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Groundwater, surface-water, and water-chemistry data, Black Mesa area, northeastern Arizona—2013–2015

The Navajo (N) aquifer is an extensive aquifer and the primary source of groundwater in the 5,400-square-mile Black Mesa area in northeastern Arizona. Availability of water is an important issue in northeastern Arizona because of continued water requirements for industrial and municipal use by a growing population and because of low precipitation in the arid climate of the Black Mesa area. Precipitation in the area typically is between 6 and 16 inches per year. The U.S. Geological Survey water-monitoring program in the Black Mesa area began in 1971 and provides information about the long-term effects of groundwater withdrawals from the N aquifer for industrial and municipal uses. This report presents results of data collected as part of the monitoring program in the Black Mesa area from January 2013 to December 2015. The monitoring program includes measurements of (1) groundwater withdrawals (pumping), (2) groundwater levels, (3) spring discharge, (4) surface-water discharge, and (5) groundwater chemistry. In 2013, total groundwater withdrawals were 3,980 acre-feet (ft), in 2014 total withdrawals were 4,170 acre-ft, and in 2015 total withdrawals were 3,970 acre-ft. From 2013 to 2015 total withdrawals varied by less than 5 percent. From 2014 to 2015, annually measured water levels in the Black Mesa area declined in 9 of 15 wells that were available for comparison in the unconfined areas of the N aquifer, and the median change was -0.1 feet. Water levels declined in 3 of 16 wells measured in the confined area of the aquifer. The median change for the confined area of the aquifer was 0.6 feet. From the prestress period (prior to 1965) to 2015, the median water-level change for 34 wells in both the confined and unconfined areas was -13.2 feet; the median water-level changes were -1.7 feet for 16 wells measured in the unconfined areas and -42.3 feet for 18 wells measured in the confined area. Spring flow was measured at four springs in 2014. Flow fluctuated during the period of record for Burro Spring and Unnamed Spring near Dennehotso, but a decreasing trend was statistically significant (p<0.05) at Moenkopi School Spring and Pasture Canyon Spring. Discharge at Burro Spring has remained relatively constant since it was first measured in the 1980s and discharge at Unnamed Spring near Dennehotso has fluctuated for the period of record. Trend analysis for discharge at Moenkopi and Pasture Canyon Springs yielded a slope significantly different (p<0.05) from zero. Continuous records of surface-water discharge in the Black Mesa area were collected from streamflow-gaging stations at the following sites: Moenkopi Wash at Moenkopi 09401260 (1976 to 2015), Dinnebito Wash near Sand Springs 09401110 (1993 to 2015), Polacca Wash near Second Mesa 09400568 (1994 to 2015), and Pasture Canyon Springs 09401265 (2004 to 2015). Median winter flows (November through February) of each water year were used as an index of the amount of groundwater discharge at the above-named sites. For the period of record of each streamflow-gaging station, the median winter flows have generally remained constant, which suggests no change in groundwater discharge. In 2014, water samples collected from four springs in the Black Mesa area were analyzed for selected chemical constituents, and the results were compared with previous analyses. Dissolved solids, chloride, and sulfate concentrations increased at Moenkopi School Spring during the more than 25 years of record at that site. Concentrations of dissolved solids, chloride, and sulfate at Pasture Canyon Spring have not varied significantly (p>0.05) since the early 1980s, and there is no increasing or decreasing trend in those data. Concentrations of dissolved solids, chloride, and sulfate at Burro Spring and Unnamed Spring near Dennehotso have varied for the period of record, but there is no increasing or decreasing statistical trend in the data.

Arizona

Analysis of water use associated with hydraulic fracturing and determination of baseline water quality in watersheds within the shale play of eastern Ohio, 2021–23

The U.S. Geological Survey, in cooperation with the Ohio Department of Natural Resources, performed a two-part study to (1) assess water use and temporal trends and changes in streamflow, and to (2) characterize 2021–23 baseline water quality, as they relate to oil and gas extraction activities in selected eastern Ohio watersheds. Between calendar years 2010 and 2019, hydraulic fracturing water withdrawals totaling about 27,168 million gallons were reported at 643 locations in Ohio. In 2021, wells developed with hydraulic fracturing were the source of most of the oil and gas produced in Ohio. Daily streamflow time-series data from seven study gages and two reference gages were used to assess temporal trends and changes in streamflow. The study gages were in basins with reported water withdrawals for hydraulic fracturing. The reference gages, which have long periods of record and were subject to minimal streamflow regulation, were in nearby basins with no hydraulic fracturing water withdrawals. Trend slopes for the period of record annual minimum and median daily streamflows and for annual daily streamflow nonexceedance probabilities less than 0.9 were all uniformly positive at the study and reference gages. This trend indicates a consistently increasing pattern over the periods of record, except for high flows. In addition, analyses of annual streamflow statistics showed no general indication that low flows or extreme low flows at the reference or study gages have lowered, become more frequent, or lengthened in duration since 2010, when records for hydraulic fracturing water withdrawals began in Ohio. In fact, in almost all cases, the opposite was indicated. Nonexceedance percentiles of daily streamflows were compared between the full and pre-2012 periods of record for reference and study gages. The streamflows associated with nonexceedance percentiles in the lower quartile of daily streamflows determined for the full period of record were larger than or equal to those determined for the pre-2012 period of record for all study and reference gages. This indicates that low flows did not decrease during the post-2011 period of record when water was withdrawn for hydraulic fracturing. Water-quality data were collected eight times at each of eight sampling sites (six of which were colocated with the study gages). Sampling was done during a variety of flow conditions to assess baseline water quality. In 2021, the 8 sampling sites had drainage basins that were wholly or partially within 7 of the 10 most active counties in Ohio for oil and gas development. As part of the record of baseline conditions, water-quality data were used to assess (1) water types based on major-ion chemistry; (2) sources of salinity to streams; (3) exceedances of aquatic life use criteria; and (4) the correlations between water chemistry and drainage-basin characteristics, such as density of oil and gas wells, density of wastewater treatment plants, or the percentage of different types of land cover (agriculture, developed, forest). Seven of the water-quality sampling sites were designated as coal-mine impacted based on criteria developed for assessing mine-drainage impacts in Ohio. Mine drainage from historical coal mining in the region likely affected the quality of these streams and complicated the use of some constituents typically used as indicators of oil and gas influence. Based on major-ion chemistry, three main types of water were in the study area―sulfate (three sites), calcium-bicarbonate (one site), and mixed bicarbonate-chloride (four sites) type waters. One site had samples with a higher proportion of sodium and chloride ions than other stream samples, indicating potential contamination with oil-field brine or road salt. Binary mixing curves revealed that 11 samples from 4 of the sampling sites likely contained a component of brine. The results of the baseline assessment of surface-water quality in the study area showed no exceedances of Ohio Environmental Protection Agency aquatic life use criteria. Spearman’s rank correlation coefficients indicated no significant positive correlations with the density of vertical or horizontal oil and gas wells.

Ohio

Optical resolution of rotenoids

Optical resolution of selected rotenoids containing 1-3 asymmetric centers in dihydrobenzopyranofuroben-zopyranone and dihydrobisbenzopyranopyranone series has been achieved on two chiral high-performance liquid chromatographic (hplc) stationary phases. In most cases, the absolute stereochemistry at the cis -B/C ring junction of the rotenoidal antipodes can be related to their elution order. Generally, the 6a&alpha;,12a&alpha;-enantiomers were more strongly retained by the chiral substrate than their corresponding optical antipodes. The elution-configuration relationship provides potential utility for predicting the absolute configuration of related rotenoidal compounds. Chiral phase hplc on amino-acid-bonded-silica yielded results explicable in terms of Pirkle's bonding schemes for chiral recognition. Resolution data for 12a-hydroxy-, 12a-methoxy-, and 12-hydroxyiminorotenoids further corroborate the mechanistic rationale, and demonstrate that nonpolar &pi;-&pi; interactions appeared to be important for enantiomeric separation on helic poly-triphenylmethylacryl-ate-silica (CPOT). In the latter system, steric effects and conformational factors in association with the modification of E-ring structures might play significant roles in the chiral separation process in view of the reversal to the elution order observed for all methoxylated rotenoids and elliptone derivatives including the parent deguelin. The unique separability (&alpha; = 1.44) of 12a-hydroxyelliptone on CPOT was suggestive of structural effects of the 5-side chain on the resolution of the rotenoids having a five-membered-E-ring. The results obtained with two different types of chiral phases are complementary and useful for optical resolution of a wide variety of natural and synthetic rotenoidal compounds.

Journal of Heterocyclic Chemistry

Groundwater, surface-water, and water-chemistry data, Black Mesa area, northeastern Arizona - 2010-2011

The Navajo (N) aquifer is an extensive aquifer and the primary source of groundwater in the 5,400-square-mile Black Mesa area in northeastern Arizona. Availability of water is an important issue in northeastern Arizona because of continued water requirements for industrial and municipal use by a growing population and because of low precipitation in the arid climate of the Black Mesa area. Precipitation in the area is typically between 6 to 14 inches per year. The U.S. Geological Survey water-monitoring program in the Black Mesa area began in 1971 and provides information about the long-term effects of groundwater withdrawals from the N aquifer for industrial and municipal uses. This report presents results of data collected as part of the monitoring program in the Black Mesa area from January 2010 to September 2011. The monitoring program includes measurements of (1) groundwater withdrawals, (2) groundwater levels, (3) spring discharge, (4) surface-water discharge, and (5) groundwater chemistry. In 2010, total groundwater withdrawals were 4,040 acre-ft, industrial withdrawals were 1,170 acre-ft, and municipal withdrawals were 2,870 acre-ft. Total withdrawals during 2010 were about 42 percent less than total withdrawals in 2005 because of Peabody Western Coal Company's discontinued use of water to transport coal in a slurry. From 2009 to 2010 total withdrawals decreased by 5 percent; industrial withdrawals decreased by approximately 16 percent, and total municipal withdrawals increased by 1 percent. From 2010 to 2011, annually measured water levels in the Black Mesa area declined in 7 of 15 wells that were available for comparison in the unconfined areas of the N aquifer, and the median change was 0.0 foot. Water levels declined in 11 of 18 wells measured in the confined area of the aquifer. The median change for the confined area of the aquifer was -0.7 foot. From the prestress period (prior to 1965) to 2011, the median water-level change for 33 wells in both the confined and unconfined areas was -15.0 feet. Also, from the prestress period to 2011, the median water-level changes were -1.2 foot for 15 wells measured in the unconfined areas and -41.2 feet for 18 wells measured in the confined area. Spring flow was measured at three springs in 2011. Flow fluctuated during the period of record, but a decreasing trend was apparent at Moenkopi School Spring and Pasture Canyon Spring. Discharge at Burro Spring has remained relatively constant since it was first measured in the 1980s. Continuous records of surface-water discharge in the Black Mesa area were collected from streamflow-gaging stations at the following sites: Moenkopi Wash at Moenkopi 09401260 (1976 to 2010), Dinnebito Wash near Sand Springs 09401110 (1993 to 2010), Polacca Wash near Second Mesa 09400568 (1994 to 2010), and Pasture Canyon Springs 09401265 (2004 to 2010). Median winter flows (November through February) of each water year were used as an index of the amount of groundwater discharge at the above-named sites. For the period of record of each streamflow-gaging station, the median winter flows have generally remained constant, which suggests no change in groundwater discharge. In 2011, water samples collected from 11 wells and 4 springs in the Black Mesa area were analyzed for selected chemical constituents, and the results were compared with previous analyses. Concentrations of dissolved solids, chloride, and sulfate have varied at all 11 wells for the period of record, but neither increasing nor decreasing trends over time were found. Dissolved-solids, chloride, and sulfate concentrations increased at Moenkopi School Spring during the more than 12 years of record at that site. Concentrations of dissolved solids, chloride, and sulfate at Pasture Canyon Spring have not varied much since the early 1980s, and there is no increasing or decreasing trend in those data. Concentrations of dissolved solids, chloride, and sulfate at Burro Spring and Unnamed Spring near Dennehotso have varied for the period of record, but there is no increasing or decreasing trend in the data.

Arizona

Completion summary for boreholes USGS 148, 148A, and 149 at the Materials and Fuels Complex, Idaho National Laboratory, Idaho

In 2019, the U.S. Geological Survey (USGS), in cooperation with the U.S. Department of Energy, drilled and constructed boreholes USGS 148A and USGS 149 for stratigraphic framework analyses and long-term groundwater monitoring of the eastern Snake River Plain aquifer at the Idaho National Laboratory (INL) in southeastern Idaho. Initially, boreholes USGS 148A and USGS 149 were continuously cored to allow the USGS and INL subcontractor to collect select geophysical and seismic data and evaluate properties of recovered core material. The USGS geophysical data and descriptions of core material are described in this report; however, data collected by the INL contractor, including seismic data, are not included as part of the report. The unsaturated zone at both borehole locations is relatively thick, depth to water was measured at approximately 663.6 feet (ft) below land surface (BLS) in USGS 148A, and at approximately 654.1 ft BLS at USGS 149. On completion of coring and data collection, both boreholes (USGS 148A and USGS 149) were repurposed as monitoring wells. Well USGS 148A was constructed to a depth of 759 ft BLS and instrumented with a dedicated submersible pump and measurement line; well USGS 149 was constructed to a depth of 974 ft BLS and instrumented with a multilevel monitoring system (Westbay TM ). Geophysical data, collected by the USGS, were used to characterize the subsurface geology and aquifer conditions. Natural gamma log measurements were used to assess sediment-layer thickness and location. Neutron and gamma-gamma source logs were used to confirm fractured and vesicular basalt identified for aquifer testing and multilevel monitoring well zone testing. Acoustic televiewer logs, collected for well USGS 149, were used to identify fractures and assess groundwater movement when compared with neutron measurements. Furthermore, gyroscopic deviation measurements were used to measure horizontal and vertical displacement for the constructed boreholes USGS 148A and USGS 149. A single-well aquifer test was done in well USGS 148A during November 6–7, 2019, to provide estimates of transmissivity and hydraulic conductivity. Estimates for transmissivity and hydraulic conductivity were 6.34×10 3 feet squared per day and 3.17 feet per day, respectively. The aquifer test was run overnight (21.3 hours) and measured drawdown was relatively small (0.09 ft) at sustained pumping rates ranging from 15.7 to 16.1 gallons per minute. The transmissivity estimates for well USGS 148A were slightly lower than those determined from previous aquifer tests for wells near the Materials and Fuels Complex, but well within range of other aquifer tests done at the INL. Water-quality samples, collected from well USGS 148A and from four zones in well USGS 149, were analyzed for cations, anions, metals, nutrients, volatile organic compounds, stable isotopes, and radionuclides. Water samples for most of the inorganic constituents showed similar chemistry in USGS 148A and all four zones in USGS 149. Water samples for stable isotopes of oxygen and hydrogen indicated some possible influence of irrigation on the water quality. Nitrate plus nitrite concentrations indicated influence from anthropogenic sources. The volatile organic compound and radiochemical data indicated that wastewater disposal practices at the Materials and Fuels Complex or from drilling had no detectable influence on these wells.

Idaho

Studies on geological background and source of fluorine in drinking water in the North China Plate fluorosis areas

Endemic fluorosis in northern China is usually produced by high fluorine (F) content in drinking water. Thirty-one samples of drinking waters, mainly well waters and nearly 200 samples of rocks, loess, and coal were analyzed for F content using the combustion hydrolysis-fluoride-ion selective electrode (ISE) method. The geologic cross sections of two well-known fluorosis basins were studied. The solubility of F in different rock types collected from fluorosis areas was determined. Results showed that areas of endemic fluorosis in northern China are located in coal-bearing basins which are comprised of three stratagraphic portions. The lowest portion is Precambrian granitic rocks or Cambrian-Ordovician carbonates. The middle portion consists of Permo-Carboniferous or Jurassic coal-bearing sequences. The upper portion is 0-400 m Pleistocene loess. Flourine content in the Precambrian granite-gneiss contained (a) 1090-1460 ppm, in the Cambrian-Ordovician limestone and dolomite, (b) 52-133 ppm, in black shales and coal gob of Permo-Carboniferous coal-bearing strata, (c) 200-700 ppm, and (d) Pleistocene loess 454-542 ppm. The solubility of F in black shales of coal-bearing sequences was higher than in Precambrian granitic rocks, and both were more soluble than loess. F solubility from Precambrian granitic rocks was moderate, but Precambrian granitic rocks have high F content and thus contribute an appreciable amount of ion to the shallow groundwater (well water). Varying F content in shallow groundwater is controlled by geological conditions. The sources of F in the shallow groundwater from fluorosis areas in northern China are mainly derived from black shales of coal-bearing sequences and Precambrian granitic basement in the basins of northern China. ?? 2008 Taylor & Francis.

Toxicological and Environmental Chemistry

Groundwater, surface-water, and water-chemistry data, Black Mesa area, northeastern Arizona—2015–2016

The Navajo (N) aquifer is an extensive aquifer and the primary source of groundwater in the 5,400-square-mile Black Mesa area in northeastern Arizona. Availability of water is an important issue in the Black Mesa area because of continued water requirements for industrial and municipal use by a growing population and because of the arid climate. Precipitation in the area typically ranges from less than 6 to more than 16 inches per year depending on location. The U.S. Geological Survey water-monitoring program in the Black Mesa area began in 1971 and provides information about the long-term effects of groundwater withdrawals from the N aquifer for industrial and municipal uses. This report presents results of data collected as part of the monitoring program in the Black Mesa area from November 2015 to December 2016. The monitoring program includes measurements of (1) groundwater withdrawals (pumping), (2) groundwater levels, (3) spring discharge, (4) surface-water discharge, and (5) groundwater chemistry. In calendar year 2016, total groundwater withdrawals were 3,540 acre-ft, industrial withdrawals were 1,090 acre-ft, and municipal withdrawals were 2,450 acre-ft. Total withdrawals during 2016 were about 52 percent less than total withdrawals in 2005 because of Peabody Western Coal Company’s discontinued use of water to transport coal in a coal slurry pipeline. From 2015 to 2016, annually measured water levels available for comparison in wells completed in the unconfined areas of the N aquifer within the Black Mesa area declined in 9 of 16 wells, and the median change was –0.1 feet. Water levels also declined in 8 of 16 wells measured in the confined area of the aquifer. The median change for the confined area of the aquifer was 0.0 feet. From the prestress period (prior to 1965) to 2016, the median water-level change for all 32 wells in both the confined and unconfined areas was –10.2 feet; the median water-level changes were –1.6 feet for the 16 wells measured in the unconfined areas and –36.1 feet for the 16 wells measured in the confined area. Spring flow was measured at four springs in 2016. Flow fluctuated during the period of record for Burro Spring and Pasture Canyon Spring, but a decreasing trend was statistically significant (p<0.05) at Moenkopi School Spring and Unnamed Spring near Dennehotso. Discharge at Burro Spring has remained relatively constant since it was first measured in the 1980s and discharge at Pasture Canyon Spring has fluctuated for the period of record. Continuous records of surface-water discharge in the Black Mesa area were collected from streamflow-gaging stations at the following sites: Moenkopi Wash at Moenkopi 09401260 (1976 to 2016), Dinnebito Wash near Sand Springs 09401110 (1993 to 2016), Polacca Wash near Second Mesa 09400568 (1994 to 2016), and Pasture Canyon Springs 09401265 (2004 to 2016). Median winter flows (November through February) of each water year were used as an index of the amount of groundwater discharge at the above-named sites. For the period of record, the median winter flows have generally remained constant at Dinnebito Wash and Polacca Wash, whereas a decreasing trend was indicated at Moenkopi Wash and Pasture Canyon Springs. In 2016, water samples collected from three wells and four springs in the Black Mesa area were analyzed for selected chemical constituents, and the results were compared with previous analyses from the same wells and springs. Concentrations of dissolved solids, chloride, and sulfate have varied at all three wells for the period of record, but neither increasing nor decreasing trends over time were found. Dissolved solids, chloride, and sulfate concentrations increased at Moenkopi School Spring during the more than 25 years of record at that site. Concentrations of dissolved solids, chloride, and sulfate at Pasture Canyon Spring have not varied significantly (p>0.05) since the early 1980s, and there is no increasing or decreasing trend in those data. Concentrations of dissolved solids, chloride, and sulfate at Burro Spring and Unnamed Spring near Dennehotso have varied for the period of record, but there is no statistical trend in the data.

Arizona

Groundwater, surface-water, and water-chemistry data, Black Mesa area, northeastern Arizona&mdash;2009&ndash;10

The Navajo (N) aquifer is an extensive aquifer and the primary source of groundwater in the 5,400-square-mile Black Mesa area in northeastern Arizona. Availability of water is an important issue in northeastern Arizona because of continued water requirements for industrial and municipal use by a growing population and because of low precipitation in the arid climate of the Black Mesa area. Precipitation in the area is typically between 6 and 14 inches per year. The U.S. Geological Survey water-monitoring program in the Black Mesa area began in 1971 and provides information about the long-term effects of groundwater withdrawals from the N aquifer for industrial and municipal uses. This report presents results of data collected as part of the monitoring program in the Black Mesa area from January 2009 to September 2010. The monitoring program includes measurements of (1) groundwater withdrawals, (2) groundwater levels, (3) spring discharge, (4) surface-water discharge, and (5) groundwater chemistry. In 2009, total groundwater withdrawals were 4,230 acre-ft, industrial withdrawals were 1,390 acre-ft, and municipal withdrawals were 2,840 acre-ft. Total withdrawals during 2009 were about 42 percent less than total withdrawals in 2005 because of Peabody Western Coal Company's discontinued use of water in a coal slurry used for transporting coal. From 2008 to 2009 total withdrawals increased by 3 percent and industrial withdrawals increased by approximately 15 percent, but total municipal withdrawals decreased by 2 percent. From 2009 to 2010, annually measured water levels in the Black Mesa area declined in 7 of 16 wells that were available for comparison in the unconfined areas of the N aquifer, and the median change was 0.1 foot. Water levels declined in 12 of 18 wells measured in the confined area of the aquifer. The median change for the confined area of the aquifer was -0.3 foot. From the prestress period (prior to 1965) to 2010, the median water-level change for 34 wells in both the confined and unconfined area was -13.9 feet. Also, from the prestress period to 2009, the median water-level changes were -0.8 foot for 16 wells measured in the unconfined areas and -38.7 feet for 18 wells measured in the confined area. Spring flow was measured at four springs in 2010. Flow fluctuated during the period of record, but a decreasing trend was apparent at Moenkopi School Spring and Pasture Canyon Spring. Discharge at Burro Spring and Unnamed Spring near Dennehotso has remained relatively constant since they were first measured in the 1980s. Continuous records of surface-water discharge in the Black Mesa area were collected from streamflow-gaging stations at the following sites: Moenkopi Wash at Moenkopi 09401260 (1976 to 2009), Dinnebito Wash near Sand Springs 09401110 (1993 to 2009), Polacca Wash near Second Mesa 09400568 (1994 to 2009), and Pasture Canyon Springs 09401265 (2004 to 2009). Median winter flows (November through February) of each water year were used as an index of the amount of groundwater discharge at the above-named sites. For the period of record of each streamflow-gaging station, the median winter flows have generally remained constant, which suggests no change in groundwater discharge. In 2010, water samples collected from 11 wells and 4 springs in the Black Mesa area were analyzed for selected chemical constituents, and the results were compared with previous analyses. Concentrations of dissolved solids, chloride, and sulfate have varied at all 11 wells for the period of record, but neither increasing nor decreasing trends over time were found. Dissolved-solids, chloride, and sulfate concentrations increased at Moenkopi School Spring during the more than 12 years of record at that site. Concentrations of dissolved solids, chloride, and sulfate at Pasture Canyon Spring have not varied much since the early 1980s, and there is no increasing or decreasing trend in those data. Concentrations of dissolved solids, chloride, and sulfate at Burro Spring and Unnamed Spring near Dennehotso have varied for the period of record, but there is no increasing or decreasing trend in the data.

Open-File Report

Groundwater, surface-water, and water-chemistry data, Black Mesa area, northeastern Arizona—2018–2019

The Navajo (N) aquifer is an extensive aquifer and the primary source of groundwater in the 5,400-square-mile Black Mesa area in northeastern Arizona. Water availability is an important issue in the Black Mesa area because of the arid climate, past industrial water use, and continued water requirements for municipal use by a growing population. Precipitation in the area typically ranges from less than 6 to more than 16 inches per year depending on location. The U.S. Geological Survey water-monitoring program in the Black Mesa area began in 1971 and provides information about the long-term effects of groundwater withdrawals from the N aquifer for industrial and municipal uses. This report presents results of data collected as part of the monitoring program in the Black Mesa area from calendar year 2019, and additionally uses streamflow statistics from November and December 2018. The monitoring program includes measurements of (1) groundwater withdrawals (pumping), (2) groundwater levels, (3) spring discharge, (4) surface-water discharge, and (5) groundwater chemistry. In calendar year 2019, total groundwater withdrawals were estimated to be 3,070 acre-feet (acre-ft), industrial withdrawals were 670 acre-ft, and municipal withdrawals were estimated to be 2,400 acre-ft. Total withdrawals during 2019 were about 58 percent less than total withdrawals in 2005 because of Peabody Western Coal Company’s discontinued use of water to transport coal in a coal slurry pipeline after 2005 and cessation of mining operations in 2019. Water levels measured in 2019 from wells completed in the unconfined areas of the N aquifer within the Black Mesa area showed a decline in 10 of 16 wells when compared with water levels from the prestress period (prior to 1965). The changes in water levels across all 16 wells ranged from +8.2 feet (ft) to −40.0 ft, and the median change was −1.7 ft. Water levels also showed decline in 16 of 18 wells measured in the confined area of the aquifer when compared to the prestress period. The median change for the confined area of the aquifer was −38.8 ft, with changes across all 18 wells ranging from +12.9 ft to −185.0 ft. Spring flow was measured at four springs in 2019. Flow fluctuated during the period of record for Burro Spring and Pasture Canyon Spring, but a decreasing trend was statistically significant (p<0.05) at Moenkopi School Spring and Unnamed Spring near Dennehotso. Discharge at Burro Spring has remained relatively constant since it was first measured in the 1980s and discharge at Pasture Canyon Spring has fluctuated for the period of record. Continuous records of surface-water discharge in the Black Mesa area were collected from streamflow-gaging stations at the following sites: Moenkopi Wash at Moenkopi 09401260 (1976 to 2019), Dinnebito Wash near Sand Springs 09401110 (1993 to 2019), Polacca Wash near Second Mesa 09400568 (1994 to 2019), and Pasture Canyon Springs 09401265 (2004 to 2019). Median winter flows (November through February) of each winter were used as an estimate of the amount of groundwater discharge at the above-named sites. For the period of record, the median winter flows have generally remained constant at Polacca Wash and Pasture Canyon Springs, whereas a decreasing trend was indicated at Moenkopi Wash and Dinnebito Wash. In 2019, water samples collected from four springs and three wells in the Black Mesa area were analyzed for selected chemical constituents. Results from the four springs were compared with previous analyses from the same springs. Concentrations of dissolved solids, chloride, and sulfate increased at Moenkopi School Spring during the more than 30 years of record at that site. Concentrations of dissolved solids, chloride, and sulfate at Pasture Canyon Spring have not varied significantly (p>0.05) since the early 1980s, and there is no increasing or decreasing trend in those data. Concentrations of dissolved solids, chloride, and sulfate at Unnamed Spring near Dennehotso have varied for the period of record, but there is no statistical trend in the data. Concentrations of dissolved solids and chloride at Burro Spring have varied for the period of record, but there is no statistical trend in the data; however, concentrations of sulfate from Burro Spring now show a trend towards lower concentrations. No statistical trend tests were performed for the three wells sampled in 2019 since less historical water-quality data were available for comparison.

Arizona

Herbicides and nitrate in near-surface aquifers in the midcontinental United States, 1991

The occurrence and distribution of selected herbicides, atrazine metabolites, and nitrate were determined for near-surface aquifers (within 50 feet of land surface) in the corn- and soybean-producing region of the midcontinental United States. The study region included all or parts of Illinois, Indiana, Iowa, Kansas, Michigan, Minnesota, Missouri, Nebraska, North Dakota, Ohio, South Dakota, and Wisconsin. Water samples were collected during the spring and summer of 1991 from 303 wells completed in near-surface unconsolidated and near-surface bedrock aquifers. At least one herbicide or atrazine metabolite was detected in 24 percent of 579 water samples analyzed for herbicides, based on a reporting limit of 0.05 microgram per liter. However, no herbicide concentration exceeded the U.S. Environmental Protection Agency's maximum contaminant levels or health advisory levels for drinking water. The most frequently detected herbicide compound was desethylatrazine, an atrazine metabolite (18.1 percent), followed by atrazine (17.4 percent); deisopropylatrazine, an atrazine metabolite (5.7 percent); prometon (5.0 percent); metolachlor (2.7 percent); alachlor (1.7 percent); simazine (1.0 percent); metribuzin (1.0 percent); and cyanazine (0.7 percent). The herbicides ametryn, prometryn, propazine, and terbutryn were not detected during this study. Nitrate concentrations equal to or greater than 3.0 milligrams per liter (excess nitrate) were detected in 29 percent of the 599 nitrate analyses, and ammonium concentrations equal to or greater than 0.01 milligram per liter were detected in 78 percent of the 584 ammonium analyses. Nitrate concentrations equal to or greater than the U.S. Environmental Protection Agency's maximum contaminant level for drinking water of 10 milligrams per liter were found in 6 percent of the samples. The frequency of herbicide detection was, in part, affected by the analytical method's reporting limit. Results from this study show that the frequency of atrazine detection increases as the reporting limit decreases. Herbicide metabolite concentrations are critical to understanding the detection of herbicide residues. The frequency of detection of atrazine residue (atrazine + desethylatrazine + deisopropylatrazine) was 22.1 percent, which was more than the frequency of detection of atrazine alone (17.4 percent). Prometon was detected more frequently than every other herbicide except atrazine. The prometon appears to be derived from areas of nonagricultural land use, such as golf courses and residential areas. Herbicides and excess nitrate were both rarely detected in the eastern part of the study region, even though this is an area of intense herbicide and nitrogen-fertilizer use. Hydrogeologic factors, land use, agricultural practices, local features, and water chemistry were analyzed for possible relation to herbicide and excess-nitrate detections. Herbicides and excess nitrate were detected more frequently in near-surface unconsolidated aquifers than in nearsurface bedrock aquifers. The depth to the top of the aquifer was inversely related to the frequency of detection of herbicides and excess nitrate. The proximity of streams to sampled wells also affected the frequency of herbicide detection. Significant seasonal differences were determined for the frequency of herbicide detection, but not for the frequency of excess nitrate.

Illinois, Indiana, Iowa, Kansas, Michigan, Minneso

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

Groundwater, surface-water, and water-chemistry data, Black Mesa area, northeastern Arizona—2019–2021

The Navajo (N) aquifer is an extensive aquifer and the primary source of groundwater in the 5,400-square-mile Black Mesa area in northeastern Arizona. Water availability is an important issue in the Black Mesa area because of the arid climate, past industrial water use, and continued water requirements for municipal use by a growing population. Precipitation in the area typically ranges from less than 6 to more than 16 inches per year, depending on location. The U.S. Geological Survey water-monitoring program in the Black Mesa area began in 1971 and provides information about the long-term effects of groundwater withdrawals from the N aquifer for industrial and municipal uses. This report presents the results of data collected as part of the monitoring program in the Black Mesa area from calendar years 2020–2021 and, additionally, uses streamflow statistics from November and December 2019. The monitoring program includes measurements of (1) groundwater withdrawals (pumping), (2) groundwater levels, (3) spring discharge, (4) surface-water discharge, and (5) groundwater chemistry. In calendar year 2020, total groundwater withdrawals were estimated to be 2,680 acre-feet (acre-ft), and, in 2021, total withdrawals were estimated to be 2,570 acre-ft. Total withdrawals during 2021 were about 65 percent less than total withdrawals in 2005 because the Peabody Western Coal Company discontinued its use of water to transport coal in a coal slurry pipeline after 2005 and ceased mining operations in 2019. Owing to Navajo Nation and Hopi Reservation access restrictions during the Coronavirus pandemic, water levels were not collected from municipal wells in 2020 or 2021. Water levels measured in 2021 from wells completed in the unconfined areas of the N aquifer within the Black Mesa area showed a decline in 7 of 13 wells when compared with water levels from the prestress period (prior to 1965). The changes in water levels across all 13 wells ranged from +8.4 feet (ft) to −42.4 ft, and the median change was −0.4 ft. Water levels also showed decline in 11 of 12 wells measured in the confined area of the aquifer when compared to the prestress period. The median change for the confined area of the aquifer was −25.9 ft, with changes across all 12 wells ranging from +17.3 ft to −133.7 ft. Spring flow was measured at four springs between 2020 and 2021. Flow fluctuated during the period of record for Burro Spring and Pasture Canyon Spring, but a decreasing trend was statistically significant (p<0.05) at Moenkopi School Spring and Unnamed Spring near Dennehotso, Arizona. Discharge at Burro Spring has remained relatively constant since it was first measured in the 1980s, and discharge at Pasture Canyon Spring has fluctuated for the period of record. Continuous records of surface-water discharge in the Black Mesa area were collected from streamflow-gaging stations at the following sites: Moenkopi Wash at Moenkopi 09401260 (1976–2021), Dinnebito Wash near Sand Springs 09401110 (1993–2020), Polacca Wash near Second Mesa 09400568 (1994–2020), and Pasture Canyon Springs 09401265 (2004–2021). Median winter flows (November through February) of each winter were used as an estimate of the amount of groundwater discharge at the above-named sites. For the period of record, the median winter flows have generally remained constant at Polacca Wash and Pasture Canyon Springs, whereas a decreasing trend was observed at Moenkopi Wash and Dinnebito Wash. In 2020 and 2021, water samples were collected from a total of four springs in the Black Mesa area and analyzed for selected chemical constituents. Results from the four springs were compared with previous analyses from the same springs. Dissolved solids, chloride, and sulfate concentrations increased at Moenkopi School Spring during the more than 30 years of record at that site. Concentrations of dissolved solids and sulfate at Pasture Canyon Spring have not varied significantly (p>0.05) since the early 1980s, and there is no increasing or decreasing trend in those data. However, concentrations of chloride from Pasture Canyon Spring show a diminishing trend. Concentrations of dissolved solids, chloride, and sulfate at Unnamed Spring near Dennehotso have varied for the period of record, but there is no statistical trend in the data. Concentrations of dissolved solids at Burro Spring have varied for the period of record, but there is no statistical trend in the data. However, concentrations of chloride and sulfate from Burro Spring show a trend towards lower concentrations.

Arizona

Hydrogeology, hydrologic budget, and water chemistry of the Medina Lake area, Texas

A three-phase study of the Medina Lake area in Texas was done to assess the hydrogeology and hydrology of Medina and Diversion Lakes combined (the lake system) and to determine what fraction of seepage losses from the lake system might enter the regional ground-water-flow system of the Edwards and (or) Trinity aquifers. Phase 1 consisted of revising the geologic framework for the Medina Lake area. Results of field mapping show that the upper member of the Glen Rose Limestone underlies Medina Lake and the intervening stream channel from the outflow of Medina Lake to the midpoint of Diversion Lake, where the Diversion Lake fault intersects Diversion Lake. A thin sequence of strata consisting primarily of the basal nodular and dolomitic members of the Kainer Formation of the Edwards Group, is present in the southern part of the study area. On the southern side of Medina Lake, the contact between the upper member of the Glen Rose Limestone and the basal nodular member is approximately 1,000 feet above mean sea level, and the contact between the basal nodular member and the dolomitic member is approximately 1,050 feet above mean sea level. The most porous and permeable part of the basal nodular member is about 1,045 feet above mean sea level. At these altitudes, Medina Lake is in hydrologic connection with rocks in the Edwards aquifer recharge zone, and Medina Lake appears to lose more water to the ground-water system along this bedding plane contact. Hydrologic budgets calculated during phase 2 for Medina Lake, Diversion Lake, and Medina/Diversion Lakes combined indicate that: (1) losses from Medina and Diversion Lakes can be quantified; (2) a portion of those losses are entering the Edwards aquifer; and (3) losses to the Trinity aquifer in the Medina Lake area are minimal and within the error of the hydrologic budgets. Hydrologic budgets based on streamflow, precipitation, evaporation, and change in lake storage were used to quantify losses (recharge) to the ground-water system from Medina Lake, Diversion Lake, and Medina/Diversion Lakes combined during October 1995–September 1996. Water losses from Medina Lake to the Edwards/Trinity aquifers ranged from -14.0 to 135 acre-feet per day; Diversion Lake ranged from -1.2 to 93.1 acre-feet per day; and Medina/Diversion Lakes combined ranged from 36.1 to 119 acre-feet per day. Monthly average recharge during December 1995–July 1996 was estimated using an alternative method developed during this study (current study method) and compared to monthly average recharge during December 1995–July 1996 estimated using the existing USGS method and the Trans-Texas method. Recharge to the Edwards aquifer estimated using the current study method was about 69 and 73 percent of the recharge estimated using the USGS and Trans-Texas methods, respectively. The USGS and Trans-Texas methods overestimated recharge from Medina Lake compared to the recharge estimated with the current study method when Medina Lake stage was between about 1,027 and 1,032 feet above mean sea level and underestimated recharge from Medina Lake when lake stage was between about 1,036 and 1,045 feet above mean sea level. The USGS and Trans-Texas methods underestimated recharge from Diversion Lake compared to the recharge estimated with the current study method when Diversion Lake stage was greater than 913 feet above mean sea level and overestimated recharge from Diversion Lake when lake stage was less than 913 feet above mean sea level. The water quality of Medina Lake and Medina River and in selected wells and springs in the Edwards and Trinity aquifers was characterized during phase 3 of the study. Environmental isotope analyses and geochemical modeling also were used to determine where water losses from the lake system might be entering the ground-water-flow system. Isotopic ratios of deuterium, oxygen, and strontium were analyzed in selected surface-water, lake-water, and ground-water samples to trace the isotopic “signature” of the lake water as it mixes with the ground water and to determine the fraction of lake water and ground water in selected Edwards aquifer wells. Isotopic data and geochemical modeling were used to show that lake water is moving into the Edwards aquifer in two fault blocks in the eastern Medina storage unit. One fault block is bounded on the north by the Vandenburg School fault and on the south by the Haby Crossing fault, and the second fault block is bounded on the north by the Diversion Lake fault and on the south by the Haby Crossing fault. In selected Edwards aquifer wells located southwest of Medina Lake and west of Diversion Lake, the proportion of lake water ranged from about 10 to 45 percent. Geochemical modeling using NETPATH confirms the degree of mixing between lake water and aquifer water shown by the isotopes.

Texas

Groundwater, surface-water, and water-chemistry data, Black Mesa area, northeastern Arizona: 2011-2012

The Navajo (N) aquifer is an extensive aquifer and the primary source of groundwater in the 5,400-square-mile Black Mesa area in northeastern Arizona. Availability of water is an important issue in northeastern Arizona because of continued water requirements for industrial and municipal use by a growing population and because of low precipitation in the arid climate of the Black Mesa area. Precipitation in the area typically is between 6 and 14 inches per year. The U.S. Geological Survey water-monitoring program in the Black Mesa area began in 1971 and provides information about the long-term effects of groundwater withdrawals from the N aquifer for industrial and municipal uses. This report presents results of data collected as part of the monitoring program in the Black Mesa area from January 2011 to September 2012. The monitoring program includes measurements of (1) groundwater withdrawals, (2) groundwater levels, (3) spring discharge, (4) surface-water discharge, and (5) groundwater chemistry. In 2011, total groundwater withdrawals were 4,480 acre-ft, industrial withdrawals were 1,390 acre-ft, and municipal withdrawals were 3,090 acre-ft. Total withdrawals during 2011 were about 39 percent less than total withdrawals in 2005 because of Peabody Western Coal Company’s discontinued use of water to transport coal in a slurry. From 2010 to 2011 total withdrawals increased by 11 percent; industrial withdrawals increased by approximately 19 percent, and total municipal withdrawals increased by 8 percent. From 2011 to 2012, annually measured water levels in the Black Mesa area declined in 8 of 15 wells that were available for comparison in the unconfined areas of the N aquifer, and the median change was -0.1 feet. Water levels declined in 9 of 18 wells measured in the confined area of the aquifer. The median change for the confined area of the aquifer was 0.0 feet. From the prestress period (prior to 1965) to 2012, the median water-level change for 34 wells in both the confined and unconfined areas was -13.4 feet; the median water-level changes were -2.1 feet for 16 wells measured in the unconfined areas and -39.1 feet for 18 wells measured in the confined area. Spring flow was measured at four springs in 2012. Flow fluctuated during the period of record for Burro and Unnamed Spring near Dennehotso, but a decreasing trend was apparent at Moenkopi School Spring and Pasture Canyon Spring. Discharge at Burro Spring has remained relatively constant since it was first measured in the 1980s and discharge at Unnamed Spring near Dennehotso has fluctuated for the period of record. Trend analysis for discharge at Moenkopi and Pasture Canyon Springs yielded a slope significantly different from zero. Continuous records of surface-water discharge in the Black Mesa area were collected from streamflow-gaging stations at the following sites: Moenkopi Wash at Moenkopi 09401260 (1976 to 2010), Dinnebito Wash near Sand Springs 09401110 (1993 to 2010), Polacca Wash near Second Mesa 09400568 (1994 to 2010), and Pasture Canyon Springs 09401265 (2004 to 2010). Median winter flows (November through February) of each water year were used as an index of the amount of groundwater discharge at the above-named sites. For the period of record of each streamflow-gaging station, the median winter flows have generally remained constant, and there are no significant statistical trends in groundwater discharge. In 2012, water samples collected from 10 wells and 4 springs in the Black Mesa area were analyzed for selected chemical constituents, and the results were compared with previous analyses. Concentrations of dissolved solids, chloride, and sulfate have varied at all 10 wells for the period of record, but neither increasing nor decreasing trends over time were found. Dissolved solids, chloride, and sulfate concentrations increased at Moenkopi School Spring during the more than 12 years of record at that site. Concentrations of dissolved solids, chloride, and sulfate at Pasture Canyon Spring have not varied significantly since the early 1980s, and there is no increasing or decreasing trend in those data. Concentrations of dissolved solids, chloride, and sulfate at Burro Spring and Unnamed Spring near Dennehotso have varied for the period of record, but there is no increasing or decreasing trend in the data.

Arizona

Groundwater, surface-water, and water-chemistry data, Black Mesa area, northeastern Arizona—2012–2013

The Navajo (N) aquifer is an extensive aquifer and the primary source of groundwater in the 5,400-square-mile Black Mesa area in northeastern Arizona. Availability of water is an important issue in northeastern Arizona because of continued water requirements for industrial and municipal use by a growing population and because of low precipitation in the arid climate of the Black Mesa area. Precipitation in the area typically is between 6 and 14 inches per year. The U.S. Geological Survey water-monitoring program in the Black Mesa area began in 1971 and provides information about the long-term effects of groundwater withdrawals from the N aquifer for industrial and municipal uses. This report presents results of data collected as part of the monitoring program in the Black Mesa area from January 2012 to September 2013. The monitoring program includes measurements of (1) groundwater withdrawals, (2) groundwater levels, (3) spring discharge, (4) surface-water discharge, and (5) groundwater chemistry. In calendar year 2012, total groundwater withdrawals were 4,010 acre-ft, industrial withdrawals were 1,370 acre-ft, and municipal withdrawals were 2,640 acre-ft. Total withdrawals during 2012 were about 45 percent less than total withdrawals in 2005 because of Peabody Western Coal Company’s discontinued use of water to transport coal in a coal slurry pipeline. From 2011 to 2012 total withdrawals decreased by 10 percent; industrial withdrawals decreased by approximately 1 percent, and total municipal withdrawals decreased by 15 percent. From 2012 to 2013, annually measured water levels in the Black Mesa area declined in 6 of 16 wells that were available for comparison in the unconfined areas of the N aquifer, and the median change was 0.8 feet. Water levels declined in 5 of 16 wells measured in the confined area of the aquifer. The median change for the confined area of the aquifer was 0.3 feet. From the prestress period (prior to 1965) to 2013, the median water-level change for 34 wells in both the confined and unconfined areas was -13.5 feet; the median water-level changes were -0.8 feet for 16 wells measured in the unconfined areas and -51.0 feet for 16 wells measured in the confined area. Spring flow was measured at four springs in 2013; Burro, Unnamed Spring near Dennehotso, Moenkopi School, and Pasture Canyon Springs. Flow fluctuated during the period of record for Burro and Unnamed Springs near Dennehotso, but a decreasing trend was apparent at Moenkopi School Spring and Pasture Canyon Spring. Discharge at Burro Spring has remained relatively constant since it was first measured in the 1980s and discharge at Unnamed Spring near Dennehotso has fluctuated for the period of record at each spring. Trend analysis for discharge at Moenkopi School and Pasture Canyon Springs showed a decreasing trend. Continuous records of surface-water discharge in the Black Mesa area were collected from streamflow-gaging stations at the following sites: Moenkopi Wash at Moenkopi 09401260 (1976 to 2013), Dinnebito Wash near Sand Springs 09401110 (1993 to 2013), Polacca Wash near Second Mesa 09400568 (1994 to 2013), and Pasture Canyon Springs 09401265 (2004 to 2013). Median winter flows (November through February) from these sites for each water year were used as an index of the amount of groundwater discharge. For the period of record of each streamflow-gaging station, the median winter flows have generally remained constant, which suggests no change in groundwater discharge. In 2013, water samples collected from 12 wells and 4 springs in the Black Mesa area were analyzed for selected chemical constituents, and the results were compared with previous analyses. Concentrations of dissolved solids, chloride, and sulfate have varied at all 12 wells for the period of record, but neither increasing nor decreasing trends over time were found. Dissolved solids, chloride, and sulfate concentrations increased at Moenkopi School Spring during the more than 13 years of record at that site. Concentrations of dissolved solids, chloride, and sulfate at Pasture Canyon Spring have not varied significantly since the early 1980s. Concentrations of dissolved solids, chloride, and sulfate at Burro Spring and Unnamed Spring near Dennehotso have varied for the period of record with no increasing or decreasing trend in the data.

Arizona

Tolerance of freshwater test organisms to formulated sediments for use as control materials in whole-sediment toxicity tests

A method is described for preparing formulated sediments for use intoxicity testing. Ingredients used to prepare formulated sediments included commercially available silt, clay, sand, humic acid, dolomite, and α-cellulose (as a source of organic carbon). α-Cellulose was selected as the source of organic carbon because it is commercially available, consistent from batch to batch, and low in contaminant concentrations. The tolerance of freshwater test organisms to formulated sediments for use as control materials in whole-sediment toxicity testing was evaluated. Sediment exposures were conducted for 10 d with the amphipod Hyalella azteca , the midges Chironomus riparius and C. tentans , and the oligochaete Lumbriculus variegatus and for 28 d with H. azteca . Responses of organisms in formulated sediments was compared with a field-collected control sediment that has routinely been used to determine test acceptability. Tolerance of organisms to formulated sediments was evaluated by determining responses to varying levels of α-cellulose, to varying levels of grain size, to evaluation of different food types, or to evaluation of different sources of overlying water. In the 10-d exposures, survival of organisms exposed to the formulated sediments routinely met or exceeded the responses of test organisms exposed to the control sediment and routinely met test acceptability criteria required in standard methods. Growth of amphipods and oligochaetes in 10-d exposures with formulated sediment was often less than growth of organisms in the field-collected control sediment. Additional research is needed, using the method employed to prepare formulated sediment, to determine if conditioning formulated sediments before starting 10-d tests would improve the growth of amphipods. In the 28-d exposures, survival of H. azteca was low when reconstituted water was used as the source of overlying water. However, when well water was used as the source of overlying water in 28-d exposures, consistent responses of amphipods were observed in both formulated and control sediments.

Environmental Toxicology and Chemistry

Workshop 3.5: Closing the gap between exposure and effects in monitoring studies

A major challenge to contaminant monitoring programs is the selection of an appropriate suite of measurements for assessing exposure and effects. Early monitoring programs relied solely on residue analysis to detect the organochlorine compounds that were in use at that time. A shift to the use of more transient, less persistent chemicals required that a new set of tools be developed to determine if an organism had been exposed. This led to the development of cellular and biochemical assays that could indicate the presence of these types of chemicals in biota and the environment. However, it was recognized that measures of contaminant presence alone were insufficient to assess the health of biota. As a result, considerable research began to be directed toward development of diagnostic tools for measuring chemical effects in fish and wildlife. Today, contaminant monitoring programs follow a paradigm for study design that emphasizes not only the use of measures of exposure, but also measures of effect. Using data from our monitoring and research studies for hormonally active substances, we discuss a variety of metrics of exposure and effects and their application to specific chemicals, and the current information gaps. We conclude that although several bioindicators of exposure and effect have been promoted and used, to date there continues to be a poor association between cause and effect for endocrine active substances. In part, this is due to the limited number of diagnostic tools that are available and to a lack of basic toxicological information concerning toxicokinetics and mechanisms of action of hormonally active chemicals in fish and wildlife species. In the foreseeable future, both tissue and environmental residue data, despite the many limitations, will continue to be an important component of monitoring programs for hormonally active chemicals as we continue to develop and validate more specific bioindicators of exposure and effects.

Pure and Applied Chemistry

Herbicides and their transformation products in source-water aquifers tapped by public-supply wells in Illinois, 2001-02

During 2001-02, ground-water samples were collected from 117 public-supply wells distributed throughout Illinois to evaluate the occurrence of herbicides and their transformation products in the State?s source-water aquifers. Wells were selected using a stratified-random method to ensure representation of the major types of source-water aquifers in the State. Samples were analyzed for 18 herbicides and 18 transformation products, including 3 triazine and 14 chloroacetanilide products. Herbicide compounds (field-applied parent herbicides and their transformation products) were detected in 34 percent of samples. A subset of samples was collected unfiltered to determine if analytical results for herbicides in unfiltered samples are similar to those in paired filtered samples and, thus, can be considered equally representative of herbicide concentrations in ground water supplied to the public. The study by the U.S. Geological Survey was done in cooperation with the Illinois Environmental Protection Agency. Parent herbicides were detected in only 4 percent of all samples. The six most frequently detected herbicide compounds (from 5 to 28 percent of samples) were chloroacetanilide transformation products. The frequent occurrence of transformation products and their higher concentrations relative to those of most parent herbicides confirm the importance of obtaining information on transformation products to understand the mobility and fate of herbicides in ground-water systems. No sample concentrations determined during this study exceeded current (2003) Federal or State drinking-water standards; however, standards are established for only seven parent herbicides. Factors related to the occurrence of herbicide compounds in the State?s source-water aquifers include unconsolidated and unconfined conditions, various hydrogeologic characteristics and well-construction aspects at shallow depths, and proximity to streams. Generally, the closer an aquifer (or well location) is to a recharge area and (or) the stronger the hydraulic connection between an aquifer and a recharge area, the younger the ground water and the more vulnerable the aquifer will be to contamination by herbicide compounds. The weak relation between current (2001) statewide application rates of herbicides and current (2001-02) occurrence of herbicide compounds in source-water aquifers indicates that additional factors must be considered when relating herbicide-application rates to occurrence. These factors include historical application rates and the mobility and persistence of the various herbicide compounds in ground-water systems. Frequency of detection and concentrations of herbicides compounds in the State?s source-water aquifers are indicated to be highest during the spring, when crops are planted and herbicides primarily are applied. Excess nitrate (concentrations of nitrate, as nitrogen, higher than 3 milligrams per liter) in ground water strongly indicates the co-occurrence of herbicide compounds. However, nitrate concentrations are not a reliable indicator of herbicide-compound concentrations. The inverse relation found between current use of land for corn and soybean production and current occurrence of herbicide compounds in underlying aquifers indicates that various factors, along with current agricultural land use, contribute to herbicide occurrence. These factors include, among others, land-use history, ground-water age, ground-water-flow patterns, geology, soil microbiology, and chemistry and persistence of the herbicide compounds. Detection of agriculture-specific herbicide compounds in 71 percent of samples from urban areas with no current or recent agricultural land use near the sampled wells indicates that recharge to certain high-capacity supply wells may originate at considerable distances (up to about 10 miles) from the wells. Essentially no difference was found between the analytical results for herbicides in paired unfiltered and filtered samples,

Water-Resources Investigations Report