 ) 3 F]. Speciation modeling of As in anoxic-Fe groundwater (iron-reducing conditions) showed that samples were supersaturated with orpiment (As 2 S 3 ), indicating that mineral precipitation may be responsible for low As concentrations observed in reducing groundwater. In contrast, U concentrations showed significant negative correlations to groundwater age and to pH. Higher U concentrations generally occurred in samples for which geochemical modeling indicated that the uncharged ternary complex Ca 2 UO 2 (CO 3 ) 3 was the dominant aqueous U species. This uncharged complex is not attracted to the charged surfaces of minerals and thus increases U solubility. Formation of Ca 2 UO 2 (CO 3 ) 3 was greater in younger groundwaters because calcium and uranium concentrations generally were lower in older groundwaters, likely due to cation-exchange processes and precipitation of the mineral calcite as groundwater pH increased. Co-precipitation of U with the calcite (CaCO 3 ) may remove U from the aqueous phase. Saturation indices indicated that the anoxic-Fe groundwaters from the Colorado River study area were supersaturated with the mineral uraninite (UO 2 ), suggesting that UO 2 precipitation may be responsible for the low concentrations of U observed in these samples. Concentrations of strontium, which exists primarily in a cationic form (Sr 2+ ), were not significantly correlated with either groundwater age or pH. Strontium concentrations showed a strong positive correlation with total dissolved solids (TDS). Dissolved constituents, such as Sr, that interact with mineral surfaces through outer-sphere complexation become increasingly soluble with increasing TDS concentrations of groundwater. Boron concentrations also showed a significant positive correlation with TDS, indicating the B may interact to a large degree with mineral surfaces through outer-sphere complexation.

California↗

USGS2018

Status and understanding of groundwater quality in the Monterey-Salinas Shallow Aquifer Study Unit, 2012–13: California GAMA Priority Basin Project

Groundwater quality in the approximately 7,820-square-kilometer (km 2 ) Monterey-Salinas Shallow Aquifer (MS-SA) study unit was investigated from October 2012 to May 2013 as part of the second phase of the Priority Basin Project of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The study unit is in the central coast region of California in the counties of Santa Cruz, Monterey, and San Luis Obispo. The GAMA Priority Basin Project is being conducted by the California State Water Resources Control Board in cooperation with the U.S. Geological Survey and the Lawrence Livermore National Laboratory. The MS-SA study was designed to provide a statistically robust assessment of untreated-groundwater quality in the shallow aquifer systems. The assessment was based on water-quality samples collected by the U.S. Geological Survey from 100 groundwater sites and 70 household tap sites, along with ancillary data such as land use and well-construction information. The shallow aquifer systems were defined by the depth interval of wells associated with domestic supply. The MS-SA study unit consisted of four study areas—Santa Cruz (210 km 2 ), Pajaro Valley (360 km 2 ), Salinas Valley (2,000 km 2 ), and Highlands (5,250 km 2 ). This study had two primary components: the status assessment and the understanding assessment . The first primary component of this study—the status assessment —assessed the quality of the groundwater resource indicated by data from samples analyzed for volatile organic compounds (VOCs), pesticides, and naturally present inorganic constituents, such as major ions and trace elements. The status assessment is intended to characterize the quality of groundwater resources in the shallow aquifer system of the MS-SA study unit, not the treated drinking water delivered to consumers by water purveyors. As opposed to the public wells, however, water from private wells, which often tap the shallow aquifer, is usually consumed without any treatment. The second component of this study—the understanding assessment —identified the natural and human factors that potentially affect groundwater quality by evaluating land-use characteristics, measures of location, geologic factors, groundwater age, and geochemical conditions of the shallow aquifer. An additional component of this study was a comparison of MS-SA water-quality results to those of the GAMA Monterey Bay and Salinas Valley Groundwater Basins study unit. This study unit covered much of the same areal extent as the MS-SA, but assessed the deeper, public drinking-water aquifer system. Relative concentrations (sample concentration divided by the benchmark concentration) were used to evaluate concentrations of constituents in groundwater samples relative to water-quality benchmarks for those constituents that have Federal or California benchmarks, such as maximum contaminant levels. For organic and special-interest constituents, relative concentrations were classified as high, greater than 1.0; moderate, greater than 0.1 and less than or equal to 1.0; or low, less than or equal to 0.1. For inorganic constituents, relative concentrations were classified as high, greater than 1.0; moderate, greater than 0.5 and less than or equal to 1.0; or low, less than or equal to 0.5. A relative concentration greater than 1.0 indicates that the concentration was greater than a benchmark. Aquifer-scale proportions were used to quantify regional-scale groundwater quality. The aquifer-scale proportions are the areal percentages of the shallow aquifer system where relative concentrations for a given constituent or class of constituents were high, moderate, or low. Inorganic constituents were measured at high and moderate relative concentrations more frequently than organic constituents. In the MS-SA study unit, inorganic constituents with benchmarks were detected at high relative concentrations in 51 percent of the study unit. The greatest proportions of high relative concentrations of trace elements and radioactive constituents were in the Highlands and Santa Cruz study areas, whereas high relative concentrations of nutrients were most often detected in the Salinas Valley and Pajaro Valley study areas and salinity indicators were most often detected in the Highlands and Salinas Valley study areas. The trace elements detected at high relative concentrations were arsenic, boron, iron, manganese, molybdenum, selenium, and strontium. The radioactive constituents detected at high relative concentrations were adjusted gross alpha radioactivity and uranium. The nutrient detected at high relative concentrations was nitrate plus nitrite. The salinity indicators detected at high relative concentrations were chloride, sulfate, and total dissolved solids. Organic constituents (VOCs and pesticides) were not detected at high relative concentrations in any of the study areas. The fumigant 1,2-dichloropropane was detected at moderate relative concentrations. The VOC chloroform and the pesticide simazine were the only organic constituents detected in more than 10 percent of samples. The constituents of special interest NDMA ( N -nitrosodimethylamine) and perchlorate were detected at high relative concentrations in the MS-SA study unit. Selected constituents were evaluated with explanatory factors to identify potential sources or processes that could explain their presence and distribution. Trace elements and radioactive constituents came from natural sources and were not elevated by anthropogenic sources or processes, except for selenium and the radioactive constituent uranium. Arsenic, manganese, iron, selenium, and uranium concentrations were all influenced by oxidation-reduction conditions. Unlike other trace elements and radioactive constituents, uranium and selenium can be affected by agricultural practices. Uranium and selenium can be released from aquifer sediments as a result of irrigation recharge water interacting with bicarbonate systems. Nitrate can be strongly affected by anthropogenic sources. Nitrate concentrations were significantly higher in modern groundwater, indicating recent inputs of nitrate to the shallow aquifer system. Nitrate was positively correlated with agricultural land use, indicating that irrigation-return water could be leaching nitrogen fertilizer and naturally present nitrate to elevate nitrate concentrations in shallow groundwater. The salinity indicators total dissolved solids, chloride, and sulfate all had natural sources in the MS-SA study unit, primarily marine sediments. Concentrations of the constituents were elevated as a result of evaporative concentration of irrigation water or precipitation. Sulfate concentrations were significantly correlated to agricultural land use, indicating that agricultural land-use practices are a contributing source of sulfate to groundwater. The samples with most of the detections of VOCs were from sites in the Pajaro Valley and northern part of the Salinas Valley. Most of the samples with pesticide detections were from sites in the Salinas Valley study area. The herbicide simazine was positively correlated to the percentage of agricultural land use, and its concentrations were higher in modern groundwater than in pre-modern groundwater. Perchlorate, similar to nitrate, has natural and anthropogenic sources. Correlations of perchlorate to dissolved oxygen, nitrate, and percentage of agricultural land use indicated that the irrigation-return water could be leaching naturally present perchlorate, as well as perchlorate from historical applications of Chilean nitrate fertilizer, to increase perchlorate concentrations in groundwater. The quality of the water in the shallow aquifer system from this study was compared with the quality of water in the public drinking-water aquifer in a previous GAMA (MS-PA) study in the same area. The shallow system was more oxic and had more sites with modern groundwater than the public drinking-water aquifer, which was more anoxic and had sites with more pre-modern groundwater. Arsenic and selenium were found at high relative concentrations in a greater proportion of the shallow system. Manganese and iron were found at high relative concentrations in a greater proportion of the public drinking-water aquifer. Uranium was found at higher relative concentrations in a greater proportion of the shallow system. Concentrations of arsenic, iron, manganese, and molybdenum are not likely to change much as groundwater percolates from the shallow system to the public drinking-water aquifer because there are no anthropogenic sources affecting these constituents. Uranium and selenium concentrations in the public drinking-water aquifer could be affected by the higher concentrations in the shallow system because of irrigation-return water, however. Nitrate and salinity indicators had concentrations that were much higher in the shallow system than the deeper public drinking-water aquifer. High concentrations of these constituents in the shallow system could lead to increased concentrations in the public drinking-water aquifer in parts of the study units because of land-use practices, such as irrigated agriculture. Organic constituents were detected more frequently in the public drinking-water aquifer than in the shallow system, possibly because more of the sites sampled in the public drinking-water aquifer were in urban areas compared to the sites sampled for the shallow system or because sources of contamination have decreased as a result of changes in use at the land surface.

California↗

USGS2012

Status and understanding of groundwater quality in the Tahoe-Martis, Central Sierra, and Southern Sierra study units, 2006-2007--California GAMA Priority Basin Project

Groundwater quality in the Tahoe-Martis, Central Sierra, and Southern Sierra study units was investigated as part of the Priority Basin Project of the California Groundwater Ambient Monitoring and Assessment (GAMA) Program. The three study units are located in the Sierra Nevada region of California in parts of Nevada, Placer, El Dorado, Madera, Tulare, and Kern Counties. The GAMA Priority Basin Project is being conducted by the California State Water Resources Control Board, in collaboration with the U.S. Geological Survey (USGS) and the Lawrence Livermore National Laboratory. The project was designed to provide statistically robust assessments of untreated groundwater quality within the primary aquifer systems used for drinking water. The primary aquifer systems (hereinafter, primary aquifers) for each study unit are defined by the depth of the screened or open intervals of the wells listed in the California Department of Public Health (CDPH) database of wells used for municipal and community drinking-water supply. The quality of groundwater in shallower or deeper water-bearing zones may differ from that in the primary aquifers; shallower groundwater may be more vulnerable to contamination from the surface. The assessments for the Tahoe-Martis, Central Sierra, and Southern Sierra study units were based on water-quality and ancillary data collected by the USGS from 132 wells in the three study units during 2006 and 2007 and water-quality data reported in the CDPH database. Two types of assessments were made: (1) status, assessment of the current quality of the groundwater resource, and (2) understanding, identification of the natural and human factors affecting groundwater quality. The assessments characterize untreated groundwater quality, not the quality of treated drinking water delivered to consumers by water purveyors. Relative-concentrations (sample concentrations divided by benchmark concentrations) were used for evaluating groundwater quality for those constituents that have Federal or California regulatory or non-regulatory benchmarks for drinking-water quality. A relative-concentration (RC) greater than (>) 1.0 indicates a concentration above a benchmark. RCs for organic constituents (volatile organic compounds and pesticides) and special-interest constituents were classified as "high" (RC > 1.0), "moderate" (1.0 ≥ RC > 0.1), or "low" (RC ≤ 0.1). For inorganic constituents (major ions, trace elements, nutrients, and radioactive constituents), the boundary between low and moderate RCs was set at 0.5. A new metric, aquifer-scale proportion, was used in the status assessment as the primary metric for evaluating regional-scale groundwater quality. High aquifer-scale proportion is defined as the percentage of the area of the primary aquifers with RC > 1.0 for a particular constituent or class of constituents; moderate and low aquifer-scale proportions are defined as the percentages of the area of the primary aquifer with moderate and low RCs, respectively. Percentages are based on an areal rather than a volumetric basis. Two statistical approaches—grid-based, which used one value per grid cell, and spatially weighted, which used multiple values per grid cell—were used to calculate aquifer-scale proportions for individual constituents and classes of constituents. The spatially weighted estimates of high aquifer-scale proportions were within the 90-percent (%) confidence intervals of the grid-based estimates in all cases. The status assessment showed that inorganic constituents had greater high and moderate aquifer-scale proportions than did organic constituents in all three study units. In the Tahoe-Martis study unit, RCs for inorganic constituents with health-based benchmarks (primarily arsenic) were high in 20% of the primary aquifer, moderate in 13%, and low in 67%. In the Central Sierra study unit, aquifer-scale proportions for inorganic constituents with health-based benchmarks (primarily arsenic, uranium, fluoride, and molybdenum) were 41% high, 36% moderate, and 23% low. In the Southern Sierra study unit, 32, 34, and 34% of the primary aquifer had high, moderate, and low RCs of inorganic constituents with health-based benchmarks (primarily arsenic, uranium, fluoride, boron, and nitrate). The high aquifer-scale proportions for inorganic constituents with non-health-based benchmarks were 14, 34, and 24% for the Tahoe-Martis, Central Sierra, and Southern Sierra study units, respectively, and the primary constituent was manganese for all three study units. Organic constituents with health-based benchmarks were not present at high RCs in the primary aquifers of the Central Sierra and Southern Sierra study units, and were present at high RCs in only 1% of the Tahoe-Martis study unit. Moderate aquifer-scale proportions for organic constituents were < 5% in all three study units. Of the 173 organic constituents analyzed, 22 were detected, and of those 22, 17 have health-based benchmarks. Organic constituents were detected in 20, 27, and 40% of the primary aquifers in the Tahoe-Martis, Central Sierra, and Southern Sierra study units, respectively. Four organic constituents had study-unit detection frequencies of > 10%: the trihalomethane chloroform in the Tahoe-Martis study unit; chloroform and the herbicide simazine in the Central Sierra study unit; and chloroform, simazine, the herbicide atrazine, and the solvent perchloroethene in the Southern Sierra study unit. The second component of this study, the understanding assessment, identified the natural and human factors that may have affected groundwater quality in the three study units by evaluating statistical correlations between water-quality constituents and potential explanatory factors. The potential explanatory factors evaluated were land use, septic tank density, climate, relative position in the regional flow system, aquifer lithology, geographic location, well depth and depth to the top of the screened or open interval in the well, groundwater age distribution, pH, and dissolved oxygen concentration. Results of the statistical evaluations were used to explain the occurrence and distribution of constituents in the study units. Aquifer lithology (granitic, metamorphic, sedimentary, or volcanic rocks), groundwater age distribution [modern (recharged since 1952), pre-modern (recharged before 1952), or mixed (containing both modern and pre-modern recharge)], geographic location, pH, and dissolved oxygen were the most significant factors explaining the occurrence patterns of most inorganic constituents. High and moderate RCs of arsenic were associated with pre-modern and mixed-age groundwater and two distinct sets of geochemical conditions: (1) oxic, high-pH conditions, particularly in volcanic rocks, and (2) low-oxygen to anoxic conditions and low- to neutral-pH conditions, particularly in granitic rocks. In granitic and metamorphic rocks, high and moderate RCs of uranium were associated with pre-modern and mixed-age groundwater, low-oxygen to anoxic conditions, and location within parts of the Central Sierra and Southern Sierra study units known to have rocks with anomalously high uranium content compared to other parts of the Sierra Nevada. High and moderate RCs of uranium in sedimentary rocks were associated with pre-modern-age groundwater, oxic and high-pH conditions, and location in the Tahoe Valley South subbasin within the Tahoe-Martis study unit. Land use within 500 meters of the well and groundwater age were the most significant factors explaining occurrence patterns of organic constituents. Herbicide detections were most strongly associated with modern- and mixed-age groundwater from wells with agricultural land use. Trihalomethane detections were most strongly associated with modern- and mixed-age groundwater from wells with > 10% urban land use and (or) septic tank density > 7 tanks per square kilometer. Solvent detections were not significantly related to groundwater age. Eighty-three percent of the wells with modern- or mixed-age groundwater, and 86% of wells with detections of herbicides and (or) THMs had depths to the top of the screened or open interval of < 170 feet. These observations suggest that modern groundwater has infiltrated to depths of approximately 170 feet below land surface. Land use and occurrence of herbicides and solvents were the most significant factors explaining the occurrence of nitrate. Wells with > 5% agricultural land use and detection of a herbicide or solvent had the highest nitrate concentrations. Comparison between observed and predicted detection frequencies of perchlorate suggests that the perchlorate detected at concentrations < 1 microgram per liter likely reflects the distribution of perchlorate under natural conditions, and that the perchlorate detected at higher concentrations may reflect redistribution of originally natural perchlorate salts by irrigation in the agricultural areas of the Southern Sierra study unit.

California↗

USGS2017

Estimated dissolved-solids loads and trends at selected streams in and near the Uinta Basin, Utah, Water Years 1989–2013

The U.S. Geological Survey (USGS), in cooperation with the Colorado River Basin Salinity Control Forum, studied trends in dissolved-solids loads at selected sites in and near the Uinta Basin, Utah. The Uinta Basin study area includes the Duchesne River Basin and the Middle Green River Basin in Utah from below Flaming Gorge Reservoir to the town of Green River. Annual dissolved-solids loads for water years (WY) 1989 through 2013 were estimated for 16 gaging stations in the study area using streamflow and water-quality data from the USGS National Water Information System database. Eight gaging stations that monitored catchments with limited or no agricultural land use (natural subbasins) were used to assess loads from natural sources. Four gaging stations that monitored catchments with agricultural land in the Duchesne River Basin were used to assess loads from agricultural sources. Four other gaging stations were included in the dissolved-solids load and trend analysis to help assess the effects of agricultural areas that drain to the Green River in the Uinta Basin, but outside of the Duchesne River Basin. Estimated mean annual dissolved-solids loads for WY 1989–2013 ranged from 1,520 tons at Lake Fork River above Moon Lake, near Mountain Home, Utah (UT), to 1,760,000 tons at Green River near Green River, UT. The flow-normalized loads at gaging stations upstream of agricultural activities showed no trend or a relatively small change. The largest net change in modeled flow-normalized load was -352,000 tons (a 17.8-percent decrease) at Green River near Green River, UT. Annual streamflow and modeled dissolved-solids loads at the gaging stations were balanced between upstream and downstream sites to determine how much water and dissolved solids were transported to the Duchesne River and a section of the Green River, and how much was picked up in each drainage area. Mass-balance calculations of WY 1989–2013 mean annual dissolved-solids loads at the studied sites show that Green River near Jensen, UT, accounts for 64 percent of the load in the river at Green River, UT, while the Duchesne River and White River contribute 10 and 13 percent, respectively. Annual streamflow and modeled dissolved-solids loads at the gaging stations were balanced between upstream and downstream sites to determine how much water and dissolved solids were transported to the Duchesne River and a section of the Green River, and how much was picked up in each drainage area. Mass-balance calculations of WY 1989–2013 mean annual dissolved-solids loads at the studied sites show that Green River near Jensen, UT, accounts for 64 percent of the load in the river at Green River, UT, while the Duchesne River and White River contribute 10 and 13 percent, respectively. The flow-normalized dissolved-solids loads estimated at Duchesne River near Randlett, UT, and White River near Watson, UT, decreased by 68,000 and 55,300 tons, or 27.8 and 20.8 percent respectively, when comparing 1989 to 2013. The drainage basins for both rivers have undergone salinity-control projects since the early 1980s to reduce the dissolved-solids load entering the Colorado River. Approximately 19 percent of the net change in flow-normalized load at Green River at Green River, UT, is from changes in load modeled at Duchesne River near Randlett, UT, and 16 percent from changes in load modeled at White River near Watson, UT. The net change in flow-normalized load estimated at Green River near Greendale, UT, for WY 1989–2013 accounts for about 45 percent of the net change estimated at Green River at Green River, UT. Mass-balance calculations of WY 1989–2013 mean annual dissolved-solids loads at the studied sites in the Duchesne River Basin show that 75,400 tons or 44 percent of the load at the Duchesne River near Randlett, UT, gaging station was not accounted for at any of the upstream gages. Most of this unmonitored load is derived from tributary inflow, groundwater discharge, unconsumed irrigation water, and irrigation tail water. A mass balance of WY 1989–2013 flow-normalized loads estimated at sites in the Duchesne River Basin indicates that the flow-normalized load of unmonitored inflow to the Duchesne River between the Myton and Randlett gaging stations decreased by 38 percent. The total net decrease in flow-normalized load calculated for unmonitored inflow in the drainage basin accounts for 94 percent of the decrease in WY 1989–2013 flow-normalized load modeled at the Duchesne River near Randlett, UT, gaging station. Irrigation improvements in the drainage basin have likely contributed to the decrease in flow-normalized load. Reductions in dissolved-solids load estimated by the Natural Resources Conservation Service (NRCS) and the Bureau of Reclamation (Reclamation) from on- and off-farm improvements in the Uinta Basin totaled about 135,000 tons in 2013 (81,900 tons from on-farm improvements and 53,300 tons from off-farm improvements). The reduction in dissolved-solids load resulting from on- and off-farm improvements facilitated by the NRCS and Reclamation in the Price River Basin from 1989 to 2013 was estimated to be 64,800 tons. The amount of sprinkler-irrigated land mapped in the drainage area or subbasin area for a gaging station was used to estimate the reduction in load resulting from the conversion from flood to sprinkler irrigation. Sprinkler-irrigated land mapped in the Uinta Basin totaled 109,630 acres in 2012. Assuming conversion to wheel-line sprinklers, a reduction in dissolved-solids load in the Uinta Basin of 95,800 tons in 2012 was calculated using the sprinkler-irrigation acreage and a pre-salinity-control project dissolved-solids yield of 1.04 tons per acre. A reduction of 72,800 tons in dissolved-solids load from irrigation improvements was determined from sprinkler-irrigated lands in the Ashley Valley and Jensen, Pelican Lake, and Pleasant Valley areas (mapped in 2012); and in the Price River Basin (mapped in 2011). This decrease in dissolved-solids load is 8,800 tons more than the decrease in unmonitored flow-normalized dissolved-solids load (-64,000 tons) determined for the Green River between the Jensen and Green River gaging stations. The net WY 1989–2013 change in flow-normalized dissolved-solids load at the Duchesne River near Randlett, UT, and the Green River between the Jensen and Green River, UT, gaging stations determined from mass-balance calculations was compared to reported reductions in dissolved-solids load from on- and off-farm improvements and estimated reductions in load determined from mapped sprinkler-irrigated areas in the Duchesne River Basin and the area draining to the Green River between the Jensen and Green River gaging stations. The combined NRCS and Reclamation estimates of reduction in dissolved-solids load from on- and off-farm improvements in the study area (200,000 tons) is more than the reduction in load estimated using the acreage with sprinkler improvements (136,000 tons) or the mass-balance of flow-normalized load (132,000 tons).

Utah↗

USGS2023

Comprehensive water-quality trend analysis for selected sites and constituents in the International Souris River Basin, Saskatchewan and Manitoba, Canada, and North Dakota, United States, 1970–2020

The Souris River Basin is an international basin in southeast Saskatchewan, north-central North Dakota, and southwest Manitoba. Sustained exceedances of water-quality objectives for total phosphorus, sodium, sulfate, total dissolved solids, and total iron have been reported since the late 1990s at the two binational sites on the Souris River (Souris River near Sherwood, North Dakota [U.S. Geological Survey station 05114000] and Souris River near Westhope, N. Dak. [U.S. Geological Survey station 05124000]). To understand conditions at the binational sites, it is important to understand water-quality changes on a basin-wide scale. Because streamflow is highly variable in the basin and changes in streamflow affect water-quality conditions, it is particularly important to use a trend-analysis method that accounts for changes in streamflow. Trends in water-quality concentrations can be affected by human-induced changes on the landscape or natural changes in land-runoff interactions that are driven by climate patterns and reflected by changes in streamflow (commonly referred to as “hydroclimatic variability”). In the primarily agricultural Souris River Basin, human-induced changes that are likely to affect trends are widespread changes in agricultural management such as fertilizer application, tilling practices, and crop types, as well as dam emplacement and artificial drainage. Around 1970, there was a long-term natural (hydroclimatic) change in the basin in which a significant transition from a dry climate state to a wet climate state resulted in higher streamflow in the basin. To assist the International Souris River Board in assessing current water-quality conditions in the Souris River Basin and exceedances of water-quality objectives at the binational sites, the U.S. Geological Survey, in cooperation with the International Joint Commission, completed a comprehensive analysis for selected ions, nutrients, and trace metals for many sites in the basin that included descriptive water-quality statistics, trend analysis using a trend method that considers interannual hydroclimatic variability, and an assessment of exceedances of the water-quality objectives for the binational sites. Water-quality and streamflow or reservoir inflow or outflow data were compiled for 34 sites (30 stream sites and four reservoir sites) and 23 constituents with established water-quality objectives from 1970 to 2020 in the Souris River Basin and were used for descriptive statistics and water-quality trend analysis. Median total dissolved solids, sulfate, and sodium concentrations were low in the headwaters of the Souris River and some of the highest median concentrations were measured in the upper basin. At main-stem Souris River sites, all median sodium concentrations were greater than the binational water-quality objective. Median total phosphorus concentrations in the Souris River Basin were highest in the headwaters of the Souris River and all sites had median concentrations greater than the water-quality objective. Median total iron concentrations were highly variable across the basin, and for most main-stem sites, median concentrations were greater than or equal to the water-quality objective. During the recent period (2009–19), the annual flow-averaged concentrations of total dissolved solids and sulfate increased for nearly all stream sites with most sites having mildly significant or significant increases. One-half of the sites had an annual flow-averaged geometric mean concentration greater than the total dissolved solids water-quality objective, and four sites had sulfate increases greater than 100 milligrams per liter. Trends in annual flow-averaged concentrations of sodium and chloride generally were small and nonsignificant. Most sites had concentrations greater than the sodium water-quality objective, whereas all sites had concentrations much less than the chloride water-quality objective. Annual flow-averaged geometric mean concentration of total phosphorus decreased for nearly all sites across the Souris River Basin, but all sites had concentrations greater than the total phosphorus water-quality objective for the entire period. Small and nonsignificant changes in annual flow-averaged geometric mean concentration of total iron were detected at all sites but the binational site at Sherwood, N. Dak., and by 2019 all sites had concentrations greater than the total iron water-quality objective. For the reservoir sites, during 2000–15, mostly significant increases for total dissolved solids, sulfate, and sodium were detected, whereas changes in total phosphorus and total iron were mixed. During the historical period (1976–2019), large and consistent increases in total dissolved solids and sulfate have occurred since the late 1980s, with the largest increases and the most sites with mildly significant or significant increases generally occurring during the middle period (1988–2005). Large and significant or mildly significant increases in sodium concentrations occurred at eight of 10 sites in the middle period (1988–2005), and by the late period (2005–19) changes were small and nonsignificant. Similar to other basins in the region, such as the Red River of the North and Heart River, large and overall consistent increases since the late 1980s in total dissolved solids and sulfate in the Souris River Basin suggest that long-term natural (hydroclimatic) processes are large contributors to increases in the concentration of salts in streams and reservoirs associated with the onset of wetter conditions. The concurrent increases in sulfate and sodium concentrations at all sites during the middle period (1988–2005) suggest that sodium-sulfate evaporite dissolution may be a factor contributing to increases. Total phosphorus concentrations oscillated between increasing and decreasing during the historical period, with concentrations increasing during the first trend period (1976–88) and decreasing in the fourth trend period (2009–19) to the lowest flow-averaged geometric mean concentration by 2019 for most sites. During the historical period, changes in total iron concentrations were mostly nonsignificant and generally small, and variability in total iron concentrations likely affected the ability to detect statistically significant changes in concentration. The probability of exceeding the water-quality objective for total dissolved solids, sulfate, and sodium increased between 1976 and 2019 for the binational sites, especially for sulfate, which more than doubled for Souris River near Sherwood, N. Dak. and increased more than seven times for Souris River near Westhope, N. Dak. Total phosphorus and total iron concentrations for the binational sites were likely to exceed the water-quality objective for most of the year, but seasonal patterns of total phosphorus and total iron concentrations were different between the sites, suggesting that different factors may affect concentrations at different times of the year. For sodium, total phosphorus, and total iron, exceedance of the water-quality objective most of the time is not unexpected given that the flow-averaged geometric mean concentration for these three constituents for most sites across the basin are greater than the water-quality objective for most of the period. If natural processes are affecting total dissolved solids and sulfate concentrations, concentrations would be expected to vary with time, and as a result, extended periods of concentrations greater or less than the water-quality objective are likely to occur depending upon climatic conditions. A better understanding of the state of water quality across the Souris River Basin is beneficial to understanding and interpreting water-quality conditions at the two Souris River binational sites. The most consistent spatial and temporal change observed for this study was large and consistent increases in sulfate and total dissolved solids among tributary and main-stem sites since the late 1980s. For sulfate and total dissolved solids, wetter climatic conditions combined with naturally occurring and abundant sources of sulfate likely contributed to sustained exceedances of water-quality objectives in recent decades, and extended periods of concentrations greater than or less than the water-quality objective are likely to occur depending on climatic conditions. For sodium, total iron, and total phosphorus, sustained exceedances of the current water-quality objective likely will continue because most sites across the basin had flow-averaged geometric mean concentrations greater than the water-quality objective; and during the 43-year period of analysis, regardless of climatic conditions, exceedances were consistently greater than the water-quality objective. Further investigation into the factors causing increasing sulfate concentrations and a better understanding of reservoir dynamics would enhance the understanding of changes in water-quality conditions in the Souris River Basin. The basin-wide approach of this report provided an improved understanding of water-quality conditions in the Souris River Basin, and results can be used to inform the current water-quality objectives, inform potential changes to water management in the basin, and serve as a starting point for tracking future progress. Gaps in understanding of water-quality conditions can be closed through continued monitoring and further investigation into causes behind changes in water-quality conditions identified in this report.

Manitoba, North Dakota, Saskatchewan↗

USGS2017

Baseline assessment of groundwater quality in Pike County, Pennsylvania, 2015

The Devonian-age Marcellus Shale and the Ordovician-age Utica Shale, which have the potential for natural gas development, underlie Pike County and neighboring counties in northeastern Pennsylvania. In 2015, the U.S. Geological Survey, in cooperation with the Pike County Conservation District, conducted a study that expanded on a previous more limited 2012 study to assess baseline shallow groundwater quality in bedrock aquifers in Pike County prior to possible extensive shale-gas development. Seventy-nine water wells ranging in depths from 80 to 610 feet were sampled during June through September 2015 to provide data on the presence of methane and other aspects of existing groundwater quality in the various bedrock geologic units throughout the county, including concentrations of inorganic constituents commonly present at low values in shallow, fresh groundwater but elevated in brines associated with fluids extracted from geologic formations during shale-gas development. All groundwater samples collected in 2015 were analyzed for bacteria, dissolved and total major ions, nutrients, selected dissolved and total inorganic trace constituents (including metals and other elements), radon-222, gross alpha- and gross beta-particle activity, dissolved gases (methane, ethane, and propane), and, if sufficient methane was present, the isotopic composition of methane. Additionally, samples from 20 wells distributed throughout the county were analyzed for selected man-made volatile organic compounds, and samples from 13 wells where waters had detectable gross alpha activity were analyzed for radium-226 on the basis of relatively elevated gross alpha-particle activity. Results of the 2015 study show that groundwater quality generally met most drinking-water standards for constituents and properties included in analyses, but groundwater samples from some wells had one or more constituents or properties, including arsenic, iron, manganese, pH, bacteria, sodium, chloride, sulfate, total dissolved solids, and radon-222, that did not meet (commonly termed failed or exceeded) primary or secondary maximum contaminant levels (MCLs) or Health Advisories (HA) for drinking water. Except for iron, dissolved and total concentrations of major ions and most trace constituents generally were similar. Only 1 of 79 well-water samples had any constituent that exceeded a MCL, with an arsenic concentration of about 30 micrograms per liter (µg/L) that was higher than the MCL of 10 µg/L. However, total arsenic concentrations were higher than the HA of 2 µg/L in samples from another 12 of 79 wells (about 15 percent). Secondary maximum contaminant levels (SMCLs) were exceeded most frequently by pH and concentrations of iron and manganese. The pH was outside of the SMCL range of 6.5–8.5 in samples from 24 of 79 wells (30 percent), ranging from 5.5 to 9.2; more samples had pH values less than 6.5 than had pH values greater than 8.5. Total iron concentrations typically were much greater than dissolved iron concentrations, indicating substantial presence of iron in particulate phase, and exceeded the SMCL of 300 µg/L more often [35 of 79 samples (44 percent)] than dissolved iron concentrations [samples from 8 of 79 wells (10 percent)]. Total manganese concentrations exceeded the SMCL of 50 µg/L in samples from 31 of 79 wells (39 percent) and the HA of 300 µg/L in samples from 13 of 79 wells (about 16 percent). A few (1–2) samples had concentrations of sodium, chloride, sulfate, or TDS higher than the SMCLs of 60, 250, 250, and 500 mg/L, respectively. However, dissolved sodium concentrations were higher than the HA of 20 mg/L in samples from 15 of 79 wells (nearly 20 percent). Total coliform bacteria were detected in samples from 25 of 79 wells (32 percent) but Escherichia coli were not detected in any sample. Radon-222 activities ranged from 11 to 5,100 picocuries per liter (pCi/L), with a median of 1,440 pCi/L, and exceeded the proposed and the alternate proposed drinking-water standards of 300 and 4,000 pCi/L, respectively, in samples from 60 of 79 wells (75 percent) and in samples from 2 of 79 wells (3 percent), respectively. Groundwater samples from all wells were analyzed for dissolved methane by one contract laboratory that determined water from 19 of the 79 wells (24 percent) had concentrations of methane greater than the reporting level of 0.010 milligrams per liter (mg/L) with a maximum methane concentration of 2.5 mg/L. Methane concentrations in 18 replicate samples submitted to a second laboratory for dissolved gas and isotopic analysis generally were higher by as much as a factor of 2.7 from those determined by the first laboratory, indicating potential bias related to combined sampling and analytical methods, and therefore, caution needs to be used when comparing methane results determined by different methods. The isotopic composition of methane in 9 of 10 samples with sufficient dissolved methane (about 0.3 mg/L) for isotopic analysis is consistent with values reported for methane of microbial origin produced through carbon dioxide reduction; an isotopic shift in 1 or 2 samples may indicate subsequent methane oxidation. The low concentrations of ethane relative to methane in these samples further indicate that the methane may be of microbial origin. Groundwater samples with relatively elevated methane concentrations (near or greater than 0.3 mg/L) also had chemical compositions that differed in some respects from groundwater with relatively low methane concentrations (less than 0.3 mg/L) by having higher pH (greater than 8) and higher concentrations of sodium, lithium, boron, fluoride, arsenic, and bromide and chloride/bromide ratios indicative of mixing with a small amount of brine of probable natural occurrence. The spatial distribution of groundwater compositions differs by topographic setting and lithology and generally shows that (1) relatively dilute, slightly acidic, oxygenated, calcium-carbonate type waters tend to occur in the uplands underlain by the undivided Poplar Gap and Packerton members of the Catskill Formation in southwestern Pike County; (2) waters of near neutral pH with the highest amounts of hardness (calcium and magnesium) generally occur in areas of intermediate altitudes underlain by other members of the Catskill Formation; and (3) waters with pH values greater than 8, low oxygen concentrations, and the highest arsenic, sodium, lithium, bromide, and methane concentrations can be present in deep wells in uplands but most frequently occur in stream valleys, especially at low altitudes (less than about 1,200 feet above North American Vertical Datum of 1988) where groundwater may be discharging regionally, such as to the Delaware River in northern and eastern Pike County. Thus, the baseline assessment of groundwater quality in Pike County prior to gas-well development shows that shallow (less than about 1,000 feet deep) groundwater generally meets primary drinking-water standards for inorganic constituents but varies spatially, with methane and some constituents present in high concentrations in brine (and connate waters from gas and oil reservoirs) present at low to moderate concentrations in some parts of Pike County.

Pennsylvania↗

USGS2016

Groundwater and surface-water interaction, water quality, and processes affecting loads of dissolved solids, selenium, and uranium in Fountain Creek, near Pueblo, Colorado, 2012–2014

In 2012, the U.S. Geological Survey, in cooperation with the Arkansas River Basin Regional Resource Planning Group, initiated a study of groundwater and surface-water interaction, water quality, and loading of dissolved solids, selenium, and uranium to Fountain Creek near Pueblo, Colorado, to improve understanding of sources and processes affecting loading of these constituents to streams in the Arkansas River Basin. Fourteen monitoring wells were installed in a series of three transects across Fountain Creek near Pueblo, and temporary streamgages were established at each transect to facilitate data collection for the study. Groundwater and surface-water interaction was characterized by using hydrogeologic mapping, groundwater and stream-surface levels, groundwater and stream temperatures, vertical hydraulic-head gradients and ratios of oxygen and hydrogen isotopes in the hyporheic zone, and streamflow mass-balance measurements. Water quality was characterized by collecting periodic samples from groundwater, surface water, and the hyporheic zone for analysis of dissolved solids, selenium, uranium, and other selected constituents and by evaluating the oxidation-reduction condition for each groundwater sample under different hydrologic conditions throughout the study period. Groundwater loads to Fountain Creek and in-stream loads were computed for the study area, and processes affecting loads of dissolved solids, selenium, and uranium were evaluated on the basis of geology, geochemical conditions, land and water use, and evapoconcentration. During the study period, the groundwater-flow system generally contributed flow to Fountain Creek and its hyporheic zone (as a single system) except for the reach between the north and middle transects. However, the direction of flow between the stream, the hyporheic zone, and the near-stream aquifer was variable in response to streamflow and stage. During periods of low streamflow, Fountain Creek generally gained flow from groundwater. However, during periods of high streamflow, the hydraulic gradient between groundwater and the stream temporarily reversed, causing the stream to lose flow to groundwater. Concentrations of dissolved solids, selenium, and uranium in groundwater generally had greater spatial variability than surface water or hyporheic-zone samples, and constituent concentrations in groundwater generally were greater than in surface water. Constituent concentrations in the hyporheic zone typically were similar to or intermediate between concentrations in groundwater and surface water. Concentrations of dissolved solids, selenium, uranium, and other constituents in groundwater samples collected from wells located on the east side of the north monitoring well transect were substantially greater than for other groundwater, surface-water, and hyporheic-zone samples. With one exception, groundwater samples collected from wells on the east side of the north transect exhibited oxic to mixed (oxic-anoxic) conditions, whereas most other groundwater samples exhibited anoxic to suboxic conditions. Concentrations of dissolved solids, selenium, and uranium in surface water generally increased in a downstream direction along Fountain Creek from the north transect to the south transect and exhibited an inverse relation to streamflow with highest concentration occurring during periods of low streamflow and lowest concentrations occurring during periods of high streamflow. Groundwater loads of dissolved solids, selenium, and uranium to Fountain Creek were small because of the small amount of groundwater flowing to the stream under typical low-streamflow conditions. In-stream loads of dissolved solids, selenium, and uranium in Fountain Creek varied by date, primarily in relation to streamflow at each transect and were much larger than computed constituent loads from groundwater. In-stream loads generally decreased with decreases in streamflow and increased as streamflow increased. In-stream loads of dissolved solids and selenium increased between the north and middle transects but generally decreased between the middle and south transects. By contrast, uranium loads generally decreased between the north and middle transects but increased between the middle and south transects. In-stream load differences between transects appear primarily to be related to differences in streamflow. However, because groundwater typically flows to Fountain Creek under low-flow conditions, and groundwater has greater concentrations of dissolved solids, selenium, and uranium than surface water in Fountain Creek, increases in loads between transects likely are affected by inflow of groundwater to the stream, which can account for a substantial proportion of the in-stream load difference between transects. When loads decreased between transects, the primary cause likely was decreased streamflow as a result of losses to groundwater and flow through the hyporheic zone. However, localized groundwater inflow likely attenuated the magnitude by which the in-stream loads decreased. The combination of localized soluble geologic sources and oxic conditions likely is the primary reason for the occurrence of high concentrations of dissolved solids, selenium, and uranium in groundwater on the east side of the north monitoring well transect. To evaluate conditions potentially responsible for differences in water quality and redox conditions, physical characteristics such as depth to water, saturated thickness, screen depth below the water table, screen height above bedrock, and aquifer hydraulic conductivity were compared by using Wilcoxon rank-sum tests. Results indicated no significant difference between depth to water, screen height above bedrock, and hydraulic conductivity for groundwater samples collected from wells on the east side of the north transect and groundwater samples from all other wells. However, saturated thickness and screen depth below the water table both were significantly smaller for groundwater samples collected from wells on the east side of the north transect than for groundwater samples from other wells, indicating that these characteristics might be related to the elevated constituent concentrations found at that location. Similarly, saturated thickness and screen depth below the water table were significantly smaller for groundwater samples under oxic or mixed (oxic-anoxic) conditions than for those under anoxic to suboxic conditions. The greater constituent concentrations at wells on the east side of the north transect also could, in part, be related to groundwater discharge from an unnamed alluvial drainage located directly upgradient from that location. Although the quantity and quality of water discharging from the drainage is not known, the drainage appears to collect water from a residential area located upgradient to the east of the wells, and groundwater could become concentrated in nitrate and other dissolved constituents before flowing through the drainage. High levels of nitrate, whether from anthropogenic or natural geologic sources, could promote more soluble forms of selenium and other constituents by affecting the redox condition of groundwater. Whether oxic conditions at wells on the east side of the north transect are the result of physical characteristics or of groundwater inflow from the alluvial drainage, the oxic conditions appear to cause increased dissolution of minerals from the shallow shale bedrock at that location. Because ratios of hydrogen and oxygen isotopes indicate evaporation likely has not had a substantial effect on groundwater, constituent concentrations at that location likely are not the result of evapoconcentration.

Colorado↗

USGS2016

Baseline assessment of groundwater quality in Wayne County, Pennsylvania, 2014

The Devonian-age Marcellus Shale and the Ordovician-age Utica Shale, geologic formations which have potential for natural gas development, underlie Wayne County and neighboring counties in northeastern Pennsylvania. In 2014, the U.S. Geological Survey, in cooperation with the Wayne Conservation District, conducted a study to assess baseline shallow groundwater quality in bedrock aquifers in Wayne County prior to potential extensive shale-gas development. The 2014 study expanded on previous, more limited studies that included sampling of groundwater from 2 wells in 2011 and 32 wells in 2013 in Wayne County. Eighty-nine water wells were sampled in summer 2014 to provide data on the presence of methane and other aspects of existing groundwater quality throughout the county, including concentrations of inorganic constituents commonly present at low levels in shallow, fresh groundwater but elevated in brines associated with fluids extracted from geologic formations during shale-gas development. Depths of sampled wells ranged from 85 to 1,300 feet (ft) with a median of 291 ft. All of the groundwater samples collected in 2014 were analyzed for bacteria, major ions, nutrients, selected inorganic trace constituents (including metals and other elements), radon-222, gross alpha- and gross beta-particle activity, selected man-made organic compounds (including volatile organic compounds and glycols), dissolved gases (methane, ethane, and propane), and, if sufficient methane was present, the isotopic composition of methane. Results of the 2014 study show that groundwater quality generally met most drinking-water standards, but some well-water samples had one or more constituents or properties, including arsenic, iron, pH, bacteria, and radon-222, that exceeded primary or secondary maximum contaminant levels (MCLs). Arsenic concentrations were higher than the MCL of 10 micrograms per liter (µg/L) in 4 of 89 samples (4.5 percent) with concentrations as high as 20 µg/L; arsenic concentrations were higher than the Health Advisory level of 2 µg/L in 27 of 89 samples (30 percent). Total iron concentrations exceeded the secondary maximum contaminant level (SMCL) of 300 µg/L in 9 of 89 samples (10 percent). The pH ranged from 5.4 to 9.3 and did not meet the SMCL range of greater than 6.5 to less than 8.5 in 27 samples (30 percent); 22 samples had pH values less than 6.5, and 5 samples had pH values greater than 8.5. Total coliform bacteria were detected in 22 of 89 samples (25 percent); Escherichia coli were detected in only 2 of those 22 samples. Radon-222 activities ranged from 25 to 7,400 picocuries per liter (pCi/L), with a median of 2,120 pCi/L, and exceeded the proposed drinking-water standard of 300 pCi/L in 86 of 89 samples (97 percent); radon-222 activities were higher than the alternative proposed standard of 4,000 pCi/L in 12 of 89 samples (13.5 percent). Water from 8 of the 89 wells (9 percent) had concentrations of methane greater than the reporting level of 0.24 milligrams per liter (mg/L) with the detectable methane concentrations ranging from 0.74 to 9.6 mg/L. Of 16 replicate samples submitted to another laboratory with a lower reporting level of 0.0002 mg/L, 15 samples had detectable methane concentrations that ranged from 0.0011 to 9.7 mg/L. Of these 15 samples, low levels of ethane (0.00032 to 0.0017 mg/L) were detected in 6 of 7 samples with methane concentrations greater than 0.75 mg/L. The isotopic composition of methane in 6 of 8 samples with sufficient dissolved methane (about 1 mg/L) for isotopic analysis is consistent with a predominantly thermogenic methane source (sample carbon isotopic ratio δ13C CH4 values ranging from -56.36 to -45.97 parts per thousand (‰) and hydrogen isotopic ratio δD CH4 values ranging from -233.1 to -141.1 ‰). However, the low levels of ethane relative to methane indicate that the methane may be of microbial origin and subsequently underwent oxidation. Isotopic compositions indicated a possibly mixed thermogenic and microbial source (carbon dioxide reduction process) for the methane in 1 of the 8 samples (δ 13 C CH4 of -63.72 and δD CH4 of -192.3 ‰) and potential oxidation of microbial and (or) thermogenic methane in the remaining sample (δ 13 C CH4 of -46.56 and δD CH4 of -79.7 ‰). Groundwater samples with relatively elevated methane concentrations (near or greater than 1 mg/L) had a chemical composition that differed in some respects (pH, selected major ions, and inorganic trace constituents) from groundwater with relatively low methane concentrations (less than 0.75 mg/L). The seven well-water samples with the highest methane concentrations (from about 1 to 9.6 mg/L) also had among the highest pH values (8.1 to 9.3, respectively) and the highest 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. 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, by volume) similar in composition to that reported for gas and oil well brines in Pennsylvania. Most other samples with low methane concentrations (less than about 1 mg/L) had chloride/bromide ratios that indicate predominantly man-made sources of chloride, such as road salt, septic systems, and (or) animal waste. Although naturally occurring brines may originate from deeper parts of the aquifer system, the man-made sources are likely to affect shallow groundwater. Geochemical modeling showed that the water chemistry of samples with elevated pH, sodium, lithium, bromide, and alkalinity could result from dissolution of calcite (calcium carbonate) combined with cation exchange and mixing with a small amount of brine. Through cation exchange reactions (which are equivalent to processes in a water softener) calcium ions released by calcite dissolution are exchanged for sodium ions on clay minerals. The spatial distribution of groundwater compositions generally shows that (1) relatively dilute, slightly acidic, oxygenated, calcium-carbonate type waters tend to occur in the uplands along the western border of Wayne County; (2) waters of near neutral pH with the highest amounts of hardness (calcium and magnesium) generally occur in areas of intermediate altitudes; and (3) waters with pH values greater than 8, low oxygen concentrations, and the highest arsenic, sodium, lithium, bromide, and methane concentrations can occur in deep wells in uplands but most frequently occur in stream valleys, especially at low elevations (less than about 1,200 ft above North American Vertical Datum of 1988) where groundwater may be discharging regionally, such as to the Delaware River. Thus, the baseline assessment of groundwater quality in Wayne County prior to gas-well development shows that shallow (less than about 1,000 ft deep) groundwater is generally of good quality, but methane and some constituents present in high concentrations in brine (and produced waters from gas and oil wells) may be present at low to moderate concentrations in some parts of Wayne County.

Pennsylvania↗

USGS2012

Status and understanding of groundwater quality in the two southern San Joaquin Valley study units, 2005-2006 - California GAMA Priority Basin Project

Groundwater quality in the southern San Joaquin Valley was investigated from October 2005 through March 2006 as part of the Priority Basin Project of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA Priority Basin Project is conducted by the U.S. Geological Survey (USGS) in collaboration with the California State Water Resources Control Board and the Lawrence Livermore National Laboratory. There are two study units located in the southern San Joaquin Valley: the Southeast San Joaquin Valley (SESJ) study unit and the Kern County Subbasin (KERN) study unit. The GAMA Priority Basin Project in the SESJ and KERN study units was designed to provide a statistically unbiased, spatially distributed assessment of untreated groundwater quality within the primary aquifers. The status assessment is based on water-quality and ancillary data collected in 2005 and 2006 by the USGS from 130 wells on a spatially distributed grid, and water-quality data from the California Department of Public Health (CDPH) database. Data was collected from an additional 19 wells for the understanding assessment. The aquifer systems (hereinafter referred to as primary aquifers) were defined as that part of the aquifer corresponding to the perforation interval of wells listed in the CDPH database for the SESJ and KERN study units. The status assessment of groundwater quality used data from samples analyzed for anthropogenic constituents such as volatile organic compounds (VOCs) and pesticides, as well as naturally occurring inorganic constituents such as major ions and trace elements. The status assessment is intended to characterize the quality of untreated groundwater resources within the primary aquifers in the SESJ and KERN study units, not the quality of drinking water delivered to consumers. Although the status assessment applies to untreated groundwater, Federal and California regulatory and non-regulatory water-quality benchmarks that apply to drinking water are used to provide context for the results. Relative-concentrations (sample concentration divided by benchmark concentration) were used for evaluating groundwater. A relative-concentration greater than 1.0 indicates a concentration greater than the benchmark and is classified as high. The relative-concentration threshold for classifying inorganic constituents as moderate or low was 0.5; for organic constituents the threshold between moderate and low was 0.1. Aquifer-scale proportion was used as the primary metric for assessing the quality of untreated groundwater for the study units. High aquifer-scale proportion is defined as the areal percentage of the primary aquifers with a high relative-concentration for a particular constituent or class of constituents. Moderate and low aquifer-scale proportions were defined as the areal percentage of the primary aquifers 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 for the two study units in the southern San Joaquin Valley (within 90 percent confidence intervals). The status assessment showed that inorganic constituents were more prevalent than organic constituents and that relative-concentrations were higher for inorganic constituents than for organic constituents. For inorganic constituents with human-health benchmarks, the relative-concentration of at least one constituent in the SESJ study unit was high in 30 percent of the primary aquifers. In the KERN study unit, the relative-concentration of at least one constituent was high in 23 percent of the primary aquifers. In the SESJ and KERN study units, the inorganic constituents with human-health benchmarks detected at high relative-concentrations in more than 2 percent of the primary aquifers were arsenic, boron, vanadium, nitrate, uranium, and gross alpha radioactivity. Additional constituents with human-health benchmarks—antimony, radium, and fluoride—were detected at high relative-concentrations in the KERN study unit. For inorganic constituents with aesthetic benchmarks (secondary maximum contaminant levels, SMCLs), the relative-concentration of at least one constituent in the SESJ study unit was high in 6.6 percent of the primary aquifers. In the KERN study unit, the relative-concentration of at least one constituent was high in 22 percent of the primary aquifers. Inorganic constituents with aesthetic benchmarks detected at high relative-concentrations in the primary aquifers in the SESJ and KERN study units were iron and manganese. Additional constituents with aesthetic benchmarks—total dissolved solids (TDS), sulfate, and chloride—were detected at high relative-concentrations in the KERN study unit. In contrast, the status assessment for organic constituents with human-health benchmarks showed that relative-concentrations were high in 4.8 percent and 2.1 percent of the primary aquifers in the SESJ and KERN study units, respectively. The special-interest constituent, perchlorate, was detected at high relative-concentrations in 1.2 percent of the primary aquifers in the SESJ study unit. Twenty-eight of the 78 VOCs (not including fumigants) analyzed were detected. Of these 28 VOCs, benzene had high relative-concentrations in the SESJ study unit, and relative-concentrations for the other 27 VOCs were moderate and low. Five of the 10 fumigants were detected; 1,2-dibromo-3-chloropropane (DBCP) was the only fumigant with high relative-concentrations in the SESJ and KERN study units. Of the 136 pesticides and pesticide degradates analyzed, 33 were detected. Human-health benchmarks were established for eighteen of the detected pesticides. Dieldrin was detected at moderate relative-concentrations in the SESJ and KERN study units. All other pesticides detected with human-health benchmarks were present at low relative-concentrations. The detection frequencies for two of these pesticides—simazine and atrazine—were greater than or equal to 10 percent in the SESJ and KERN study units. The understanding assessment of groundwater quality included an analysis of correlations of selected water-quality constituents or classes of constituents with potential explanatory factors. The understanding assessment indicated that the concentrations of many trace elements and major ions were correlated to well depth, groundwater age, and/or geochemical conditions. Many trace elements were positively correlated with depth. Arsenic, boron, vanadium, fluoride, manganese, and iron concentrations increased with well depth or depth to top-of-perforations. The concentrations for these trace elements also were higher in older (pre-modern) groundwater. In contrast, uranium concentrations decreased with increasing depth and groundwater age. Most trace elements were correlated to geochemical conditions. Arsenic, antimony, boron, fluoride, manganese, and iron concentrations generally were higher wherever the pH of the groundwater was greater than 7.6. Concentrations for these constituents generally were higher at low concentrations of dissolved oxygen (DO). Uranium was the exception; uranium concentrations generally were lower at high pH and at high concentrations of DO. Nitrate concentrations generally were lower in deeper wells. Nitrate concentrations also were higher in groundwater with higher DO. Total dissolved solids, sulfate, and chloride concentrations were higher in the KERN study unit than in the SESJ study unit. Total dissolved solids were negatively correlated with pH in the KERN study unit. Total dissolved solids and sulfate were higher in areas with more agricultural land use. Chloride concentrations increased with depth to top-of-perforations in the KERN study unit. Organic constituents and constituents of special interest, like many inorganic constituents, were correlated with well depth, groundwater age, and DO. Unlike most trace elements, however, solvent and pesticide detections, and total trihalomethanes (THM), DBCP, and perchlorate concentrations decreased with increasing well depth. Volatile organic compound, solvent, and pesticide detections, and THM concentrations also were lower in older (pre-modern) groundwater than in modern-age groundwater. Solvent detections and total THM, DBCP, and perchlorate concentrations increased with increasing DO concentrations.

California↗

USGS2012

Water-quality characteristics and trend analyses for the Tongue, Powder, Cheyenne, and Belle Fourche River drainage basins, Wyoming and Montana, for selected periods, water years 1991 through 2010

The Powder River structural basin in northeastern Wyoming and southeastern Montana is an area of ongoing coalbed natural gas (CBNG) development. Waters produced during CBNG development are managed with a variety of techniques, including surface impoundments and discharges into stream drainages. The interaction of CBNG-produced waters with the atmosphere and the semiarid soils of the Powder River structural basin can affect water chemistry in several ways. Specific conductance and sodium adsorption ratios (SAR) of CBNG-produced waters that are discharged to streams have been of particular concern because they have the potential to affect the use of the water for irrigation. Water-quality monitoring has been conducted since 2001 at main-stem and tributary sites in the Tongue, Powder, Cheyenne, and Belle Fourche River drainage basins in response to concerns about CBNG effects. A study was conducted to summarize characteristics of stream-water quality for water years 2001–10 (October 1, 2000, to September 30, 2010) and examine trends in specific conductance, SAR, and primary constituents that contribute to specific conductance and SAR for changes through time (water years 1991–2010) that may have occurred as a result of CBNG development. Specific conductance and SAR are the focus characteristics of this report. Dissolved calcium, magnesium, and sodium, which are primary contributors to specific conductance and SAR, as well as dissolved alkalinity, chloride, and sulfate, which are other primary contributors to specific conductance, also are described. Stream-water quality in the Tongue, Powder, Cheyenne, and Belle Fourche River drainage basins was variable during water years 2001–10, in part because of variations in streamflow. In general, annual runoff was less than average during water years 2001–06 and near or above average during water years 2007–10. Stream water of the Tongue River had the smallest specific conductance values, sodium adsorption ratios, and major ion concentrations of the main-stem streams. Sites in the Tongue River drainage basin typically had the smallest range of specific conductance and SAR values. The water chemistry of sites in the Powder River drainage basin generally was the most variable as a result of diverse characteristics of that basin. Plains tributaries in the Powder River drainage basin had the largest range of specific conductance and SAR values, in part due to the many tributaries that receive CBNG-produced waters. Trends were analyzed using the seasonal Kendall test with flow-adjusted concentrations to determine changes to water quality through time at sites in the Tongue, Powder, Cheyenne, and Belle Fourche River drainage basins. Trends were evaluated for water years 2001–10 for 17 sites, which generally were on the main-stem streams and primary tributaries. Trends were evaluated for water years 2005–10 for 26 sites to increase the spatial coverage of sites. Trends were evaluated for water years 1991–2010 for eight sites to include water-quality data collected prior to widespread CBNG development and expand the temporal context of trends. Consistent patterns were not observed in trend results for water years 2001–10 for flow-adjusted specific conductance and SAR values in the Tongue, Powder, and Belle Fourche River drainage basins. Significant (p-values less than 0.05) upward trends in flow-adjusted specific conductance values were determined for 3 sites, a downward trend was determined for 1 site, and no significant (p-value greater than 0.05) trends were determined for 13 sites. One of the sites with a significant upward trend was the Tongue River at the Wyoming-Montana State line. No trend in flow-adjusted specific conductance values was determined for the Powder River at Moorhead, Mont. Significant upward trends in flow-adjusted SAR values were determined for 2 sites and no significant trends were determined for 15 sites. No trends in flow-adjusted SAR values were determined for the Tongue River at the Wyoming-Montana State line or for the Powder River at Moorhead, Mont. One of the sites with a significant upward trend in flow-adjusted SAR values was the Powder River at Arvada, Wyo. For water years 2005–10, significant upward trends in flow-adjusted specific conductance values were determined no significant trends were determined for 13 sites. A significant upward trend was determined for flow-adjusted specific conductance values for the Tongue River at the Wyoming-Montana State line. No trend in flow-adjusted specific conductance values was determined for the Powder River at Moorhead, Mont. Significant upward trends in flow-adjusted SAR values were determined for 4 sites, downward trends were determined for 5 sites, and no significant trend was determined for 17 sites. No trends in flow-adjusted SAR values were determined for the Tongue River at the Wyoming-Montana State line or for the Powder River at Moorhead, Mont. Results of the seasonal Kendall test applied to flow-adjusted specific conductance values for water years 1991–2010 indicated no significant trend for eight sites in the Tongue, Powder, and Belle Fourche River drainage basins. No significant trend in flow-adjusted specific conductance was determined for the Tongue River at the Wyoming-Montana State line or the Powder River at Moorhead, Mont. Results of the seasonal Kendall test applied to flow-adjusted SAR values for water years 1991–2010 indicated an upward trend for one site and no significant trend for four sites in the Powder and Belle Fourche River drainage basins. The significant upward trend in flow-adjusted SAR values was determined for the Powder River at Arvada, Wyo., for water years 1991–2010. Results indicate that CBNG development in the Powder River structural basin may have contributed to some trends, such as the upward trend in flow-adjusted SAR for the Powder River at Arvada, Wyo., for water years 1991–2010. An upward trend in flow-adjusted alkalinity concentrations for water years 2001–10 also was determined for the Powder River at Arvada, Wyo. Trend results are consistent with changes that can occur from the addition of sodium and bicarbonate associated with CBNG-produced waters to the Powder River. Upward trends in constituents at other sites, including the Belle Fourche River, may be the result of declining CBNG development, indicating that CBNG-produced waters may have had a dilution effect on some streams. The factors affecting other trends could not be determined because multiple factors could have been affecting the stream-water quality or because trends were observed at sites upstream from CBNG development that may have affected water-quality trends at sites downstream.

Wyoming;Montana↗

USGS2013

The effects of artificial recharge on groundwater levels and water quality in the west hydrogeologic unit of the Warren subbasin, San Bernardino County, California

Between the late 1940s and 1994, groundwater levels in the Warren subbasin, California, declined by as much as 300 feet because pumping exceeded sparse natural recharge. In response, the local water district, Hi-Desert Water District, implemented an artificial-recharge program in early 1995 using imported water from the California State Water Project. Subsequently, the water table rose by as much as 250 feet; however, a study done by the U.S. Geological Survey found that the rising water table entrained high-nitrate septic effluent, which caused nitrate (as nitrogen) concentrations in some wells to increase to more than the U.S. Environmental Protection Agency maximum contaminant level of 10 milligrams per liter.. A new artificial-recharge site (site 3) was constructed in 2006 and this study, which started in 2004, was done to address concerns about the possible migration of nitrates in the unsaturated zone. The objectives of this study were to: (1) characterize the hydraulic, chemical, and microbiological properties of the unsaturated zone; (2) monitor changes in water levels and water quality in response to the artificial-recharge program at site 3; (3) determine if nitrates from septic effluent infiltrated through the unsaturated zone to the water table; (4) determine the potential for nitrates within the unsaturated zone to mobilize and contaminate the groundwater as the water table rises in response to artificial recharge; and (5) determine the presence and amount of dissolved organic carbon because of its potential to react with disinfection byproducts during the treatment of water for public use. Two monitoring sites were installed and instrumented with heat-dissipation probes, advanced tensiometers, suction-cup lysimeters, and wells so that the arrival and effects of recharging water from the State Water Project through the 250 to 425 foot-thick unsaturated zone and groundwater system could be closely observed. Monitoring site YVUZ-1 was located between two recharge ponds in the middle of site 3, and YVUZ-2 was located approximately 1,200 feet down-gradient and to the southeast in an area where septic systems have been in use since about 1960. Site YVUZ-3 only went to a depth of 42 feet and was used to sample the upper part of the unsaturated zone near a golf course. Prior to the start of artificial recharge at site 3, nitrate concentrations reported as nitrogen from the soil leachate below YVUZ-1 did not exceed 1.58 milligrams per kilogram. Nitrate-reducing bacteria concentrations of 4,300 most probable number were found at about 220 feet below land surface and at the top of the water table at YVUZ-1. Nitrate concentrations at YVUZ-2 reached a maximum concentration of about 25 milligrams per kilogram between about 100 and 121 feet below land surface; concentrations of nitrate-reducing or denitrifying bacteria were as high as 21,000 most probable number at 36 feet below land surface but did not exceed 40 most probable number below about 150 feet below land surface. Between June 2006 and September 2009, more than 9,800 acre feet of water from the State Water Project was released to site 3 ponds. The infiltration of the recharge water was predominantly vertical with limited lateral spreading to a depth of about 200 feet below land surface at YVUZ-1. Lateral spreading of the recharge water with depth was caused by geologic heterogeneities within the unsaturated zone, and resulted in varied arrival times of the recharge water to the instruments and slower rates of vertical movement with depth. No abrupt changes in soil moisture were observed at YVUZ-2, indicating that the recharge water had not reached that site by September 2009. Water levels from the monitoring wells at both sites and from five production wells nearby showed that the water table rose at a mean rate of about 0.08 feet per day between June 2006 and January 2009. The arrival of the water from the State Water Project caused relatively rapid changes in the stable-isotopic ratios from the lysimeters at YVUZ-1. The estimated average rate of infiltration of the recharge water through the unsaturated zone ranged from 3.7 to 25 feet per day. The recharge water arrived at the monitoring well below the recharge ponds between August 2007 and March 2008; the rate of vertical movement to the monitoring well was between 0.6 and 0.9 feet per day. By September 2008, a production well located 375 feet west of site 3 was producing almost 100 percent infiltrated recharge water. By contrast, the stable-isotope data from the lysimeters at YVUZ-2 showed that the recharge water had not reached this site by September 2009, but that septic effluent in the unsaturated zone likely had mixed with the native pore water to at least 154 feet below land surface. Assuming vertical infiltration, the minimum rate of infiltration of septic effluent since 1960 was about 3 feet per year. The isotopic data from the lysimeters at YVUZ-3 indicated two different sources of water to the upper 43 feet–irrigation-return flow and precipitation. Nitrate concentrations of the water from the State Water Project did not exceed 1 milligram per liter. Prior to artificial recharge, nitrate concentrations of the pore water at YVUZ-1 ranged between 6 to 18.2 milligrams per liter. After the arrival of the recharge water, the nitrate concentrations from the lysimeters and well at YVUZ-1 decreased to less than 1 milligram per liter, with the exception of samples collected at 205.5 feet, which did not exceed 4.12 milligrams per liter. The decrease in nitrate concentrations after artificial recharge indicated that the rising water table did not result in an increase of nitrates below YVUZ-1. At YVUZ-2, nitrate concentrations ranged between 12 to 479 milligrams per liter. The highest nitrate concentrations were at 92 feet below land surface and were almost seven times that of samples collected from a nearby septic tank. Nitrate concentrations from the lysimeter at 273 feet below land surface increased from 6 to almost 58 milligrams per liter after it was saturated by the rising water table in December 2007. These increases could be the result of the mobilization of high-nitrate water from regional sources of septic effluent after saturation, or the result of high-nitrate water present at the top of the water table that may be diluted deeper in the aquifer. Nitrate concentrations in groundwater from five nearby production wells and from both monitoring wells were less than 5 milligrams per liter before artificial recharge started. Nitrate concentrations decreased to less than 3 milligrams per liter in three of the production wells and the monitoring well below the recharge ponds after artificial recharge. Dissolved organic carbon concentrations were measured in the recharge water and groundwater because of the potential for dissolved organic carbon to react with chlorine to form trihalomethanes during the water-treatment process. The dissolved organic carbon concentrations of the recharge water were 3.1 milligrams per liter or less, and dissolved organic carbon concentrations of the groundwater were less than 1 milligram per liter. Even though recharge water was present in some of the wells by September 2008, the concentrations of both dissolved organic carbon and trihalomethane formation potential in the groundwater did not increase. Interpretation of these data suggests that the dissolved organic carbon from the recharge water is altered or metabolized in the unsaturated zone, either by absorption to the grain particles in the soil or by microbiological processes.

California↗

USGS2013

Groundwater and surface-water interactions near White Bear Lake, Minnesota, through 2011

The U.S. Geological Survey, in cooperation with the White Bear Lake Conservation District, the Minnesota Pollution Control Agency, the Minnesota Department of Natural Resources, and other State, county, municipal, and regional planning agencies, watershed organizations, and private organizations, conducted a study to characterize groundwater and surface-water interactions near White Bear Lake through 2011. During 2010 and 2011, White Bear Lake and other lakes in the northeastern part of the Twin Cities Metropolitan Area were at historically low levels. Previous periods of lower water levels in White Bear Lake correlate with periods of lower precipitation; however, recent urban expansion and increased pumping from the Prairie du Chien-Jordan aquifer have raised the question of whether a decline in precipitation is the primary cause for the recent water-level decline in White Bear Lake. Understanding and quantifying the amount of groundwater inflow to a lake and water discharge from a lake to aquifers is commonly difficult but is important in the management of lake levels. Three methods were used in the study to assess groundwater and surface-water interactions on White Bear Lake: (1) a historical assessment (1978-2011) of levels in White Bear Lake, local groundwater levels, and their relation to historical precipitation and groundwater withdrawals in the White Bear Lake area; (2) recent (2010-11) hydrologic and water-quality data collected from White Bear Lake, other lakes, and wells; and (3) water-balance assessments for White Bear Lake in March and August 2011. An analysis of covariance between average annual lake-level change and annual precipitation indicated the relation between the two variables was significantly different from 2003 through 2011 compared with 1978 through 2002, requiring an average of 4 more inches of precipitation per year to maintain the lake level. This shift in the linear relation between annual lake-level change and annual precipitation indicated the net effect of the non-precipitation terms on the water balance has changed relative to precipitation. The average amount of precipitation required each year to maintain the lake level has increased from 33 inches per year during 1978-2002 to 37 inches per year during 2003-11. The combination of lower precipitation and an increase in groundwater withdrawals can explain the change in the lake-level response to precipitation. Annual and summer groundwater withdrawals from the Prairie du Chien-Jordan aquifer have more than doubled from 1980 through 2010. Results from a regression model constructed with annual lake-level change, annual precipitation minus evaporation, and annual volume of groundwater withdrawn from the Prairie du Chien-Jordan aquifer indicated groundwater withdrawals had a greater effect than precipitation minus evaporation on water levels in the White Bear Lake area for all years since 2003. The recent (2003-11) decline in White Bear Lake reflects the declining water levels in the Prairie du Chien-Jordan aquifer; increases in groundwater withdrawals from this aquifer are a likely cause for declines in groundwater levels and lake levels. Synoptic, static groundwater-level and lake-level measurements in March/April and August 2011 indicated groundwater was potentially flowing into White Bear Lake from glacial aquifers to the northeast and south, and lake water was potentially discharging from White Bear Lake to the underlying glacial and Prairie du Chien-Jordan aquifers and glacial aquifers to the northwest. Groundwater levels in the Prairie du Chien-Jordan aquifer below White Bear Lake are approximately 0 to 19 feet lower than surface-water levels in the lake, indicating groundwater from the aquifer likely does not flow into White Bear Lake, but lake water may discharge into the aquifer. Groundwater levels from March/April to August 2011 declined more than 10 feet in the Prairie du Chien-Jordan aquifer south of White Bear Lake and to the north in Hugo, Minnesota. Water-quality analyses of pore water from nearshore lake-sediment and well-water samples, seepage-meter measurements, and hydraulic-head differences measured in White Bear Lake also indicated groundwater was potentially flowing into White Bear Lake from shallow glacial aquifers to the east and south. Negative temperature anomalies determined in shallow waters in the water-quality survey conducted in White Bear Lake indicated several shallow-water areas where groundwater may be flowing into the lake from glacial aquifers below the lake. Cool lake-sediment temperatures (less than 18 degrees Celsius) were measured in eight areas along the northeast, east, south, and southwest shores of White Bear Lake, indicating potential areas where groundwater may flow into the lake. Stable isotope analyses of well-water, precipitation, and lake-water samples indicated wells downgradient from White Bear Lake screened in the glacial buried aquifer or open to the Prairie du Chien-Jordan aquifer receive a mixture of surface water and groundwater; the largest surface-water contributions are in wells closer to White Bear Lake. A wide range in oxygen-18/oxygen-16 and deuterium/protium ratios was measured in well-water samples, indicating different sources of water are supplying water to the wells. Well water with oxygen-18/oxygen-16 and deuterium/protium ratios that plot close to the meteoric water line consisted mostly of groundwater because deuterium/protium ratios for most groundwater usually are similar to ratios for rainwater and snow, plotting close to meteoric water lines. Well water with oxygen-18/oxygen-16 and deuterium/protium ratios that plot between the meteoric water line and ratios for the surface-water samples from White Bear Lake consists of a mixture of surface water and groundwater; the percentage of each source varies relative to its ratios. White Bear Lake is the likely source of the surface water to the wells that have a mixture of surface water and groundwater because (1) it is the only large, deep lake near these wells; (2) these wells are near and downgradient from White Bear Lake; and (3) these wells obtain their water from relatively deep depths, and White Bear Lake is the deepest lake in that area. The percentages of surface-water contribution to the three wells screened in the glacial buried aquifer receiving surface water were 16, 48, and 83 percent. The percentages of surface-water contribution ranged from 5 to 79 percent for the five wells open to the Prairie du Chien-Jordan aquifer receiving surface water; wells closest to White Bear Lake had the largest percentages of surface-water contribution. Water-balance analysis of White Bear Lake in March and August 2011 indicated a potential discharge of 2.8 and 4.5 inches per month, respectively, over the area of the lake from the lake to local aquifers. Most of the sediments from a 12.4-foot lake core collected at the deepest part of White Bear Lake consisted of silts, sands, and gravels likely slumped from shallower waters, with a very low amount of low-permeability, organic material.

Minnesota↗

USGS2010

Hydrogeomorphic segments and hydraulic microhabitats of the Niobrara River, Nebraska— With special emphasis on the Niobrara National Scenic River

The Niobrara River is an ecologically and economically important resource in Nebraska. The Nebraska Department of Natural Resources’ recent designation of the hydraulically connected surface- and groundwater resources of the Niobrara River Basin as “fully appropriated” has emphasized the importance of understanding linkages between the physical and ecological dynamics of the Niobrara River so it can be sustainably managed. In cooperation with the Nebraska Game and Parks Commission, the U.S. Geological Survey investigated the hydrogeomorphic and hydraulic attributes of the Niobrara River in northern Nebraska. This report presents the results of an analysis of hydrogeomorphic segments and hydraulic microhabitats of the Niobrara River and its valley for the approximately 330-mile reach from Dunlap Diversion Dam to its confluence with the Missouri River. Two spatial scales were used to examine and quantify the hydrogeomorphic segments and hydraulic microhabitats of the Niobrara River: a basin scale and a reach scale. At the basin scale, digital spatial data and hydrologic data were analyzed to (1) test for differences between 36 previously determined longitudinal hydrogeomorphic segments; (2) quantitatively describe the hydrogeomorphic characteristics of the river and its valley; and (3) evaluate differences in hydraulic microhabitat over a range of flow regimes among three fluvial geomorphic provinces. The statistical analysis of hydrogeomorphic segments resulted in reclassification rates of 3 to 28 percent of the segments for the four descriptive geomorphic elements. The reassignment of classes by discriminant analysis resulted in a reduction from 36 to 25 total hydrogeomorphic segments because several adjoining segments shared the same ultimate class assignments. Virtually all of the segment mergers were in the Canyons and Restricted Bottoms (CRB) fluvial geomorphic province. The most frequent classes among hydrogeomorphic segments, and the dominant classes per unit length of river, are: a width-restricted valley confinement condition, sinuous-planview pattern, irregular channel width, and an alternate bar configuration. The Niobrara River in the study area flows through a diversity of fluvial geomorphic settings in its traverse across northern Nebraska. In the Meandering Bottoms (MB) fluvial geomorphic province, river discharge magnitudes are low, and the valley exerts little control on the channel-planview pattern. Within the CRB province, the river flows over a diversity of geologic formations, and the valley and river narrow and expand in approximate synchronicity. In the Braided Bottoms (BB) fluvial geomorphic province, the river primarily flows over Cretaceous Pierre Shale, the valley and channel are persistently wide, and the channel slope is generally uniform. The existence of vegetated islands and consequent multithread channel environments, indicated by a higher braided index, mostly coincided with reaches having gentler slopes and less unit stream power. Longitudinal hydrology curves indicate that the flow of the Niobrara River likely is dominated by groundwater as far downstream as Norden. Unit stream power values in the study area vary between 0 and almost 2 pounds per foot per second. Within the MB province, unit stream power steadily increases as the Niobrara gains discharge from groundwater inflow, and the channel slope steepens. The combination of steep slopes, a constrained channel width, and persistent flow within the CRB province results in unit stream power values that are between three and five times greater than those in less confined segments with comparable or greater discharges. With the exception of hydrogeomorphic segment 3, which is affected by Spencer Dam, unit stream power values in the BB province are generally uniform. Channel sinuosity values in the study area varied generally between 1 and 2.5, but with locally higher values measured in the MB province and at the entrenched bedrock meanders of hydrogeomorphic segment 18 in the CRB province. The differences in channel morphology and hydraulic geometries between fluvial geomorphic provinces are evident in the types, relative abundance, and response of hydraulic microhabitats to changing discharges. The four gaging stations chosen for hydraulic microhabitat analysis are distributed among three different fluvial geomorphic provinces. In the MB province, the smaller channel and lower discharges resulted in the dominance of shallow and intermediate-depth hydraulic environments with the vast majority of hydraulic microhabitat restricted to shallow categories even during upper-decile discharges. In the CRB province, intermediate depth hydraulic conditions, particularly intermediate-swift, dominate over all ranges of discharge. Hydraulic microhabitat conditions were most diverse in the BB province, with most hydraulic microhabitat categories present over the entire range of discharges analyzed. The calculated differences in hydraulic microhabitat distributions, abundance, and adjustments between streamflow-gaging stations were the result of differences in physical structure of the channel and subsequent channel hydraulic geometry. At the reach scale, field measurements made in water years 2008 and 2009 in four study reaches within the Scenic Reach were used to (1) characterize the elevation and geomorphic processes associated with fluvial landforms, (2) build hydraulic geometry relations, (3) examine flow hydraulics over a range of discharges, and (4) examine the types and responses of hydraulic microhabitats to a range of flow magnitudes. Four landform groups were identified and named in order of increasing elevation: low flood plains, intermediate flood plains, low terraces, and high terraces. The terraces were poorly characterized because the surveys did not extend across the full width of the alluvial valley bottom. The two lowest fluvial landforms are likely active in the modern hydroclimatic regime. Sediment samples obtained in the study reaches indicate that the primary bed material in the active channel ranged in size from coarse silt to coarse sand. Grain-size distributions from samples also indicate that the bed of the Niobrara River among the study reaches coarsens and has increasing grainsize variability in the downstream direction. Values of at-a-station hydraulic geometry exponents indicate that the Niobrara River in the study reaches adjusts its geometry to changing discharges primarily through increases in flow depth and velocity. Relations at one cross section indicated that, at least locally, changes in width were also an important channel adjustment mechanism. Hydraulic behavior over the range of flows measured was not consistent among all study reaches, but two general modes of hydraulic behavior were observed in the reaches with substantial coverage of the bed by fine sediment. At the Sunny Brook and Muleshoe study reaches, average boundary-shear stress remained approximately constant, and hydraulic resistance decreased, for discharges below 900 cubic feet per second (ft 3 /s). Above 900 ft 3 /s, average boundary shear stress and hydraulic resistance both increased. The Rock Barn study reach did not exhibit the same two-mode hydraulic behavior observed at the Sunny Brook and Muleshoe reaches. The coincident increase in boundary shear stress above 900 ft 3 /s observed at the Sunny Brook and Muleshoe study reaches represents a potential hydraulic threshold above which bedload transport rates were likely to increase markedly. No consistent bed-adjustment pattern (scour or fill) was identified in the study reaches over the range of flows or over the measurement season. Analysis of hydraulic microhabitats over the range of discharges measured at the study reaches indicates that some percentage of most habitat niche categories was available for at least one discharge condition, but the majority of hydraulic habitat available was within the intermediate-swift and deepswift habitat niche categories. Deep-swift conditions dominated nearly all study reaches under all measured discharge conditions. Slight differences in habitat distributions were observed between the study reaches with substantial coverage of the bed by fine sediment—Sunny Brook, Muleshoe, and Rock Barn—and the bedrock-dominated reach, Crooked Creek. Although the four study reaches occupy three different hydrogeomorphic segments, the types, relative abundance, and response of hydraulic microhabitat niche distributions to changing discharge conditions generally were similar among all reaches.

Nebraska↗

USGS2017

Groundwater quality in the Western San Joaquin Valley study unit, 2010: California GAMA Priority Basin Project

Water quality in groundwater resources used for public drinking-water supply in the Western San Joaquin Valley (WSJV) was investigated by the USGS in cooperation with the California State Water Resources Control Board (SWRCB) as part of its Groundwater Ambient Monitoring and Assessment (GAMA) Program Priority Basin Project. The WSJV includes two study areas: the Delta–Mendota and Westside subbasins of the San Joaquin Valley groundwater basin. Study objectives for the WSJV study unit included two assessment types: (1) a status assessment yielding quantitative estimates of the current (2010) status of groundwater quality in the groundwater resources used for public drinking water, and (2) an evaluation of natural and anthropogenic factors that could be affecting the groundwater quality. The assessments characterized the quality of untreated groundwater, not the quality of treated drinking water delivered to consumers by water distributors. The status assessment was based on data collected from 43 wells sampled by the U.S. Geological Survey for the GAMA Priority Basin Project (USGS-GAMA) in 2010 and data compiled in the SWRCB Division of Drinking Water (SWRCB-DDW) database for 74 additional public-supply wells sampled for regulatory compliance purposes between 2007 and 2010. To provide context, concentrations of constituents measured in groundwater were compared to U.S. Environmental Protection Agency (EPA) and SWRCB-DDW regulatory and non-regulatory benchmarks for drinking-water quality. The status assessment used a spatially weighted, grid-based method to estimate the proportion of the groundwater resources used for public drinking water that has concentrations for particular constituents or class of constituents approaching or above benchmark concentrations. This method provides statistically unbiased results at the study-area scale within the WSJV study unit, and permits comparison of the two study areas to other areas assessed by the GAMA Priority Basin Project statewide. Groundwater resources used for public drinking water in the WSJV study unit are among the most saline and most affected by high concentrations of inorganic constituents of all groundwater resources used for public drinking water that have been assessed by the GAMA Priority Basin Project statewide. Among the 82 GAMA Priority Basin Project study areas statewide, the Delta–Mendota study area ranked above the 90th percentile for aquifer-scale proportions of groundwater resources having concentrations of total dissolved solids (TDS), sulfate, chloride, manganese, boron, chromium(VI), selenium, and strontium above benchmarks, and the Westside study area ranked above the 90th percentile for TDS, sulfate, manganese, and boron. In the WSJV study unit as a whole, one or more inorganic constituents with regulatory or non-regulatory, health-based benchmarks were present at concentrations above benchmarks in about 53 percent of the groundwater resources used for public drinking water, and one or more organic constituents with regulatory health-based benchmarks were detected at concentrations above benchmarks in about 3 percent of the resource. Individual constituents present at concentrations greater than health-based benchmarks in greater than 2 percent of groundwater resources used for public drinking water included: boron (51 percent, SWRCB-DDW notification level), chromium(VI) (25 percent, SWRCB-DDW maximum contaminant level (MCL)), arsenic (10 percent, EPA MCL), strontium (5.1 percent, EPA Lifetime health advisory level (HAL)), nitrate (3.9 percent, EPA MCL), molybdenum (3.8 percent, EPA HAL), selenium (2.6 percent, EPA MCL), and benzene (2.6 percent, SWRCB-DDW MCL). In addition, 50 percent of the resource had TDS concentrations greater than non-regulatory, aesthetic-based SWRCB-DDW upper secondary maximum contaminant level (SMCL), and 44 percent had manganese concentrations greater than the SWRCB-DDW SMCL. Natural and anthropogenic factors that could affect the groundwater quality were evaluated by using results from statistical testing of associations between constituent concentrations and values of potential explanatory factors, inferences from geochemical and age-dating tracer results, and by considering the water-quality results in the context of the hydrogeologic setting of the WSJV study unit. Natural factors, particularly the lithologies of the source areas for groundwater recharge and of the aquifers, were the dominant factors affecting groundwater quality in most of the WSJV study unit. However, where groundwater resources used for public supply included groundwater recharged in the modern era, mobilization of constituents by recharge of water used for irrigation also affected groundwater quality. Public-supply wells in the Westside study area had a median depth of 305 m and primarily tapped groundwater recharged hundreds to thousands of years ago, whereas public-supply wells in the Delta–Mendota study area had a median depth of 85 m and primarily tapped either groundwater recharged within the last 60 years or groundwater consisting of mixtures of this modern recharge and older recharge. Public-supply wells in the WSJV study unit are screened in the Tulare Formation and zones above and below the Corcoran Clay Member are used. The Tulare Formation primarily consists of alluvial sediments derived from the Coast Ranges to the west, except along the valley trough at the eastern margin of the WSJV study unit where the Tulare Formation consists of fluvial sands derived from the Sierra Nevada to the east. Groundwater from wells screened in the Sierra Nevada sands had manganese-reducing or manganese- and iron-reducing oxidation-reduction (redox) conditions. These redox conditions commonly were associated with elevated arsenic or molybdenum concentrations, and the dominance of arsenic(III) in the dissolved arsenic supports reductive dissolution of iron and manganese oxyhydroxides as the mechanism. In addition, groundwater from many wells screened in Sierra Nevada sands contained low concentrations of nitrite or ammonium, indicating reduction of nitrate by denitrification or dissimilatory processes, respectively. Geology of the Coast Ranges westward of the study unit strongly affects groundwater quality in the WSJV. Elevated concentrations of TDS, sulfate, boron, selenium and strontium in groundwater were primarily associated with aquifer sediments and recharge derived from areas of the Coast Ranges dominated by Cretaceous-to-Miocene age, organic-rich, reduced marine shales, known as the source of selenium in WSJV soils, surface water, and groundwater. Low sulfur-isotopic values (δ34S) of dissolved sulfate indicate that the sulfate was largely derived from oxidation of biogenic pyrite from the shales, and correlations with trace element concentrations, geologic setting, and groundwater geochemical modeling indicated that distributions of sulfate, strontium, and selenium in groundwater were controlled by dissolution of secondary sulfate minerals in soils and sediments. Elevated concentrations of chromium(VI) were primarily associated with aquifer sediments and recharge derived from areas of the Coast Ranges dominated by the Franciscan Complex and ultramafic rocks. The Franciscan Complex also has boron-rich, sodium-chloride dominated hydrothermal fluids that contribute to elevated concentrations of boron and TDS. Groundwater from wells screened in Coast Ranges alluvium was primarily oxic and relatively alkaline (median pH value of 7.55) in the Delta–Mendota study area, and primarily nitrate-reducing or suboxic and alkaline (median pH value of 8.4) in the Westside study area. Many groundwater samples from those wells have elevated concentrations of arsenic(V), molybdenum, selenium, or chromium(VI), consistent with desorption of metal oxyanions from mineral surfaces under those geochemical conditions. High concentrations of benzene were associated with deep wells located in the vicinity of petroleum deposits at the southern end of the Westside study area. Groundwater from these wells had premodern age and anoxic geochemical conditions, and the ratios among concentrations of hydrocarbon constituents were different from ratios found in fuels and combustion products, which is consistent with a geogenic source for the benzene rather than contamination from anthropogenic sources. Water stable-isotope compositions, groundwater recharge temperatures, and groundwater ages were used to infer four types of groundwater: (1) groundwater derived from natural recharge of water from major rivers draining the Sierra Nevada; (2) groundwater primarily derived from natural recharge of water from Coast Ranges runoff; (3) groundwater derived from recharge of pumped groundwater applied to the land surface for irrigation; and (4) groundwater derived from recharge during a period of much cooler paleoclimate. Water previously used for irrigation was found both above and below the Corcoran Clay, supporting earlier inferences that this clay member is no longer a robust confining unit. Recharge of water used for irrigation has direct and indirect effects on groundwater quality. Elevated nitrate concentrations and detections of herbicides and fumigants in the Delta–Mendota study area generally were associated with greater agricultural land use near the well and with water recharged during the last 60 years. However, the extent of the groundwater resource affected by agricultural sources of nitrate was limited by groundwater redox conditions sufficient to reduce nitrate. The detection frequency of perchlorate in Delta–Mendota groundwater was greater than expected for natural conditions. Perchlorate, nitrate, selenium, and strontium concentrations were correlated with one another and were greater in groundwater inferred to be recharge of previously pumped groundwater used for irrigation. The source of the perchlorate, selenium, and strontium appears to be salts deposited in the soils and sediments of the arid WSJV that are dissolved and flushed into groundwater by the increased amount of recharge caused by irrigation. In the Delta–Mendota study area, the groundwater with elevated concentrations of selenium was found deeper in the aquifer system than it was reported by a previous study 25 years earlier, suggesting that this transient front of groundwater with elevated concentrations of constituents derived from dissolution of soil salts by irrigation recharge is moving down through the aquifer system and is now reaching the depth zone used for public drinking water supply.

California↗

USGS2014

U.S. Geological Survey Karst Interest Group Proceedings, Carlsbad, New Mexico, April 29-May 2, 2014

Karst aquifer systems are present throughout parts of the United States and some of its territories, and have developed in carbonate rocks (primarily limestone and dolomite) that span an interval of time encompassing more than 550 million years. The depositional environments, diagenetic processes, post-depositional tectonic events, and geochemical weathering processes that form karst aquifers are varied and complex, and involve biological, chemical, and physical changes. These factors, combined with the diverse climatic regimes under which karst development in these rocks has taken place, result in the unique dual- or triple-porosity nature of karst aquifers. These complex hydrogeologic systems typically represent challenging and unique conditions to scientists attempting to study groundwater flow and contaminant transport in these terrains. The dissolution of carbonate rocks and the subsequent development of distinct and beautiful landscapes, caverns, and springs has resulted in the most exceptional karst areas of the United States being designated as national or state parks; commercial caverns and known privately owned caves number in the tens of thousands. Both public and private properties provide access for scientists to study the flow of groundwater in situ. Likewise, the range and complexity of landforms and groundwater flow systems associated with karst terrains are enormous, perhaps more than for any other aquifer type. Karst aquifers and landscapes that form in tropical areas, such as the cockpit karst along the north coast of Puerto Rico, differ greatly from karst landforms in more arid climates, such as the Edwards Plateau in west-central Texas or the Guadalupe Mountains near Carlsbad, New Mexico, where hypogenic processes have played a major role in speleogenesis. Many of these public and private lands also contain unique flora and fauna associated with these karst hydrogeologic systems. As a result, numerous federal, state, and local agencies have a strong interest in the study of karst terrains. Many of the major springs and aquifers in the United States have developed in carbonate rocks, such as the Floridan aquifer system in Florida and parts of Alabama, Georgia, and South Carolina; the Ozark Plateaus aquifer system in parts of Arkansas, Kansas, Missouri, and Oklahoma; and the Edwards-Trinity aquifer system in west-central Texas. These aquifers, and the springs that discharge from them, serve as major water-supply sources and as unique ecological habitats. Competition for the water resources of karst aquifers is common, and urban development and the lack of attenuation of contaminants in karst areas can impact the ecosystem and water quality of these aquifers. The concept for developing a platform for interaction among scientists within the U.S. Geological Survey (USGS) working on karst-related studies evolved from the November 1999 National Ground-Water Meeting of the USGS. As a result, the Karst Interest Group (KIG) was formed in 2000. The KIG is a loose-knit, grass-roots organization of USGS and non-USGS scientists and researchers devoted to fostering better communication among scientists working on, or interested in, karst science. The primary mission of the KIG is to encourage and support interdisciplinary collaboration and technology transfer among scientists working in karst areas. Additionally, the KIG encourages collaborative studies between the different mission areas of the USGS as well as other federal and state agencies, and with researchers from academia and institutes. The KIG also encourages younger scientists by participation of students in the poster and oral sessions. To accomplish its mission, the KIG has organized a series of workshops that are held near nationally important karst areas. To date (2014) six KIG workshops, including the workshop documented in this report, have been held. The workshops typically include oral and poster sessions on selected karst-related topics and research, as well as field trips to local karst features. Proceedings of the workshops are published by the USGS and are available online at http://water.usgs.gov/ogw/karst/kig . The first KIG workshop was held in St. Petersburg, Florida, February 13–16, 2001, in the vicinity of the large springs and other karst features of the Floridan aquifer system. The second KIG workshop was held August 20–22, 2002, in Shepherdstown, West Virginia, in proximity to the carbonate aquifers of the northern Shenandoah Valley and highlighted an invited presentation on karst literature by the late Barry F. Beck of P.E. LaMoreaux and Associates. The third KIG workshop was held September 12–15, 2005, in Rapid City, South Dakota, nearby to karst features in evaporites and limestones of the Madison Group in the Black Hills of South Dakota, including Wind Cave National Park and Jewel Cave National Monument. The workshop also included a featured presentation by Thomas Casadevall, Central Region Director, USGS, on the status of earth science at the USGS and evening trips to Jewel Cave led by Mike Wiles, National Park Service (NPS) and Wind Cave led by Rod Horrocks, NPS. The fourth KIG workshop was held May 27–29, 2008, and hosted by the Hoffman Environmental Research Institute and Center for Cave and Karst Studies at Western Kentucky University in Bowling Green, Kentucky, near Mammoth Cave National Park and karst features of the Chester Upland and Pennyroyal Plateau. The workshop featured a late-night field trip into Mammoth Cave with Rickard Toomey and Rick Olsen, NPS. The fifth workshop was held April 26–29, 2011, and was a joint meeting of the USGS KIG and University of Arkansas HydroDays, hosted by the Department of Geosciences at the University of Arkansas in Fayetteville. The workshop featured an outstanding field trip to the unique karst terrain along the Buffalo National River of the southern Ozarks and a keynote presentation on paleokarst in the United States by Art and Peggy Palmer. This sixth and current 2014 KIG workshop is hosted by the National Cave and Karst Research Institute (NCKRI) in Carlsbad, New Mexico, with Director of NCKRI, George Veni, serving as co-chair of the workshop with Eve Kuniansky, USGS. The session planning committee for this sixth workshop includes Van Brahana, USGS retired and University of Arkansas Professor Emeritus; Tom Byl, USGS and Tennessee State University; Zelda Bailey, former Director of NCKRI and retired Director, National Institute of Standards and Technology, Boulder Laboratory, Colorado; Patrick Tucci, USGS retired; and Mike Bradley, Allan Clark, Geoff Delin, Daniel Doctor, James Kaufmann, Eve Kuniansky, Randy Orndorff, Larry Spangler, and Dave Weary of the USGS. The karst hydrology field trip on Thursday will be led by Lewis Land (NCKRI karst hydrologist) and the optional Friday field trip on the geology of Carlsbad Caverns National Park will be led by George Veni. The keynote speaker is Dr. Penelope Boston, Director of Cave and Karst Studies at New Mexico Tech, Socorro, and Academic Director at NCKRI, who will address the future of karst research. Additionally, there is a featured presentation “Irish karst and its management,” by Caoimhe Hickey, The Geological Survey of Ireland, preceding a panel discussion on “Collaboration During Times of Limited Resources.” The extended abstracts of USGS authors were peer reviewed and approved for publication by the U.S. Geological Survey. Articles submitted by university researchers and other federal and state agencies did not go through the formal USGS peer review and approval process, and therefore may not adhere to our editorial standards or stratigraphic nomenclature and is not research conducted or data collected by the USGS. However, all articles had at a minimum of two peer reviews, and all articles were edited for consistency of appearance in the published Proceedings. The use of trade, firm or product names in any article is for descriptive purposes only and does not imply endorsement by the U.S. Government. The USGS, Office of Groundwater, provides technical support for the Karst Interest Group website and public availability of the Proceedings from these workshops, and the USGS Groundwater Resources Program funds the publication costs. Finally, the cover illustration is the work of Ann Tihansky, USGS, used since the first KIG workshop in 2000.

Scientific Investigations Report↗

USGS2020

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↗