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Trends in streamflow and concentrations and flux of nutrients and total suspended solids in the Upper White River at Muncie, near Nora, and near Centerton, Indiana

The U.S. Geological Survey (USGS), in cooperation with The Nature Conservancy, completed a study to estimate and assess trends in streamflow and annual mean concentrations and flux of nutrients (nitrate plus nitrite, total Kjeldahl nitrogen, and total phosphorus) and total suspended solids at three USGS streamgages (hereafter referred to as “study gages”) on the Upper White River at Muncie (USGS station 03347000), near Nora (USGS station 03351000), and near Centerton (USGS station 03354000), Indiana. Water-quality data used in the analyses were collected by several agencies between calendar years 1991 and 2017, and streamflow (discharge) data were collected by the USGS. For most of the water-quality constituents, there were suitable data to facilitate an analysis of the 26-year period extending from calendar years 1991 to 2017 (water years 1992 to 2017); however, shorter analytical periods were necessary for total Kjeldahl nitrogen for the study gages at Muncie and near Centerton and for total suspended solids for the study gage near Centerton. Temporal trends in streamflows at the study gages for the period extending from water years 1978 to 2017 were assessed using Exploration and Graphics for RivEr Trends (EGRET) and Mann-Kendall and Pettitt tests. With just one exception, the annual maximum and mean daily streamflows and the annual minimum 7-day mean streamflows at the study gages demonstrated upward trends (increasing streamflows) in the EGRET analyses. The exception was the annual 7-day minimum streamflow at the study gage near Nora, which indicated no trend. Mann-Kendall tests also indicated that the average trend for the annual maximum daily, annual mean daily, and annual 7-day minimum streamflow statistics between water years 1978 and 2017 was upward at each of the study gages; however, only the trends in the annual mean daily streamflows at the study gage at Muncie and the annual maximum daily streamflows at the study gages near Nora and near Centerton were statistically significant at a 0.05 probability level. The Pettitt tests indicated that a statistically significant step trend (abrupt change) in annual mean daily streamflows occurred at each of the study gages around water year 2001. The seasonal distributions of total suspended solids, total phosphorus, nitrate plus nitrite, and total Kjeldahl nitrogen concentrations at the study gages were evaluated to identify patterns and other distinguishing characteristics by examining boxplots of concentrations as a function of month of the year. Seasonal distributions of nitrate plus nitrite concentrations and total suspended solids concentrations differed from each other but were generally similar among the three study gages for a given constituent. Median concentrations of nitrate plus nitrite were highest during the January–June months, whereas median concentrations of total suspended solids were highest during June and July. Seasonal distributions of total phosphorus concentrations were similar at the study gages near Nora and near Centerton, but the seasonal distribution was noticeably different at the study gage at Muncie, which had monthly median concentrations that were substantially lower than at the two downstream study gages (near Nora and near Centerton). The seasonal distribution of total Kjeldahl nitrogen concentrations differed in pattern among the three study gages; however, in general, some of the higher monthly median total Kjeldahl nitrogen concentrations at each study gage were associated with the late spring and summer periods. The Weighted Regressions on Time, Discharge, and Season (WRTDS) method implemented in EGRET was used to estimate water-year annual mean daily concentrations and flux of nutrients and total suspended solids, as well as estimates of concentrations and flux that were “normalized” to remove the effect of year-to-year variation in streamflow. The approximate coefficients of determination for the WRTDS regression models ranged from a high of 0.82 for total phosphorus for the study gage near Centerton to a low of 0.19 for nitrate plus nitrite for the study gage near Nora. Loads and yields of total suspended solids, total phosphorus, nitrate plus nitrite, and total Kjeldahl nitrogen were estimated for analytical periods consisting of the longest periods of concurrent record at the three study gages. Loads of each of the constituents increased sequentially from the most upstream study gage to the most downstream study gage; however, the same was not true for yields. The highest yields of total suspended solids, total phosphorus, and total Kjeldahl nitrogen occurred at the most upstream study gage (at Muncie); however, the highest yield of nitrate plus nitrite occurred at the most downstream study gage (near Centerton). WRTDS bootstrap tests were used to assess the magnitude, direction, and likelihood of changes in annual flow-normalized mean daily concentrations and flux of total suspended solids, total phosphorus, nitrate plus nitrite, and total Kjeldahl nitrogen at the study gages between water years 1997 and 2017. Changes in flow-normalized concentrations and flux of the constituents between water years 1997 and 2017 were mostly downward (decreasing). The exceptions were likely to highly likely upward (increasing) changes in (1) flow-normalized annual mean daily concentration and annual flux for total suspended solids and total phosphorus at the study gage at Muncie, (2) flow-normalized annual mean daily total phosphorus concentration at the study gage near Centerton, (3) flow-normalized annual flux of total phosphorus at the study gage near Centerton, and (4) flow-normalized annual mean daily nitrate plus nitrite concentration at the study gage near Centerton. Although an upward change in flow-normalized nitrate plus nitrite concentrations was likely at the study gage near Centerton, flow-normalized annual flux of nitrate plus nitrite at that study gage was determined to have a highly likely downward change. EGRET and Exploration and Graphics for RivEr Trends Confidence Intervals (EGRETci) analyses can be used to improve our understanding of how concentrations and flux change as functions of time and streamflow, as well as provide information on how the relations between streamflow and constituent concentrations have changed within the calendar year between any 2 years included in the analyses. Examples of those uses, illustrating changes between calendar years 1992 and 2017, were given for total suspended solids concentrations at the study gage near Nora and for nitrate plus nitrite concentrations at the study gage near Centerton.

Indiana↗

Evaluation of salinity and nutrient conditions in the Heart River Basin, North Dakota, 1970–2020

The Heart River Basin is predominantly an agricultural basin in western North Dakota and is approximately 3,350 square miles. The U.S. Geological Survey, in cooperation with the U.S. Department of Agriculture Natural Resources Conservation Service and the Grant County Soil Conservation District, completed a study to assess spatial and temporal patterns of water quality in the Heart River Basin. The purpose of this report is to describe the methods and results of a study to evaluate salinity and nutrients in the Heart River Basin in western North Dakota. Water-quality and streamflow data used in the study were compiled from 1970 to 2020 using the National Water Quality Monitoring Council Water Quality Portal and National Water Information System. Changes in streamflow characteristics were investigated at three sites from 1970 to 2020, and changes in water quality were investigated at four sites from 1974 to 2019. Streamflow analysis indicated decreasing streamflow from 1970 until the late 1990s followed by increasing streamflow through 2020, with the largest increase in the 7-day minimum streamflow or base flow. For the historical water-quality trend period (1974–2019), total dissolved solids, sulfate, sodium, chloride, and sodium adsorption ratio concentrations have increased since the mid-1970s through 2019. Potassium concentrations during the historical period remained mostly constant with some small fluctuations. Calcium and magnesium concentrations increased since the mid-1970s at all sites, except for a decrease at one site between 1974 and 1999. During the recent trend period (1999–2019), increasing concentrations in total dissolved solids, sulfate, sodium, chloride, calcium, magnesium, and sodium adsorption ratios were observed across the Heart River Basin. The magnitude of the increases was smaller at tributary sites compared to main-stem sites. During the recent period, potassium was mostly constant, although small (−0.9 milligram per liter or less) decreases on tributaries and minor (1.3 milligrams per liter) increases on the main-stem sites were detected. Unlike dissolved ion concentrations, significant increases in nutrient concentrations were not detected from 1999 to 2019, but nitrate plus nitrite concentrations most likely decreased upstream from Lake Tschida. Inverse modeling for period 1 (1974–99) in model zone 1 (Heart River reach from site 5 to site 6) had eight reasonable models that indicated the clay mineral-water interactions and dissolution of evaporites control the geochemistry. Results of the inverse modeling for period 2 (1999–2019) in model zone 1 also had eight reasonable models that indicated that the dissolution of evaporites was the major geochemical control. Results of the geochemical modeling for period 1 (1974–99) in model zone 2 (Heart River and Sweetbriar Creek reach from sites 20 and 21 to site 22) produced seven reasonable models, and the geochemical control of the system was the dissolution of sulfate evaporite minerals. Geochemical modeling results for period 2 (1999–2019) in model zone 2 produced 11 reasonable models and was also controlled by the dissolution of sulfate evaporite minerals. Differences between the two model zones indicated that geology controls some of the water-quality changes in the Heart River Basin. Loads were estimated for total dissolved solids, sulfate, sodium, and chloride and total phosphorus. Annual loads estimated for the Heart River from 2013 through 2020 at the Heart River site upstream from Lake Tschida (site 5) and near Mandan (site 22) were generally greatest in 2014 and least in 2016 for total dissolved solids, sulfate, sodium, and chloride. Most of the annual loads of total dissolved solids, sulfate, sodium, and chloride are delivered in March through July in the Heart River at these sites and are likely from snowmelt and spring and summer rains. The mean annual yields of total dissolved solids and sodium from 2013 to 2020 generally were largest in Big Muddy Creek (site 18), whereas yields of sulfate and chloride were largest at Sweetbriar Creek (site 21) compared to the other selected sites in the Heart River Basin. Larger yields of total dissolved solids, sulfate, sodium, and chloride at sites located on Big Muddy Creek and Sweet Briar Creek in the lower Heart River Basin were likely a result of differences in geology and soils upstream from the selected sites. A mass balance of total dissolved solids, sulfate, sodium, and chloride was estimated for the lower Heart River Basin, specifically the reach below Lake Tschida to Mandan (site 7 to site 22). Intervening flow was the largest contributor to the dissolved ion loads in the lower Heart River Basin and is an important part of understanding the transport of dissolved ions in the basin. The intervening load can include groundwater discharge, irrigation return flow, local runoff, and input from smaller ephemeral tributaries. Tributaries in the lower Heart River Basin contributed portions of the total dissolved solids, sulfate, sodium, and chloride loads at the Heart River near Mandan (site 22) that generally were proportional to the streamflow contributions. Annual loads for total phosphorus between 2013 and 2020 at the Heart River site upstream from Lake Tschida (site 5) and near Mandan (site 22) generally were largest in 2019 and smallest in 2016. Most of the total phosphorus loads for main-stem sites 5 and 22 were transported in March, April, and June, likely from snowmelt and early summer rains. The mean annual yields of total phosphorus for 2013–20 were largest on the main-stem site upstream from Lake Tschida (site 5) and Sweetbriar Creek (site 21), whereas the smallest yields were in Big Muddy Creek (site 18). Much of the phosphorus that enters Lake Tschida from the upper basin does not get transported downstream to the lower basin, and much of the phosphorus in the lower basin was attributed to intervening flow.

North Dakota↗

Quality of water from crystalline rock aquifers in New England, New Jersey, and New York, 1995-2007

Crystalline bedrock aquifers in New England and parts of New Jersey and New York (NECR aquifers) are a major source of drinking water. Because the quality of water in these aquifers is highly variable, the U.S. Geological Survey (USGS) statistically analyzed chemical data on samples of untreated groundwater collected from 117 domestic bedrock wells in New England, New York, and New Jersey, and from 4,775 public-supply bedrock wells in New England to characterize the quality of the groundwater. The domestic-well data were from samples collected by the USGS National Water-Quality Assessment (NAWQA) Program from 1995 through 2007. The public-supply-well data were from samples collected for the U.S. Environmental Protection Agency (USEPA) Safe Drinking Water Act (SDWA) Program from 1997 through 2007. Chemical data compiled from the domestic wells include pH, specific conductance, dissolved oxygen, alkalinity, and turbidity; 6 nitrogen and phosphorus compounds, 14 major ions, 23 trace elements, 222 radon gas (radon), 48 pesticide compounds, and 82 volatile organic compounds (VOCs). Additional samples were collected from the domestic wells for the analysis of gross alpha- and gross beta-particle radioactivity, radium isotopes, chlorofluorocarbon isotopes, and the dissolved gases methane, carbon dioxide, nitrogen, and argon. Chemical data compiled from the public-supply wells include pH, specific conductance, nitrate, iron, manganese, sodium, chloride, fluoride, arsenic, uranium, radon, combined radium ( 226 radium plus 228 radium), gross alpha-particle radioactivity, and methyl tert -butyl ether (M t BE). Patterns in fluoride, arsenic, uranium, and radon distributions were discernable when the data were compared to lithology groupings of the bedrock, indicating that the type of bedrock has an effect on the quality of groundwater from NECR aquifers. Fluoride concentrations were significantly higher in groundwater samples from the alkali granite, peraluminous granite, and metaluminous granite lithology groups than from samples in the other lithology groups. Water samples from 1.4 percent of 2,167 studied wells had fluoride concentrations that were equal to or greater than the maximum contaminant level (MCL) of 4 milligrams per liter (mg/L) and 7.5 percent of the wells had fluoride concentrations that were equal to or greater than the secondary MCL of 2 mg/L. For arsenic, groundwater samples from the calcareous metasedimentary rocks in the New Hampshire-Maine geologic province, peraluminous granite, and pelitic rocks lithology groups had higher concentrations than did samples from the other lithology groups. Water samples from 13.3 percent of 2,054 studied wells had arsenic concentrations that were equal to or greater than the MCL of 10 micrograms per liter (μg/L), about double the national rate of occurrence in community-supply systems and in domestic wells of the United States. Uranium concentrations were significantly higher in groundwater samples from the peraluminous granite, alkali granite, and calcareous metasedimentary rocks in the New Hampshire-Maine geologic province lithology groups than from samples in the other lithology groups. Water samples from 14.2 percent of 556 studied wells had uranium concentrations equal to or greater than the MCL of 30 μg/L. Radon activities were equal to or greater than the proposed MCL of 300 picocuries per liter (pCi/L) in 95 percent of 943 studied wells, and 33 percent of the wells had radon activities were equal to or greater than the proposed alternative maximum contaminant level (AMCL) of 4,000 pCi/L. Radon activities exceeded the proposed AMCL in 20 percent or more of groundwater samples in each of the studied lithology groups with a minimum of 9 samples, but radon activities were significantly higher in groundwater samples from the alkali granite, peraluminous granite, and Narragansett basin metasedimentary rocks lithology groups. Water samples from 3.2 percent of 564 studied wells had combined radium activities equal to or greater than the MCL of 5 pCi/L; however, combined radium activities were not significantly different among the studied lithology groups. Land use and population density also were evaluated to explain patterns in water quality. Concentrations of nitrate, sodium, chloride, and MtBE from the studied wells were significantly greater in areas of high population density (≥50 persons per square kilometer) than in areas of low population density (<50 persons per square kilometer). Concentrations of sodium, chloride, and M t BE from the studied wells were significantly greater in areas classified as developed (urban lands) than in areas classified as undeveloped (forested), agricultural, or mixed (no dominant land use). Nitrate concentrations from the public-supply wells were not significantly different among the four land use categories, but nitrate concentrations from the domestic wells were significantly greater in areas classified as developed than in areas classified as undeveloped, agricultural, or mixed. Chloride to bromide mass ratios in the domestic well samples indicate that the groundwater was probably affected by at least three halogen sources: local precipitation and recharge waters, remnant seawater and connate waters evolved from seawater, and recharge waters affected by road salt. The groundwater in the NECR aquifers generally contained low concentrations of nitrate, VOCs, and pesticides. Less than 1 percent of water samples from 4,781 studied wells had concentrations of nitrate greater than the MCL of 10 mg/L. Less than 1 percent of water samples from 1,299 studied wells exceeded the USEPA advisory level of 20 to 40 μg/L for M t BE. None of the other studied VOCs exceeded a human health benchmark. M t BE (36 percent frequency detection) and chloroform (32.9 percent frequency detection) were the most frequently detected (>0.02 μg/L) VOCs in the domestic wells. M t BE was detected more often in water samples with apparent ages of less than 25 years than in water samples with apparent ages greater than 25 years. This finding is consistent with the time period of high M t BE use in areas in the United States where reformulated gasoline was mandated. The largest pesticide concentration was an estimated concentration of 0.06 μg/L for the herbicide metolachlor. Deethylatrazine, a degradate of atrazine, (18 percent frequency detection) and atrazine (8 percent frequency detection) were the only pesticide compounds detected (>0.001 μg/L) in more than 3 percent of the domestic wells. None of the detected pesticide compounds exceeded human health benchmarks. Concentrations of nitrate and gross alpha-particle activities were significantly greater in the water samples from the domestic wells than in samples from the public-supply wells. Concentrations of sodium, chloride, iron, manganese, and uranium were significantly greater in the water samples from the public-supply wells than in the samples from the domestic wells. One possible explanation may be related to differences in field processing (filtered samples from the domestic wells compared to unfiltered samples from the public-supply wells). The high frequency of detections for a wide variety of manmade and naturally occurring contaminants in both domestic and public-supply wells shows the vulnerability of NECR aquifers to contamination. The highly variable water quality and the association with highly variable lithology of crystalline bedrock underscores the importance of testing individual wells to determine if concentrations for the most commonly detected contaminants exceed human health benchmarks.

Connecticut, Maine, Massachusetts, New Hampshire, ↗

Occurrence and hydrogeochemistry of radiochemical constituents in groundwater of Jefferson County and surrounding areas, southwestern Montana, 2007 through 2010

The U.S. Geological Survey, in cooperation with Jefferson County and the Jefferson Valley Conservation District, sampled groundwater in southwestern Montana to evaluate the occurrence and concentration of naturally-occurring radioactive constituents and to identify geologic settings and environmental conditions in which elevated concentrations occur. A total of 168 samples were collected from 128 wells within Broadwater, Deer Lodge, Jefferson, Lewis and Clark, Madison, Powell, and Silver Bow Counties from 2007 through 2010. Most wells were used for domestic purposes and were primary sources of drinking water for individual households. Water-quality samples were collected from wells completed within six generalized geologic units, and analyzed for constituents including uranium, radon, gross alpha-particle activity, and gross beta-particle activity. Thirty-eight wells with elevated concentrations or activities were sampled a second time to examine variability in water quality throughout time. These water-quality samples were analyzed for an expanded list of radioactive constituents including the following: three isotopes of uranium (uranium-234, uranium-235, and uranium-238), three isotopes of radium (radium-224, radium-226, and radium-228), and polonium-210. Existing U.S. Geological Survey and Montana Bureau of Mines and Geology uranium and radon water-quality data collected as part of other investigations through 2011 from wells within the study area were compiled as part of this investigation. Water-quality data from this study were compared to data collected nationwide by the U.S. Geological Survey through 2011. Radionuclide samples for this study typically were analyzed within a few days after collection, and therefore data for this study may closely represent the concentrations and activities of water being consumed locally from domestic wells. Radioactive constituents were detected in water from every well sampled during this study regardless of location or geologic unit. Nearly 41 percent of sampled wells had at least one radioactive constituent concentration that exceeded U.S. Environmental Protection Agency drinking-water standards or screening levels. Uranium concentrations were higher than the U.S. Environmental Protection Agency maximum contaminant level (MCL) of 30 micrograms per liter in samples from 14 percent of the wells. Radon concentrations exceeded a proposed MCL of 4,000 picocuries per liter in 27 percent of the wells. Combined radium (radium-226 and radium-228) exceeded the MCL of 5 picocuries per liter in samples from 10 of 47 wells. About 40 percent (42 of 104 wells) of the wells had gross alpha-particle activities (72-hour count) at or greater than a screening level of 15 pCi/L. Gross beta-particle activity exceeded the U.S. Environmental Protection Agency 50 picocuries per liter screening level in samples from 5 of 104 wells. Maximum radium-224 and polonium-210 activities in study wells were 16.1 and 3.08 picocuries per liter, respectively; these isotopes are constituents of human-health concern, but the U.S. Environmental Protection Agency has not established MCLs for them. Radioactive constituent concentrations or activities exceeded at least one established drinking-water standard, proposed drinking-water standard, or screening level in groundwater samples from five of six generalized geologic units assessed during this study. Radioactive constituent concentrations or activities were variable not only within each geologic unit, but also among wells that were completed in the same geologic unit and in close proximity to one another. Established or proposed drinking-water standards were exceeded most frequently in water from wells completed in the generalized geologic unit that includes rocks of the Boulder batholith and other Tertiary through Cretaceous igneous intrusive rocks (commonly described as granite). Specifically, of the wells completed in the Boulder batholith and related rocks sampled as part of this study, 24 percent exceeded the MCL of 30 micrograms per liter for uranium, 50 percent exceeded the proposed alternative MCL of 4,000 picocuries per liter for radon, and 27 percent exceeded the MCL of 5 micrograms per liter for combined radium-226 and radium-228. Elevated radioactive constituent values were detected in samples representing a large range of field properties and water types. Correlations between radioactive constituents and pH, dissolved oxygen, and most major ions were not statistically significant (p-value > 0.05) or were weakly correlated with Spearman correlation coefficients (rho) ranging from -0.5 to 0.5. Moderate correlations did exist between gross beta-particle activity and potassium (rho = 0.72 to 0.82), likely because one potassium isotope (potassium-40) is a beta-particle emitter. Total dissolved solids and specific conductance also were moderately correlated (rho = 0.62 to 0.71) with gross alpha-particle and gross beta-particle activity, indicating that higher radioactivity values can be associated with higher total dissolved solids. Correlations were evaluated among radioactive constituents. Moderate to strong correlations occurred between gross alpha-particle and beta-particle activities (rho = 0.77 to 0.96) and radium isotopes (rho = 0.78 to 0.92). Correlations between gross alpha-particle activity (72-hour count) and all analyzed radioactive constituents were statistically significant (p-value < 0.05), and therefore, gross alpha-particle activity likely may be used as a screening tool for determining the presence of radionuclides in area waters. In this study, gross alpha-particle activities of 7 picocuries per liter or greater were associated with all radioactive constituents whose concentrations exceeded drinking-water standards or screening levels. Radiochemical results varied temporally in samples from several of the thirty-eight wells sampled at least twice during the study. The time between successive sampling events ranged from about 1 to 10 months for 29 wells to about 3 years for the other 9 wells. Radiochemical constituents that varied by greater than 30 percent between sampling events included uranium (29 percent of the resampled wells), and radon (11 percent of the resampled wells), gross alpha-particle activity (38 percent of the resampled wells), and gross beta-particle activity (15 percent of the resampled wells). Variability in uranium concentrations from two wells was sufficiently large that concentrations were less than the MCL in the first set of samples and greater than the MCL in the second. Sample holding times affect analytical results in this study. Gross alpha-particle and gross beta-particle activities were measured twice, 72 hours and 30 days after sample collection. Gross alpha-particle activity decreased an average of 37 percent between measurements, indicating the presence of short-lived alpha-emitting radionuclides in these samples. Gross beta-particle activity increased an average of 31 percent between measurements, indicating ingrowth of longer-lived beta-emitting radionuclides.

Montana↗

Status and understanding of groundwater quality in the Cascade Range and Modoc Plateau study unit, 2010: California GAMA Priority Basin Project

Groundwater quality in the Cascade Range and Modoc Plateau study unit was investigated as part of the California State Water Resources Control Board&rsquo;s Groundwater Ambient Monitoring and Assessment (GAMA) Program Priority Basin Project. The study was designed to provide a statistically unbiased assessment of untreated groundwater quality in the primary aquifer system. The depth of the primary aquifer system for the Cascade Range and Modoc Plateau study unit was delineated by the depths of the screened or open intervals of wells in the State of California&rsquo;s database of public-supply wells. Two types of assessments were made: a status assessment that described the current quality of the groundwater resource, and an understanding assessment that made evaluations of relations between groundwater quality and potential explanatory factors representing characteristics of the primary aquifer system. The assessments characterize the quality of untreated groundwater, not the quality of treated drinking water delivered to consumers by water distributors. The status assessment was based on water-quality data collected in 2010 by the U.S. Geological Survey from 90 wells and springs (USGS-grid wells) and on water-quality data compiled from the State of California&rsquo;s regulatory compliance database for samples collected from 240 public-supply wells between September 2007 and September 2010. To provide context, the water-quality data discussed in this report were compared to California and Federal drinking-water regulatory and non-regulatory benchmarks for treated drinking water. Groundwater quality is defined in terms of relative concentrations (RCs), which are calculated by dividing the concentration of a constituent in groundwater by the concentration of the benchmark for that constituent. The RCs for inorganic constituents (major ions, trace elements, nutrients, and radioactive constituents) were classified as &ldquo;high&rdquo; (the RC is greater than 1.0, indicating that the concentration is above the benchmark), &ldquo;moderate&rdquo; (the RC is from 1.0 to greater than 0.5), or &ldquo;low&rdquo; (the RC is less than or equal to 0.5). For organic constituents (volatile organic compounds and pesticides) and special-interest constituents (perchlorate), the boundary between moderate and low RCs was set at 0.1. All benchmarks used for organic constituents were health-based. For inorganic constituents, health-based and aesthetic-based benchmarks were used. Constituents without benchmarks were not considered in the status assessment . The primary metric used for quantifying regional-scale groundwater quality was the aquifer-scale proportion&mdash;the areal percentages of the primary aquifer system with high, moderate, and low RCs for a given constituent or class of constituents. The study unit was divided into six study areas on the basis of geologic differences (Eastside Sacramento Valley, Honey Lake Valley groundwater basin, Cascade Range and Modoc Plateau Low Use Basins, Quaternary Volcanic Areas, Shasta Valley and Mount Shasta Volcanic Area, and Tertiary Volcanic Areas), and each study area was divided into equal-area grid cells. Aquifer-scale proportions were calculated for individual constituents and constituent classes for each of the six study areas and for the study unit as a whole by using grid-based (one well per cell) and spatially weighted (many wells per cell) statistical methods. The status assessment showed that inorganic constituents were present at high and moderate RCs in greater proportions of the Cascade Range and Modoc Plateau study unit than were organic constituents. One or more inorganic constituents with health-based benchmarks were present at high RCs in 9.4 percent, and at moderate RCs in 14.7 percent of the primary aquifer system. Arsenic was present at high RCs in approximately 3 percent of the primary aquifer system; boron, molybdenum, uranium, and vanadium each were present at high RCs in approximately 2 percent of the primary aquifer system. One or more inorganic constituents with aesthetic-based benchmarks were present at high RCs in 15.1 percent of the primary aquifer system and at moderate RCs in 4.9 percent. Manganese, iron, and total dissolved solids were present at high RCs in approximately 12 percent, 5 percent, and 2 percent, respectively, of the primary aquifer system. Organic constituents were not detected at high or moderate RCs in the primary aquifer system, and one or more organic constituents were detected at low RCs in approximately 40 percent of the primary aquifer system. Two classes of organic constituents were detected in more than 10 percent of the primary aquifer system: trihalomethanes (chloroform only) and herbicides. The special interest constituent perchlorate was not detected at high RCs, but was detected at moderate RCs in approximately 2 percent of the primary aquifer system. The understanding assessment relied on statistical tests to evaluate relations between concentrations of constituents and values of potential explanatory factors representing geology, land use, well construction, hydrologic conditions, groundwater age, and geochemical conditions. The majority of the high and moderate RCs of arsenic, boron, molybdenum, uranium, and total dissolved solids were in samples from the Honey Lake Valley groundwater basin study area. Groundwater mixing with hydrothermal fluids present in the study area, evaporative concentration of groundwater in the Honey Lake playa, presence of uranium-bearing sediment derived from the adjacent Sierra Nevada, and release of arsenic and other trace elements from sediments under high pH and low dissolved oxygen conditions all appeared to contribute to these elevated concentrations. Thermal springs are in many parts of the Cascade Range and Modoc Plateau study unit and could account for locally elevated concentrations of arsenic, boron, molybdenum, and total dissolved solids in samples from the other study areas. Vanadium concentrations were greater in oxic samples than in anoxic samples, but were not correlated with pH, contrary to expectations from previous studies. Organic constituents were not detected at high or moderate RCs, and the occurrence of low organic constituents at low RCs ranged from 27 percent to 73 percent of the primary aquifers system in the six study areas. The Shasta Valley and Mount Shasta Volcanic study area had significantly greater occurrence of low RCs of herbicides compared to all of the other study areas, which could reflect the greater prevalence of modern groundwater in the Shasta Valley and Mount Shasta Volcanic study area and the presence of potential sources of herbicides, including applications to timberlands and roadside rights-of-way. The Eastside Sacramento Valley study area had the greatest occurrence of low concentrations of chloroform, and chloroform occurrence was most strongly associated with the combination of septic-tank density greater than two tanks per square kilometer and urban land use greater than 10 percent within a radius of 500 meters of the well. These conditions were most prevalent in the Eastside Sacramento Valley study area. The detection frequency of low concentrations of perchlorate was consistent with the probability of occurrence expected under natural conditions, except in the Eastside Sacramento Valley study area, where detection frequencies were much higher than expected and could not be explained by known anthropogenic sources of perchlorate.

California↗

Evaluation of the expected moments algorithm and a multiple low-outlier test for flood frequency analysis at streamgaging stations in Arizona

Flooding is among the costliest natural disasters in terms of loss of life and property in Arizona, which is why the accurate estimation of flood frequency and magnitude is crucial for proper structural design and accurate floodplain mapping. Current guidelines for flood frequency analysis in the United States are described in Bulletin 17B (B17B), yet since B17B’s publication in 1982 (Interagency Advisory Committee on Water Data, 1982), several improvements have been proposed as updates for future guidelines. Two proposed updates are the Expected Moments Algorithm (EMA) to accommodate historical and censored data, and a generalized multiple Grubbs-Beck (MGB) low-outlier test. The current guidelines use a standard Grubbs-Beck (GB) method to identify low outliers, changing the determination of the moment estimators because B17B uses a conditional probability adjustment to handle low outliers while EMA censors the low outliers. B17B and EMA estimates are identical if no historical information or censored or low outliers are present in the peak-flow data. EMA with MGB (EMA-MGB) test was compared to the standard B17B (B17B-GB) method for flood frequency analysis at 328 streamgaging stations in Arizona. The methods were compared using the relative percent difference (RPD) between annual exceedance probabilities (AEPs), goodness-of-fit assessments, random resampling procedures, and Monte Carlo simulations. The AEPs were calculated and compared using both station skew and weighted skew. Streamgaging stations were classified by U.S. Geological Survey (USGS) National Water Information System (NWIS) qualification codes, used to denote historical and censored peak-flow data, to better understand the effect that nonstandard flood information has on the flood frequency analysis for each method. Streamgaging stations were also grouped according to geographic flood regions and analyzed separately to better understand regional differences caused by physiography and climate. The B17B-GB and EMA-MGB RPD-boxplot results showed that the median RPDs across all streamgaging stations for the 10-, 1-, and 0.2-percent AEPs, computed using station skew, were approximately zero. As the AEP flow estimates decreased (that is, from 10 to 0.2 percent AEP) the variability in the RPDs increased, indicating that the AEP flow estimate was greater for EMA-MGB when compared to B17B-GB. There was only one RPD greater than 100 percent for the 10- and 1-percent AEP estimates, whereas 19 RPDs exceeded 100 percent for the 0.2-percent AEP. At streamgaging stations with low-outlier data, historical peak-flow data, or both, RPDs ranged from −84 to 262 percent for the 0.2-percent AEP flow estimate. When streamgaging stations were separated by the presence of historical peak-flow data (that is, no low outliers or censored peaks) or by low outlier peak-flow data (no historical data), the results showed that RPD variability was greatest for the 0.2-AEP flow estimates, indicating that the treatment of historical and (or) low-outlier data was different between methods and that method differences were most influential when estimating the less probable AEP flows (1, 0.5, and 0.2 percent). When regional skew information was weighted with the station skew, B17B-GB estimates were generally higher than the EMA-MGB estimates for any given AEP. This was related to the different regional skews and mean square error used in the weighting procedure for each flood frequency analysis. The B17B-GB weighted skew analysis used a more positive regional skew determined in USGS Water Supply Paper 2433 (Thomas and others, 1997), while the EMA-MGB analysis used a more negative regional skew with a lower mean square error determined from a Bayesian generalized least squares analysis. Regional groupings of streamgaging stations reflected differences in physiographic and climatic characteristics. Potentially influential low flows (PILFs) were more prevalent in arid regions of the State, and generally AEP flows were larger with EMA-MGB than with B17B-GB for gaging stations with PILFs. In most cases EMA-MGB curves would fit the largest floods more accurately than B17B-GB. In areas of the State with more baseflow, such as along the Mogollon Rim and the White Mountains, streamgaging stations generally had fewer PILFs and more positive skews, causing estimated AEP flows to be larger with B17B-GB than with EMA-MGB. The effect of including regional skew was similar for all regions, and the observed pattern was increasingly greater B17B-GB flows (more negative RPDs) with each decreasing AEP quantile. A variation on a goodness-of-fit test statistic was used to describe each method’s ability to fit the largest floods. The mean absolute percent difference between the measured peak flows and the log-Pearson Type 3 (LP3)-estimated flows, for each method, was averaged over the 90th, 75th, and 50th percentiles of peak-flow data at each site. In most percentile subsets, EMA-MGB on average had smaller differences (1 to 3 percent) between the observed and fitted value, suggesting that the EMA-MGB-LP3 distribution is fitting the observed peak-flow data more precisely than B17B-GB. The smallest EMA-MGB percent differences occurred for the greatest 10 percent (90th percentile) of the peak-flow data. When stations were analyzed by USGS NWIS peak flow qualification code groups, the stations with historical peak flows and no low outliers had average percent differences as high as 11 percent greater for B17B-GB, indicating that EMA-MGB utilized the historical information to fit the largest observed floods more accurately. A resampling procedure was used in which 1,000 random subsamples were drawn, each comprising one-half of the observed data. An LP3 distribution was fit to each subsample using B17B-GB and EMA-MGB methods, and the predicted 1-percent AEP flows were compared to those generated from distributions fit to the entire dataset. With station skew, the two methods were similar in the median percent difference, but with weighted skew EMA-MGB estimates were generally better. At two gages where B17B-GB appeared to perform better, a large number of peak flows were deemed to be PILFs by the MGB test, although they did not appear to depart significantly from the trend of the data (step or dogleg appearance). At two gages where EMA-MGB performed better, the MGB identified several PILFs that were affecting the fitted distribution of the B17B-GB method. Monte Carlo simulations were run for the LP3 distribution using different skews and with different assumptions about the expected number of historical peaks. The primary benefit of running Monte Carlo simulations is that the underlying distribution statistics are known, meaning that the true 1-percent AEP is known. The results showed that EMA-MGB performed as well or better in situations where the LP3 distribution had a zero or positive skew and historical information. When the skew for the LP3 distribution was negative, EMA-MGB performed significantly better than B17B-GB and EMA-MGB estimates were less biased by more closely estimating the true 1-percent AEP for 1, 2, and 10 historical flood scenarios.

Arizona↗

Borehole geophysical investigation of a formerly used defense site, Machiasport, Maine, 2003-2006

The U.S. Geological Survey, in cooperation with the U.S. Army Corps of Engineers, collected borehole geophysical logs in 18 boreholes and interpreted the data along with logs from 19 additional boreholes as part of an ongoing, collaborative investigation at three environmental restoration sites in Machiasport, Maine. These sites, located on hilltops overlooking the seacoast, formerly were used for military defense. At each of the sites, chlorinated solvents, used as part of defense-site operations, have contaminated the fractured-rock aquifer. Borehole geophysical techniques and hydraulic methods were used to characterize bedrock lithology, fractures, and hydraulic properties. In addition, each geophysical method was evaluated for effectiveness for site characterization and for potential application for further aquifer characterization and (or) evaluation of remediation efforts. Results of borehole geophysical logging indicate the subsurface is highly fractured, metavolcanic, intrusive, metasedimentary bedrock. Selected geophysical logs were cross-plotted to assess correlations between rock properties. These plots included combinations of gamma, acoustic reflectivity, electromagnetic induction conductivity, normal resistivity, and single-point resistance. The combined use of acoustic televiewer (ATV) imaging and natural gamma logs proved to be effective for delineating rock types. Each of the rock units in the study area could be mapped in the boreholes, on the basis of the gamma and ATV reflectivity signatures. The gamma and mean ATV reflectivity data were used along with the other geophysical logs for an integrated interpretation, yielding a determination of quartz monzonite, rhyolite, metasedimentary units, or diabase/gabbro rock types. The interpretation of rock types on the basis of the geophysical logs compared well to drilling logs and geologic mapping. These results may be helpful for refining the geologic framework at depth. A stereoplot of all fractures intersecting the boreholes indicates numerous fractures, a high proportion of steeply dipping fractures, and considerable variation in fracture orientation. Low-dip-angle fractures associated with unloading and exfoliation are also present, especially at a depth of less than 100 feet below the top of casing. These sub-horizontal fractures help to connect the steeply dipping fractures, making this a highly connected fracture network. The high variability in the fracture orientations also increases the connectivity of the fracture network. A preliminary comparison of all fracture data from all the boreholes suggests fracturing decreases with depth. Because all the boreholes were not drilled to the same depth, however, there is a clear sampling bias. Hence, the deepest boreholes are analyzed separately for fracture density. For the deepest boreholes in the study, the intensity of fracturing does not decline significantly with depth. It is possible the fractures observed in these boreholes become progressively tighter or closed with depth, but this is difficult to verify with the borehole methods used in this investigation. The fact that there are more sealed fractures at depth (observed in optical televiewer logs in some of the boreholes) may indicate less opening of the sealed fractures, less water moving through the rock, and less weathering of the fracture infilling minerals. Although the fracture orientation remained fairly constant with depth, differences in the fracture patterns for the three restoration sites indicate the orientation of fractures varies across the study area. The fractures in boreholes on Miller Mountain predominantly strike northwest-southeast, and to a lesser degree they strike northeast. The fractures on or near the summit of Howard Mountain strike predominantly east-west and dip north and south, and the fractures near the Transmitter Site strike northeast-southwest and dip northwest and southeast. The fracture populations for the boreholes on or near the summit of Howard Mountain show more variation than at the other two sites. This variation may be related to the proximity of the fault, which is northeast of the summit of Howard Mountain. In a side-by-side comparison of stereoplots from selected boreholes, there was no clear correspondence between fracture orientation and proximity to the fault. There is, however, a difference in the total populations of fractures for the boreholes on or near the summit of Howard Mountain and the boreholes near the Transmitter Site. Further to the southwest and further away from the fault, the fractures at the Transmitter Site predominantly strike northeast-southwest and northwest-southeast.Heat-pulse flowmeter (HPFM) logging was used to identify transmissive fractures and to estimate the hydraulic properties along the boreholes. Ambient downflow was measured in 13 boreholes and ambient upflow was measured in 9 boreholes. In nine other bedrock boreholes, the HPFM did not detect measurable vertical flow. The observed direction of vertical flow in the boreholes generally was consistent with the conceptual flow model of downward movement in recharge locations and upward flow in discharge locations or at breaks in the slope of land surface. Under low-rate pumping or injection rates [0.25 to 1 gallon per minute (gal/min)], one to three inflow zones were identified in each borehole. Two limitations of HPFM methods are (1) the HPFM can only identify zones within 1.5 to 2 orders of magnitude of the most transmissive zone in each borehole, and (2) the HPFM cannot detect flow rates less than 0.010 + or - 0.005 gal/min, which corresponds to a transmissivity of about 1 foot squared per day (ft2/d). Consequently, the HPFM is considered an effective tool for identifying the most transmissive fractures in a borehole, down to its detection level. Transmissivities below that cut-off must be measured with another method, such as packer testing or fluid-replacement logging. Where sufficient water-level and flowmeter data were available, HPFM results were numerically modeled. For each borehole model, the fracture location and measured flow rates were specified, and the head and transmissivity of each fracture zone were adjusted until a model fit was achieved with the interpreted ambient and stressed flow profiles. The transmissivities calculated by this method are similar to the results of an open-hole slug test; with the added information from the flowmeter, however, the head and transmissivity of discrete zones also can be determined. The discrete-interval transmissivities ranged from 0.16 to 330 ft2/d. The flowmeter-derived open-hole transmissivity, which is the combined total of each of the transmissive zones, ranged from 1 to 511 ft2/d. The whole-well open-hole transmissivity values determined with HPFM methods were compared to the results of open-hole hydraulic tests. Despite the fact that the flowmeter-derived transmissivities consistently were lower than the estimates derived from open-hole hydraulic tests alone, the correlation was very strong (with a coefficient of determination, R2, of 0.9866), indicating the HPFM method provides a reasonable estimate of transmissivities for the most transmissive fractures in the borehole. Geologic framework, fracture characterization, and estimates of hydraulic properties were interpreted together to characterize the fracture network. The data and interpretation presented in this report should provide information useful for site investigators as the conceptual site groundwater flow model is refined. Collectively, the results and the conceptual site model are important for evaluating remediation options and planning or implementing the design of a well field and borehole completions that will be adequate for monitoring flow, remediation efforts, groundwater levels, and (or) water quality. Similar kinds of borehole geophysical logging (specifically the borehole imaging, gamma, fluid logs, and HPFM) should be conducted in any newly installed boreholes and integrated with interpretations of any nearby boreholes. If boreholes are installed close to existing or other new boreholes, cross-hole flowmeter surveys may be appropriate and may help characterize the aquifer properties and connections between the boreholes.

Maine↗

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↗

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 (&ge;) 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&ndash; , MoO 4 2&ndash; , and H 2 VO 4&ndash; ), 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 &ndash; ). 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↗

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↗

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 &ge; RC > 0.1), or "low" (RC &le; 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&mdash;grid-based, which used one value per grid cell, and spatially weighted, which used multiple values per grid cell&mdash;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↗

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↗

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↗

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↗

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↗

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↗

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&mdash;grid-based and spatially weighted&mdash;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&mdash;antimony, radium, and fluoride&mdash;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&mdash;total dissolved solids (TDS), sulfate, and chloride&mdash;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&mdash;simazine and atrazine&mdash;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↗

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&ndash;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&ndash;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&ndash;10, in part because of variations in streamflow. In general, annual runoff was less than average during water years 2001&ndash;06 and near or above average during water years 2007&ndash;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&ndash;10 for 17 sites, which generally were on the main-stem streams and primary tributaries. Trends were evaluated for water years 2005&ndash;10 for 26 sites to increase the spatial coverage of sites. Trends were evaluated for water years 1991&ndash;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&ndash;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&ndash;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&ndash;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&ndash;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&ndash;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&ndash;2010. An upward trend in flow-adjusted alkalinity concentrations for water years 2001&ndash;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↗