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Review of Trace-Element Field-Blank Data Collected for the California Groundwater Ambient Monitoring and Assessment (GAMA) Program, May 2004-January 2008

Trace-element quality-control samples (for example, source-solution blanks, field blanks, and field replicates) were collected as part of a statewide investigation of groundwater quality in California, known as the Priority Basins Project of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA Priority Basins Project is being conducted by the U.S. Geological Survey (USGS) in cooperation with the California State Water Resources Control Board (SWRCB) to assess and monitor the quality of groundwater resources used for drinking-water supply and to improve public knowledge of groundwater quality in California. Trace-element field blanks were collected to evaluate potential bias in the corresponding environmental data. Bias in the environmental data could result from contamination in the field during sample collection, from the groundwater coming into contact with contaminants on equipment surfaces or from other sources, or from processing, shipping, or analyzing the samples. Bias affects the interpretation of environmental data, particularly if any constituents are present solely as a result of extrinsic contamination that would have otherwise been absent from the groundwater that was sampled. Field blanks were collected, analyzed, and reviewed to identify and quantify extrinsic contamination bias. Data derived from source-solution blanks and laboratory quality-control samples also were considered in evaluating potential contamination bias. Eighty-six field-blank samples collected from May 2004 to January 2008 were analyzed for the concentrations of 25 trace elements. Results from these field blanks were used to interpret the data for the 816 samples of untreated groundwater collected over the same period. Constituents analyzed were aluminum (Al), antimony (Sb), arsenic (As), barium (Ba), beryllium (Be), boron (B), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), lead (Pb), lithium (Li), manganese (Mn), mercury (Hg), molybdenum (Mo), nickel (Ni), selenium (Se), silver (Ag), strontium (Sr), thallium (Tl), tungsten (W), uranium (U), vanadium (V), and zinc (Zn). The detection frequency and the 90th percentile concentration at greater than 90 percent confidence were determined from the field-blank data for each trace element, and these results were compared to each constituent's long-term method detection level (LT-MDL) to determine whether a study reporting level (SRL) was necessary to ensure that no more than 10 percent of the detections in groundwater samples could be attributed solely to contamination bias. Only two of the trace elements analyzed, Li and Se, had zero detections in the 86 field blanks. Ten other trace elements (Sb, As, Be, B, Cd, Co, Mo, Ag, Tl, and U) were detected in fewer than 5 percent of the field blanks. The field-blank results for these constituents did not necessitate establishing SRLs. Of the 13 constituents that were detected in more than 5 percent of the field blanks, six (Al, Ba, Cr, Mn, Hg, and V) had field-blank results that indicated a need for SRLs that were at or below the highest laboratory reporting levels (LRL) used during the sampling period; these SRLs were needed for concentrations between the LT-MDLs and LRLs. The other seven constituents with detection frequencies above 5 percent (Cu, Fe, Pb, Ni, Sr, W, and Zn) had field-blank results that necessitated SRLs greater than the highest LRLs used during the study period. SRLs for these seven constituents, each set at the 90th percentile of their concentrations in the field blanks, were at least an order of magnitude below the regulatory thresholds established for drinking water for health or aesthetic purposes; therefore, reporting values below the SRLs as less than or equal to (=) the measured value would not prevent the identification of values greater than the drinking-water thresholds. The SRLs and drinking-water thresholds, respectively, for these 7 trace elements are Cu (1.7 ?g/L and 1,300

Scientific Investigations Report↗

Groundwater-quality data in the Monterey–Salinas shallow aquifer study unit, 2013: Results from the California GAMA Program

Groundwater quality in the 3,016-square-mile Monterey–Salinas Shallow Aquifer study unit was investigated by the U.S. Geological Survey (USGS) from October 2012 to May 2013 as part of the California State Water Resources Control Board Groundwater Ambient Monitoring and Assessment (GAMA) Program’s Priority Basin Project. The GAMA Monterey–Salinas Shallow Aquifer study was designed to provide a spatially unbiased assessment of untreated-groundwater quality in the shallow-aquifer systems in parts of Monterey and San Luis Obispo Counties and to facilitate statistically consistent comparisons of untreated-groundwater quality throughout California. The shallow-aquifer system in the Monterey–Salinas Shallow Aquifer study unit was defined as those parts of the aquifer system shallower than the perforated depth intervals of public-supply wells, which generally corresponds to the part of the aquifer system used by domestic wells. Groundwater quality in the shallow aquifers can differ from the quality in the deeper water-bearing zones; shallow groundwater can be more vulnerable to surficial contamination. Samples were collected from 170 sites that were selected by using a spatially distributed, randomized grid-based method. The study unit was divided into 4 study areas, each study area was divided into grid cells, and 1 well was sampled in each of the 100 grid cells (grid wells). The grid wells were domestic wells or wells with screen depths similar to those in nearby domestic wells. A greater spatial density of data was achieved in 2 of the study areas by dividing grid cells in those study areas into subcells, and in 70 subcells, samples were collected from exterior faucets at sites where there were domestic wells or wells with screen depths similar to those in nearby domestic wells (shallow-well tap sites). Field water-quality indicators (dissolved oxygen, water temperature, pH, and specific conductance) were measured, and samples for analysis of inorganic constituents (trace elements, nutrients, major and minor ions, silica, total dissolved solids, and alkalinity) were collected at all 170 sites. In addition to these constituents, the samples from grid wells were analyzed for organic constituents (volatile organic compounds, pesticides and pesticide degradates), constituents of special interest (perchlorate and N -nitrosodimethylamine, or NDMA), radioactive constituents (radon-222 and gross-alpha and gross-beta radioactivity), and geochemical and age-dating tracers (stable isotopes of carbon in dissolved inorganic carbon, carbon-14 abundances, stable isotopes of hydrogen and oxygen in water, and tritium activities). Three types of quality-control samples (blanks, replicates, and matrix spikes) were collected at up to 11 percent of the wells in the Monterey–Salinas Shallow Aquifer study unit, and the results for these samples were used to evaluate the quality of the data from the groundwater samples. With the exception of trace elements, blanks rarely contained detectable concentrations of any constituent, indicating that contamination from sample-collection procedures was not a significant source of bias in the data for the groundwater samples. Low concentrations of some trace elements were detected in blanks; therefore, the data were re-censored at higher reporting levels. Replicate samples generally were within the limits of acceptable analytical reproducibility. The median values of matrix-spike recoveries were within the acceptable range (70 to 130 percent) for the volatile organic compounds (VOCs) and N -nitrosodimethylamine (NDMA), but were only approximately 64 percent for pesticides and pesticide degradates. The sample-collection protocols used in this study were designed to obtain representative samples of groundwater. The quality of groundwater can differ from the quality of drinking water because water chemistry can change as a result of contact with plumbing systems or the atmosphere; because of treatment, disinfection, or blending with water from other sources; or some combination of these. Water quality in domestic wells is not regulated in California, however, to provide context for the water-quality data presented in this report, results were compared to benchmarks established for drinking-water quality. The primary comparison benchmarks were maximum contaminant levels established by the U.S. Environmental Protection Agency and the State of California (MCL-US and MCL-CA, respectively). Non-regulatory benchmarks were used for constituents without maximum contaminant levels (MCLs), including Health Based Screening Levels (HBSLs) developed by the USGS and State of California secondary maximum contaminant levels (SMCL-CA) and notification levels. Most constituents detected in samples from the Monterey–Salinas Shallow Aquifer study unit had concentrations less than their respective benchmarks. Of the 148 organic constituents analyzed in the 100 grid-well samples, 38 were detected, and all concentrations were less than the benchmarks. Volatile organic compounds were detected in 26 of the grid wells, and pesticides and pesticide degradates were detected in 28 grid wells. The special-interest constituent NDMA was detected above the HBSL in three samples, one of which also had a perchlorate concentration greater than the MCL-CA. Of the inorganic constituents, 6 were detected at concentrations above their respective MCL benchmarks in grid-well samples: arsenic (5 grid wells above the MCL of 10 micrograms per liter, μg/L), selenium (3 grid wells, MCL of 50 μg/L), uranium (4 grid wells, MCL of 30 μg/L), nitrate (16 grid wells, MCL of 10 milligrams per liter, mg/L), adjusted gross alpha particle activity (10 grid wells, MCL of 15 picocuries per liter, pCi/L), and gross beta particle activity (1 grid well, MCL of 50 pCi/L). An additional 4 inorganic constituents were detected at concentrations above their respective HBSL benchmarks in grid-well samples: boron (1 grid well above the HBSL of 6,000 μg/L), manganese (8 grid wells, HBSL of 300 μg/L), molybdenum (6 grid wells, HBSL of 40 μg/L), and strontium (6 grid wells, HBSL of 4,000 μg/L). Of the inorganic constituents, 4 were detected at concentrations above their non-health based SMCL benchmarks in grid-well samples: iron (9 grid wells above the SMCL of 300 μg/L), chloride (7 grid wells, SMCL of 500 mg/L), sulfate (14 grid wells, SMCL of 500 mg/L), and total dissolved solids (27 grid wells, SMCL of 1,000 mg/L). Of the inorganic constituents analyzed in the 70 shallow-well tap sites, 10 were detected at concentrations above the benchmarks. Of the inorganic constituents, 3 were detected at concentrations above their respective MCL benchmarks in shallow-well tap sites: arsenic (2 shallow-well tap sites above the MCL of 10 μg/L), uranium (2 shallow-well tap sites, MCL of 30 μg/L), and nitrate (24 shallow-well tap sites, MCL of 10 mg/L). An additional 3 inorganic constituents were detected above their respective HBSL benchmarks in shallow-well tap sites: manganese (4 shallow-well tap sites above the HBSL of 300 μg/L), molybdenum (4 shallow-well tap sites, HBSL of 40 μg/L), and zinc (2 shallow-well tap sites, HBSL of 2,000 μg/L). Of the inorganic constituents, 4 were detected at concentrations above their non-health based SMCL benchmarks in shallow-well tap sites: iron (6 shallow-well tap sites above the SMCL of 300 μg/L), chloride (1 shallow-well tap site, SMCL of 500 mg/L), sulfate (9 shallow-well tap sites, SMCL of 500 mg/L), and total dissolved solids (15 shallow-well tap sites, SMCL of 1,000 mg/L).

California↗

Contaminants of emerging concern in the Great Lakes: Science to inform management practices for protecting the health and integrity of wildlife populations from adverse effects: GLRI action plan I, focus area 1, goal 5

Executive Summary: Under Action Plan I (2010-2014) of the Great Lakes Restoration Initiative (GLRI), Federal and Academic partners began an investigation of the presence and distribution of contaminants of emerging concern (CECs) in the Great Lakes and potential impacts on fish and wildlife. The term CECs is applied to a broad range of chemicals that are currently in use but for which we currently lack good understanding of whether fish, wildlife, or humans are being exposed and/or whether negative health or environmental effects are expected if exposure occurs. Pharmaceuticals, personal care products, flame retardants, many current use pesticides, and poly- and perfluorinated chemicals are some well-known groups of CECs, but there is no definitive or comprehensive list that can be used to support the management of CECs to reduce impacts on the Great Lakes ecosystem. Four overarching goals were identified for this collaborative investigation: 1. Evaluate the sources, occurrence, and distribution of CECs across the Great Lakes Basin. 2. Examine associations between the distribution of CECs and land-use patterns. 3. Review both scientific literature and field-generated data to determine the potential for CECs to cause adverse effects on Great Lakes fish and wildlife populations. 4. Develop efficient strategies to survey and/or monitor for threats that CECs may pose in order to take effective management actions before those threats evolve into large scale impacts on Great Lakes ecosystems or the services they provide. Achievement of these goals ensures progress towards Focus Area 1: Toxic Substances and Areas of Concern from GLRI Action Plan I, Goal 5: “ The health and integrity of wildlife populations and habitat are protected from adverse chemical and biological effects associated with the presence of toxic substances in the Great Lakes Basin ”. This large-scale research effort was comprised of individual and collaborative projects from multiple federal agencies and academic institutions, involving over 85 investigators, and overseen by the U.S. Environmental Protection Agency (EPA) Region 5, Great Lakes National Program Office. Partners include the United States Geological Survey, the National Oceanic and Atmospheric Administration, U.S. Fish and Wildlife Service, Saint Cloud State University, the U.S. EPA Office of Research and Development, and the U.S. Army Corps of Engineers. Key findings: 1. Contaminants of emerging concern were found throughout the monitored Great Lakes tributaries, but types and concentrations vary in association with regional land use. CECs were detected in nearly all samples collected. The type and concentration of the specific contaminants detected varied considerably among field sites and in association with land use type, such as urban, agricultural, wetland, 2 or forest. Contaminants were detected in the water column, sediment, and tissues of all species surveyed in the current work (mussels, aquatic insects, fish, and insect-eating birds). 2. There were over 20 contaminants for which CEC concentrations approached or exceeded those reported to cause toxicity in laboratory experiments. This was based on detection in water, sediments and or biota at one or more field sites. These contaminants represent compounds that warrant further investigation and monitoring with respect to potential impacts in certain areas of the Great Lakes basin. Based on the present investigation, compounds of greatest concern include: polycyclic aromatic hydrocarbons, associated with oil-based products and combustion of organic matter; atrazine, an herbicide; dichlorvos, an insecticide; and ibuprofen and venlafaxine, both pharmaceuticals. 3. Results suggest that mixtures of CECs presently found in most Great Lakes tributary locations surveyed may elicit subtle biological effects, but likely are not, alone, causing obvious detriment to current communities of fish and wildlife. CECs detected in the Great Lakes were associated with subtle biological effects like changes in gene expression, altered circulating glucose, etc. in both wild-caught and laboratory-reared organisms. These effects were generally not indicative of reproductive failure or mortality. However, the effects may have more serious implications when combined with other sources of stress like habitat degradation, changing climate conditions, and competition with invasive species. Due to limited historical data, it is unknown whether severe CEC-related impacts have already affected aquatic communities in waterbodies that have received long-term inputs of these contaminants. Likewise, under Action Plan I, biological effects were not necessarily evaluated at the sites where CEC concentrations exceeding laboratory toxicity thresholds were detected. As a result, strategic, ongoing surveillance and monitoring of CECs is warranted. This collaborative investigation resulted in new tools, approaches, and data that can be used to inform and support the management of CECs to reduce their impacts on Great Lakes natural resources. The following products of this research effort are available through https://communities.geoplatform.gov/glri/ or by contacting the investigators (see technical chapters found in Appendices A-F): 1. Database of CEC occurrence and concentrations in US tributary streams. The database includes CEC detections in water, sediment, and fish and wildlife tissues, and represents the most comprehensive survey of CECs in the Great Lakes Region. 2. Synopses of results and key findings. Integrated summaries of results, conclusions, and management implications of the CEC research are available through reports, topical fact sheets, and presentations. 3. Technical publications: This collaborative research effort has resulted in over 50 peer-reviewed publications, agency reports, and data releases that can be of use to resource managers, the scientific community, and members of the public. 4. Innovative tools. Innovative monitoring devices, sampling equipment, conceptual frameworks, and software applications were developed over the course of this 3 research. These tools are transferable to stakeholders via internet accessibility or via specifications, instructions, and demonstration detailed in technical publications. Hypotheses to guide CECs research under Action Plan II. Findings from 2010-2014 were used to guide further research in 2015-2018 for basin-wide surveillance of CECs and for sites warranting further study of potential biological impacts of CECs. Additional surveillance included both evaluation of additional classes of contaminants and expanded lists for chemical classes shown to be of greatest concern. Mixtures of some of the most frequently detected contaminants were also tested in laboratory studies to understand whether long term exposures to multiple contaminants may result in effects not evident from uncontrolled, short-term field experiments.

Great Lakes↗

Updated study reporting levels (SRLs) for trace-element data collected for the California Groundwater Ambient Monitoring and Assessment (GAMA) Priority Basin Project, October 2009-March 2013

Groundwater samples have been collected in California as part of statewide investigations of groundwater quality conducted by the U.S. Geological Survey for the Groundwater Ambient Monitoring and Assessment (GAMA) Priority Basin Project (PBP). The GAMA-PBP is being conducted in cooperation with the California State Water Resources Control Board to assess and monitor the quality of groundwater resources used for drinking-water supply and to improve public knowledge of groundwater quality in California. Quality-control samples (source-solution blanks, equipment blanks, and field blanks) were collected in order to ensure the quality of the groundwater sample results. Olsen and others (2010) previously determined study reporting levels (SRLs) for trace-element results based primarily on field blanks collected in California from May 2004 through January 2008. SRLs are raised reporting levels used to reduce the likelihood of reporting false detections attributable to contamination bias. The purpose of this report is to identify any changes in the frequency and concentrations of detections in field blanks since the last evaluation and update the SRLs for more recent data accordingly. Constituents analyzed were aluminum (Al), antimony (Sb), arsenic (As), barium (Ba), beryllium (Be), boron (B), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), lead (Pb), lithium (Li), manganese (Mn), molybdenum (Mo), nickel (Ni), selenium (Se), silver (Ag), strontium (Sr), thallium (Tl), tungsten (W), uranium (U), vanadium (V), and zinc (Zn). Data from 179 field blanks and equipment blanks collected from March 2006 through March 2013 by the GAMA-PBP indicated that for trace elements that had a change in detection frequency and concentration since the previous review, the shift occurred near October 2009, in conjunction with a change in the capsule filters used by the study. Results for 89 field blanks and equipment blanks collected from October 2009 through March 2013 were evaluated for potential contamination bias by using the same approach developed by Olsen and others (2010). Some data collected by the National Water-Quality Assessment (NAWQA) Program for the Southern California Coastal Drainages study unit were included to supplement the GAMA-PBP data. The detection frequency and upper threshold of potential contamination bias (BD-90/90) were determined from field-blank and equipment-blank data for each trace element. The BD-90/90 is the 90th percentile concentration of potential extrinsic contamination calculated by using the binomial probability distribution for greater than 90 percent confidence. Additionally, data from laboratory blanks and blind blanks analyzed by the National Water Quality Laboratory (NWQL) during water years 2010 through 2013, and compiled by the USGS Branch of Quality Systems (BQS), were considered for each trace element. These results were compared to each constituent’s reporting level to determine whether an SRL was necessary to minimize the potential for detections in the groundwater samples, attributed principally to contamination bias. Results of the evaluation were used to set SRLs for trace-element data for about 1,135 samples of groundwater collected by the GAMA-PBP between October 2009 and March 2013. Ten trace elements analyzed (Sb, As, Be, B, Cd, Li, Se, Ag, Tl, and U) had blank results that did not necessitate establishing SRLs during this review or the review by Olsen and others (2010). Five trace elements analyzed (Al, Ba, Cr, Sr, and V) had blank results that necessitated establishing an SRL during the previous review but did not need an SRL starting October 2009. One trace element (Fe) had field and laboratory-blank results that necessitated keeping the previous SRL (6 micrograms per liter [μg/L]). Two trace elements (Ni and W) had quality-control results that warranted decreasing the previous SRL, and five trace elements (Cu, Pb, Mn, Mo, and Zn) had field, laboratory, or blind blank results that warranted establishing an SRL for the first time or increasing the previous SRL. SRLs for Cu (2.1 μg/L), Pb (0.82 μg/L), Mn (0.66 μg/L), Mo (0.023 μg/L), Ni (0.21 μg/L), W (0.023 μg/L), and Zn (6.2 μg/L) were changed to these levels starting October 2009, based on the BD-90/90 concentration for field blanks or the 99th percentile concentration for laboratory or blind blanks. The SRL for Fe was maintained at 6 μg/L, based on the minimum laboratory reporting level for iron. SRLs for these eight constituents were at least an order of magnitude below the regulatory benchmarks established for drinking water for health and aesthetic purposes; therefore, the practice of reporting concentrations below the SRLs as less than or equal to (≤) the measured value would not prevent the identification of values greater than the drinking-water benchmarks. Co was detected in 99 percent of field blanks, and with a BD-90/90 concentration of 0.38 μg/L, all groundwater results starting October 2009 were coded as “reviewed and rejected.” Co does not currently have a regulatory benchmark for drinking water. The primary sources of contamination for trace elements inferred from this review are the equipment or processes used in the field to collect the samples or in the laboratory. In particular, contamination in field blanks of Co and Mn was attributed to the high-capacity 0.45-micrometer pore-size capsule filters that were in regular use beginning in October 2009 by several USGS programs, including the GAMA-PBP and NAWQA Program, for filtering samples for analysis of trace elements. The SRLs determined in this report are intended to be used for GAMA groundwater-quality data for samples collected October 2009 through March 2013, or for as long as quality-control data indicate contamination similar to what was observed in this report; quality-control data should be continuously reviewed and SRLs re-assessed on at least a study-unit basis.

California↗

Cassin's Sparrow (Aimophila cassinii) status assessment and conservation plan

Executive Summary Cassin’s Sparrow ( Aimophila cassinii ) is a grassland species endemic to the southwestern U.S. and northern Mexico. Its behavior and ecology have been shaped by these arid ecosystems and the health of its populations is dependent on the availability of grasslands that contain a shrub component. Populations of many grassland birds have experienced dramatic declines due to the loss and deterioration of grassland habitats, and there has been concern about the trends in Cassin’s Sparrow populations. Without better information about population trends, ecology, and effects of management activities, and without a stronger emphasis on grassland management, Cassin’s Sparrows and other grassland species may continue to experience declines. Little information exists about historic Cassin’s Sparrow population levels, and current population estimates for states in the breeding range are unknown. Significant survey-wide declines are documented by the Breeding Bird Survey (BBS) between 1966 and 1996. However, closer examination of these data suggest that the survey-wide trends are driven by population declines in the Edwards Plateau and South Texas Brushlands in Texas. No other areas within the core of its range or on the periphery show consistent, significant trends. In fact, there is consensus that in the core of its range in New Mexico Cassin’s Sparrow remains the most abundant breeding bird in grasslands with a shrub component. Understanding of population patterns in this species is complicated by large yearly fluctuations in distribution and numbers at any particular location, apparently in response to precipitation. This is particularly obvious in the periphery of its range. These dramatic fluctuations have hampered a clear assessment of population status, and our understanding has been confounded by the fact that the timing of BBS data collection does not always coincide with the peak breeding season of this species. The lack of information about the Cassin’s Sparrow’s status, ecology, and response to management activities, and the apparent declines indicated by BBS data, have been cause for concern. Habitat disturbance and degradation, mainly due to grazing and rangeland management practices such as shrub control, fire management, and planting of exotics, pose threats to Cassin’s Sparrow populations, as does habitat conversion through suburban development and agriculture. There is evidence that heavy grazing negatively affects populations, but the information is primarily available from the southwestern portion of its range (Arizona) and may not be applicable throughout the Cassin’s Sparrow’s entire range. Any management practice that results in complete removal of the shrub component, or loss of grass cover and an increase in shrub density beyond a threshold preferred by the species, also poses a threat. Lack of standardized or coordinated studies of Cassin’s Sparrow ecology and response to management practices in different geographic portions of its range has made it difficult to assess its status and make specific management recommendations. Limited data are available from the wintering grounds, and from its range (both breeding and wintering) in Mexico. The greatest needs are for determining of the causes of significant declines where they occur, determining of the effects of various management activities on Cassin’s Sparrow throughout its range, improved assessments of population and trends, and a better understanding of the annual population and distribution dynamics of this species, which shows such dramatic annual distributional fluctuations.

Wyoming, Nebraska, Kansas, Oklahoma,Texas, New Mex↗

Groundwater quality, age, and susceptibility and vulnerability to nitrate contamination with linkages to land use and groundwater flow, Upper Black Squirrel Creek Basin, Colorado, 2013

The Upper Black Squirrel Creek Basin is located about 25 kilometers east of Colorado Springs, Colorado. The primary aquifer is a productive section of unconsolidated deposits that overlies bedrock units of the Denver Basin and is a critical resource for local water needs, including irrigation, domestic, and commercial use. The primary aquifer also serves an important regional role by the export of water to nearby communities in the Colorado Springs area. Changes in land use and development over the last decade, which includes substantial growth of subdivisions in the Upper Black Squirrel Creek Basin, have led to uncertainty regarding the potential effects to water quality throughout the basin. In response, the U.S. Geological Survey, in cooperation with Cherokee Metropolitan District, El Paso County, Meridian Service Metropolitan District, Mountain View Electric Association, Upper Black Squirrel Creek Groundwater Management District, Woodmen Hills Metropolitan District, Colorado State Land Board, and Colorado Water Conservation Board, and the stakeholders represented in the Groundwater Quality Study Committee of El Paso County conducted an assessment of groundwater quality and groundwater age with an emphasis on characterizing nitrate in the groundwater. Groundwater-quality samples were collected from 50 randomly selected wells between May and June 2013. The samples were analyzed for major ions, nutrients, dissolved gases, tritium ( 3 H), chlorofluorocarbons (CFC-11, CFC-12, and CFC-113), and fuel products (such as benzene, toluene, ethylbenzene, and xylenes). None of the groundwater samples exceeded the U.S. Environmental Protection Agency (EPA) National Primary Drinking Water Regulations for primary maximum contaminant levels (MCL) for major ions. Secondary maximum contaminant levels, which are not health concerns and affect mainly taste, color, or odor of the water, were observed in rare instances for pH (2 samples), chloride (1 sample), iron (3 samples), and manganese (8 samples). The secondary maximum contaminant level for total dissolved solids was also exceeded for two samples. Nitrate (nitrite plus nitrate as nitrogen in groundwater) was elevated above the estimated background concentration of natural recharge waters of 1 milligram per liter (mg/L) in 44 of the 50 wells sampled and showed a median concentration of 5.4 mg/L. Nitrate concentrations were above the MCL of 10 mg/L in 5 of the 50 wells sampled and above half of the EPA MCL (5 mg/L) in 27 of the 50 wells sampled, which included samples above the MCL. Dissolved-oxygen concentrations exceeded 0.5 mg/L in 95 percent of reported values (40 of 42 samples) and exceeded 2.0 mg/L in 90 percent of reported values (38 of 42 samples). The oxidized conditions observed in most areas indicate that nitrate from fertilizers and animal or human waste was geochemically stable and could persist in the groundwater for decades or perhaps longer. A historical analysis of median nitrate concentrations over nearly three decades showed an increase in nitrate of approximately 1 mg/L from 4.3 to 5.4 mg/L, although the increase was not determined to be significantly different using nonparametric statistical methods. Major-ion data indicate that groundwater representative of the primary aquifer was classified as calcium-sodium bicarbonate type water. Other water samples from wells located mainly along the periphery of the primary aquifer had cation-anion compositions consistent with distinct water sources, including groundwater contributions from the underlying bedrock aquifers. The areas with differentiable water sources were located mainly where alluvial deposits were thin and geologic contacts to the underlying bedrock aquifers were relatively shallow. Nitrate concentrations in the groundwater were evaluated for relations to land use. An agricultural region was defined using a sequence of land satellite imagery. Groundwater flow directions interpreted from median water-table elevations measured from 2000 to 2013 were used in conjunction with cropland locations to define the agricultural region boundaries by encompassing potential pathways of nitrate transport in the groundwater from nitrogen-based fertilizers. A statistically significant higher median nitrate concentration was observed for areas inside the agricultural region (6.7 mg/L) compared to areas outside the agricultural region (2.3 mg/L), although median concentrations in both areas were below the MCL (10 mg/L). Median nitrate concentration was also significantly greater in land parcels with septic use (4.9 mg/L) compared to nonseptic parcels (1.7 mg/L). In general, agriculture or septic use was identified as the primary source of nitrate, depending on location, while commercial, county, grazing, and residential land uses were generally secondary sources of nitrate. Apparent groundwater ages were estimated from chlorofluorocarbons (CFC-11, CFC-12, and CFC-113) and tritium ( 3 H) data using models that assumed piston flow and binary mixing (dilution of a young component with old, tracer-free water). The mean and median groundwater ages were about 30 years and the standard deviation was 6 years, indicating that most groundwater in the primary aquifer was “young” water that had recharged to the aquifer over the last few decades (post-1950s). The median fraction of young water was about 71 percent, and the standard deviation was 29 percent. The remaining water predated the 1950s, which may have originated from deeper geologic formations or may represent slow moving groundwater within the primary aquifer. Some of the oldest groundwater ages (older than 30 years) were observed in the upper reaches of the aquifer to the northwest where the primary aquifer is thin and intersects bedrock, supporting the hypothesis of geochemically distinct groundwater entering the primary aquifer from below. Groundwater that had reached the central part of the aquifer from upgradient areas of the basin was variable in age because of differences in flow paths and travel velocities. The groundwater age analysis showed that current (2013) land-use practices could affect water quality over decades to come, and that responses to remedial actions could be slow, especially for constituents, such as nitrate, that are stable under oxidized conditions. Fuel products (including acetone, benzene, diisopropyl ether, ethylbenzene, methyl acetate, methyl tertiary butyl ether (MTBE), methyl tert-pentyl ether, m- + p-xylene, o-xylene, tert-amyl alcohol, tert-butyl alcohol, tert-butyl ethyl ether, and toluene) were analyzed in groundwater from 49 of the 50 wells. Water from seven sites had detections for fuel compounds; all concentrations were below MCL. The results provided assurance of water quality and a valuable baseline to evaluate future trends of fuel constituents as the region is further developed. Probability maps were developed from logistic regression models to examine the likelihood that nitrate concentrations in groundwater exceeded specified levels. Susceptibility analysis examined relations between mid-level (5.0 mg/L) nitrate concentrations and climatic, hydrologic, and geologic variables; the significant variables were identified as depth to groundwater, soil organic matter, and soil water storage to 25-centimeter (cm) depth. The vulnerability assessments included natural factors driving susceptibility but also human factors related to land use and septic use. Vulnerability to low-level (2.5 mg/L) nitrate was related to depth to groundwater, septic zoning, and soil organic matter. The results highlighted that septic zoning affected low-level nitrate concentrations. Vulnerability to mid-level (5.0 mg/L) nitrate was examined using all 50 samples and also with two data outliers removed, which showed relatively high nitrate concentrations but also anomalous water chemistry or were located beyond the primary study area. Vulnerability to mid-level (5.0 mg/L) nitrate using all 50 samples was related to depth to groundwater, land use, septic use within a 500-meter (m) radius, soil water storage to a 25-cm depth, soil organic matter, and whether a location was within the agricultural region. The mid-level (5.0 mg/L) vulnerability model using 48 samples (two outliers removed) produced the best overall fit and was related to the same variables as when using all samples except septic use. The results for mid-level vulnerability provided additional support that septic use was associated with low levels of nitrate in the groundwater. Soil properties and land use were identified as the main drivers of moderate nitrate concentrations. Probabilities of exceeding low-level nitrate concentrations were high in most areas with the lowest probabilities usually to the northwest along thin geologic deposits in the upper part of the basin. The results of this investigation offer the foundational information needed for developing best management practices to mitigate nitrate contamination, basic concepts on water quality to aid public education, and information to guide regulatory measures if policy makers determine this is warranted. Science-based decision making will require continued monitoring and analysis of water quality in the future.

Colorado↗