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Diagnostic tools for mixing models of stream water chemistry

Mixing models provide a useful null hypothesis against which to evaluate processes controlling stream water chemical data. Because conservative mixing of end‐members with constant concentration is a linear process, a number of simple mathematical and multivariate statistical methods can be applied to this problem. Although mixing models have been most typically used in the context of mixing soil and groundwater end‐members, an extension of the mathematics of mixing models is presented that assesses the “fit” of a multivariate data set to a lower dimensional mixing subspace without the need for explicitly identified end‐members. Diagnostic tools are developed to determine the approximate rank of the data set and to assess lack of fit of the data. This permits identification of processes that violate the assumptions of the mixing model and can suggest the dominant processes controlling stream water chemical variation. These same diagnostic tools can be used to assess the fit of the chemistry of one site into the mixing subspace of a different site, thereby permitting an assessment of the consistency of controlling end‐members across sites. This technique is applied to a number of sites at the Panola Mountain Research Watershed located near Atlanta, Georgia.

Water Resources Research

Spring runoff water-chemistry data from the Standard Mine and Elk Creek, Gunnison County, Colorado, 2010

Water samples were collected approximately every two weeks during the spring of 2010 from the Level 1 portal of the Standard Mine and from two locations on Elk Creek. The objective of the sampling was to: (1) better define the expected range and timing of variations in pH and metal concentrations in Level 1 discharge and Elk Creek during spring runoff; and (2) further evaluate possible mechanisms controlling water quality during spring runoff. Samples were analyzed for major ions, selected trace elements, and stable isotopes of oxygen and hydrogen (oxygen-18 and deuterium). The Level 1 portal sample and one of the Elk Creek samples (EC-CELK1) were collected from the same locations as samples taken in the spring of 2007, allowing comparison between the two different years. Available meteorological and hydrologic data suggest that 2010 was an average water year and 2007 was below average. Field pH and dissolved metal concentrations in Level 1 discharge had the following ranges: pH, 2.90 to 6.23; zinc, 11.2 to 26.5 mg/L; cadmium, 0.084 to 0.158 mg/L; manganese, 3.23 to 10.2 mg/L; lead, 0.0794 to 1.71 mg/L; and copper, 0.0674 to 1.14 mg/L. These ranges were generally similar to those observed in 2007. Metal concentrations near the mouth of Elk Creek (EC-CELK1) were substantially lower than in 2007. Possible explanations include remedial efforts at the Standard Mine site implemented after 2007 and greater dilution due to higher Elk Creek flows in 2010. Temporal patterns in pH and metal concentrations in Level 1 discharge were similar to those observed in 2007, with pH, zinc, cadmium, and manganese concentrations generally decreasing, and lead and copper generally increasing during the snowmelt runoff period. Zinc and cadmium concentrations were inversely correlated with flow and thus apparently dilution-controlled. Lead and copper concentrations were inversely correlated with pH and thus apparently pH-controlled. Zinc, cadmium, and manganese concentrations near the mouth of Elk Creek did not display the pronounced increase observed during high flow in 2007, again perhaps due to remedial activities at the mine site or greater dilution in 2010. Zinc and cadmium loads near the mouth of Elk Creek were generally greater than those at the Level 1 portal for the six sample days in 2010. Whereas metal loads in September 2007 suggested that Level 1 portal discharge was the primary source of metals to the creek, metal loads computed for this study suggest that this may not have been the case in the spring of 2010. d18O values are well correlated with flow, becoming lighter (more negative) during snowmelt in both Level 1 discharge and Elk Creek. Seasonal variations in the chemistry of Level 1 discharge, along with portal flow tracking very closely with creek flow, are consistent with geochemical and environmental tracer data from 2007 that indicate short residence times (<1 year) for groundwater discharging from the Standard Mine.

Colorado

Heterogeneity in hyporheic flow, pore water chemistry, and microbial community composition in an alpine streambed

The hyporheic zone, where surface water and groundwater mix, is an important microbial habitat where biogeochemical reactions influence water quality. We show that spatial variability in hyporheic flow in the East River near Crested Butte, Colorado, drives heterogeneity in streambed geochemical conditions and microbial community assemblages, but the diversity of assemblages remains nearly constant throughout the reach. In July 2018, we collected approximately 100 pore water samples at 20 cm depth and analyzed them for anions, cations, dissolved organic carbon, dissolved organic matter (DOM) quality, and basic water quality parameters. Vertical hydraulic head gradients were also measured to assess the potential for upward or downward flow, and heat tracing was used to quantify vertical flux rates at a subset of locations. We found that regions of the streambed that are more groundwater-dominated contain less dissolved oxygen, higher concentrations of reduced metals, and more microbially-processed, recalcitrant DOM, while more surface water-dominated locations contain higher dissolved oxygen concentrations and terrestrially-derived, labile DOM. 16S rRNA gene sequencing of extracted DNA revealed that microbial community composition varies with geochemical gradients related to hyporheic flow. These findings provide a better understanding of hyporheic controls on streambed biogeochemistry during the baseflow season, which is expected to lengthen with climate change in alpine watersheds due to earlier snowmelt onset and reduced snowpack.

Colorado

Water-chemistry data for selected springs, geysers, and streams in Yellowstone National Park Wyoming, 2001-2002

Water analyses are reported for one-hundred-twenty-one samples collected from hot springs and their overflow drainages, the Gibbon River, and one ambient-temperature acid stream in Yellowstone National Park (YNP) during 2001-2002. Twenty-five analyses are reported for samples collected during May 2001, fifty analyses are reported for samples collected during September 2001, eleven analyses are reported for samples collected during October 2001, and thirty-five analyses are reported for samples collected during June and July 2002. Water samples were collected and analyzed for major and trace constituents from nine areas of YNP including Norris Geyser Basin, Nymph Lake and Roadside Springs, Lower Geyser Basin, Washburn Springs, Calcite Springs, Crater Hills, Mammoth Hot Springs, West Thumb Geyser Basin, and Brimstone Basin. These water samples were collected and analyzed as part of research investigations in YNP on arsenic redox distribution in hot springs and overflow drainages, the occurrence and distribution of dissolved mercury, and sulfur redox speciation. Most samples were analyzed for major cations and anions, trace metals, and iron, arsenic, nitrogen, and sulfur redox species. Only mercury concentration, pH, and specific conductance were determined for samples collected in October 2001 as they were collected during a reconnaissance field trip. Analyses were performed at the sampling site, in an onsite mobile laboratory, or later in a U.S. Geological Survey laboratory, depending on stability of the constituent and whether it could be preserved effectively. Water samples were filtered and preserved onsite. Water temperature, specific conductance, pH, Eh, and dissolved hydrogen sulfide were measured onsite at the time of sampling. Alkalinity and acidity were determined by titration, usually within a few days of sample collection. Concentrations of thiosulfate (S 2 O 3 ) and polythionate (S n O 6 ) were determined as soon as possible (generally minutes to hours after sample collection) by ion chromatography in an onsite mobile laboratory vehicle. Total dissolved iron and ferrous iron concentrations often were measured onsite in the mobile laboratory. Concentrations of aluminum, arsenic, barium, beryllium, boron, cadmium, calcium, chromium, cobalt, copper, iron, lead, lithium, magnesium, manganese, molybdenum, nickel, potassium, selenium, silica, sodium, strontium, vanadium, and zinc were determined by inductively coupled plasma-optical emission spectrometry. Trace concentrations of antimony, cadmium, chromium, cobalt, copper, lead, and selenium were determined by Zeeman-corrected graphite-furnace atomic-absorption spectrometry. Concentrations of total arsenic and arsenite were determined by hydride-generation atomic-absorption spectrometry using a flow-injection analysis system. Concentrations of total mercury were determined by cold-vapor atomic fluorescence spectrometry. Concentrations of bromide, chloride, nitrate, and sulfate were determined by ion chromatography. Concentrations of ferrous and total iron were determined by the FerroZine colorimetric method. Concentrations of nitrite were determined by colorimetry or chemiluminescence. Concentrations of ammonia were determined by ion chromatography, with reanalysis by colorimetry when separation of sodium and ammonia peaks was poor. Dissolved organic carbon concentrations were determined by the wet persulfate oxidation method.

Wyoming

Water-chemistry data for selected springs, geysers, and streams in Yellowstone National Park, Wyoming, 2003-2005

Water analyses are reported for 157 samples collected from numerous hot springs, their overflow drainages, and Lemonade Creek in Yellowstone National Park (YNP) during 2003–2005. Water samples were collected and analyzed for major and trace constituents from ten areas of YNP including Terrace and Beryl Springs in the Gibbon Canyon area, Norris Geyser Basin, the West Nymph Creek thermal area, the area near Nymph Lake, Hazle Lake, and Frying Pan Spring, Lower Geyser Basin, Washburn Hot Springs, Mammoth Hot Springs, Potts Hot Spring Basin, the Sulphur Caldron area, and Lemonade Creek near the Solfatara Trail. These water samples were collected and analyzed as part of research investigations in YNP on arsenic, antimony, and sulfur redox distribution in hot springs and overflow drainages, and the occurrence and distribution of dissolved mercury. Most samples were analyzed for major cations and anions, trace metals, redox species of antimony, arsenic, iron, nitrogen, and sulfur, and isotopes of hydrogen and oxygen. Analyses were performed at the sampling site, in an on-site mobile laboratory vehicle, or later in a U.S. Geological Survey laboratory, depending on stability of the constituent and whether it could be preserved effectively. Water samples were filtered and preserved onsite. Water temperature, specific conductance, pH, Eh (redox potential relative to the Standard Hydrogen Electrode), and dissolved hydrogen sulfide were measured onsite at the time of sampling. Acidity was determined by titration, usually within a few days of sample collection. Alkalinity was determined by titration within 1 to 2 weeks of sample collection. Concentrations of thiosulfate and polythionate were determined as soon as possible (generally minutes to hours after sample collection) by ion chromatography in an on-site mobile laboratory vehicle. Total dissolved-iron and ferrous-iron concentrations often were measured onsite in the mobile laboratory vehicle. Concentrations of dissolved aluminum, arsenic, boron, barium, beryllium, calcium, cadmium, cobalt, chromium, copper, iron, potassium, lithium, magnesium, manganese, molybdenum, sodium, nickel, lead, selenium, silica, strontium, vanadium, and zinc were determined by inductively-coupled plasma-optical emission spectrometry. Trace concentrations of dissolved antimony, cadmium, cobalt, chromium, copper, lead, and selenium were determined by Zeeman-corrected graphite-furnace atomic-absorption spectrometry. Dissolved concentrations of total arsenic, arsenite, total antimony, and antimonite were determined by hydride-generation atomic-absorption spectrometry using a flow-injection analysis system. Dissolved concentrations of total mercury and methyl mercury were determined by cold-vapor atomic-fluorescence spectrometry. Concentrations of dissolved chloride, fluoride, nitrate, bromide, and sulfate were determined by ion chromatography. Concentrations of dissolved ferrous and total iron were determined by the FerroZine colorimetric method. Concentrations of dissolved nitrite were determined by colorimetry or chemiluminescence. Concentrations of dissolved ammonium were determined by ion chromatography, with reanalysis by colorimetry when separation of sodium and ammonia peaks was poor. Dissolved organic carbon concentrations were determined by the wet persulfate oxidation method. Hydrogen and oxygen isotope ratios were determined using the hydrogen and CO 2 equilibration techniques, respectively.

Wyoming

Water-chemistry data for selected springs, geysers, and streams in Yellowstone National Park, Wyoming, 2006-2008

Water analyses are reported for 104 samples collected from numerous thermal and non-thermal features in Yellowstone National Park (YNP) during 2006-2008. Water samples were collected and analyzed for major and trace constituents from 10 areas of YNP including Apollinaris Spring and Nymphy Creek along the Norris-Mammoth corridor, Beryl Spring in Gibbon Canyon, Norris Geyser Basin, Lower Geyser Basin, Crater Hills, the Geyser Springs Group, Nez Perce Creek, Rabbit Creek, the Mud Volcano area, and Washburn Hot Springs. These water samples were collected and analyzed as part of research investigations in YNP on arsenic, antimony, iron, nitrogen, and sulfur redox species in hot springs and overflow drainages, and the occurrence and distribution of dissolved mercury. Most samples were analyzed for major cations and anions, trace metals, redox species of antimony, arsenic, iron, nitrogen, and sulfur, and isotopes of hydrogen and oxygen. Analyses were performed at the sampling site, in an on-site mobile laboratory vehicle, or later in a U.S. Geological Survey laboratory, depending on stability of the constituent and whether it could be preserved effectively. Water samples were filtered and preserved on-site. Water temperature, specific conductance, pH, emf (electromotive force or electrical potential), and dissolved hydrogen sulfide were measured on-site at the time of sampling. Dissolved hydrogen sulfide was measured a few to several hours after sample collection by ion-specific electrode on samples preserved on-site. Acidity was determined by titration, usually within a few days of sample collection. Alkalinity was determined by titration within 1 to 2 weeks of sample collection. Concentrations of thiosulfate and polythionate were determined as soon as possible (generally a few to several hours after sample collection) by ion chromatography in an on-site mobile laboratory vehicle. Total dissolved iron and ferrous iron concentrations often were measured on-site in the mobile laboratory vehicle. Concentrations of dissolved aluminum, arsenic, boron, barium, beryllium, calcium, cadmium, cobalt, chromium, copper, iron, potassium, lithium, magnesium, manganese, molybdenum, sodium, nickel, lead, selenium, silica, strontium, vanadium, and zinc were determined by inductively coupled plasma-optical emission spectrometry. Trace concentrations of dissolved antimony, cadmium, cobalt, chromium, copper, lead, and selenium were determined by Zeeman-corrected graphite-furnace atomic-absorption spectrometry. Dissolved concentrations of total arsenic, arsenite, total antimony, and antimonite were determined by hydride generation atomic-absorption spectrometry using a flow-injection analysis system. Dissolved concentrations of total mercury and methylmercury were determined by cold-vapor atomic fluorescence spectrometry. Concentrations of dissolved chloride, fluoride, nitrate, bromide, and sulfate were determined by ion chromatography. For many samples, concentrations of dissolved fluoride also were determined by ion-specific electrode. Concentrations of dissolved ferrous and total iron were determined by the FerroZine colorimetric method. Concentrations of dissolved ammonium were determined by ion chromatography, with reanalysis by colorimetry when separation of sodium and ammonia peaks was poor. Dissolved organic carbon concentrations were determined by the wet persulfate oxidation method. Hydrogen and oxygen isotope ratios were determined using the hydrogen and CO 2 equilibration techniques, respectively.

Wyoming

Significance of ground-water chemistry in performance of North Sahara Tube wells in Algeria and Tunisia

Nine ground-water samples from the principal shallow and deep North Sahara aquifers of Algeria and Tunisia were examined to determine the relation of their chemical composition to corrosion and mineral encrustation thought to be contributing to observed decline in well capacities within a UNESCO/UNDP Special Fund Project area. Although the shallow and deep waters differ significantly in certain quality factors, all are sulfochloride types with corrosion potentials ranging from moderate to extreme. None appear to be sufficiently supersaturated with troublesome mineral species to cause rapid or severe encrustation of filter pipes or other well parts. However, calcium carbonate encrustation of deep-well cooling towers and related irrigation pipes can be expected because of loss of carbon dioxide and water during evaporative cooling. Corrosion products, particularly iron sulfide, can be expected to deposit in wells producing waters from the deep aquifers. This could reduce filterpipe openings and increase casing roughness sufficiently to cause significant reduction in well capacity. It seems likely, however, that normal pressure reduction due to exploitation of the artesian systems is a more important control of well performance. If troublesome corrosion and related encrustation are confirmed by downhole inspection, use of corrosion-resisting materials, such as fiber-glass casing and saw-slotted filter pipe (shallow wells only), or stainless-steel screen, will minimize the effects of the waters represented by these samples. A combination of corrosion-resisting stainless steel filter pipe electrically insulated from the casing with a nonconductive spacer and cathodic protection will minimize external corrosion of steel casing, if this is found to be a problem. However, such installations are difficult to make in very deep wells and difficult to control in remote areas. Both the shallow waters and the deep waters examined in this study will tend to cause soil salinization because their salt contents are relatively high, and both have sodium absorption ratios which are unfavorable to sodium-sensitive soils and vegetation. Proper drainage and soil treatment are the only means of overcoming these problems during irrigation.

Water Supply Paper

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

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

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

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 - 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

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

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— 2008–2009

The 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, which is typically about 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 2008 to September 2009. The monitoring program includes measurements of (1) groundwater withdrawals, (2) groundwater levels, (3) spring discharge, (4) surface-water discharge, and (5) groundwater chemistry. In 2008, total groundwater withdrawals were 4,110 acre-feet, industrial withdrawals were 1,210 acre-ft, and municipal withdrawals were 2,900 acre-ft. Total withdrawals during 2008 were about 44 percent less than total withdrawals in 2005. From 2007 to 2008 total withdrawals decreased by 4 percent, industrial withdrawals increased by approximately 3 percent, but total municipal withdrawals decreased by 6 percent. From 2008 to 2009, 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 11 of 18 wells measured in the confined area of the aquifer. The median change for the confined area of the aquifer was -0.2 feet. From the prestress period (prior to 1965) to 2009, the median water-level change for 34 wells in both the confined and unconfined area was -11.8 feet. Also, from the prestress period to 2009, the median water-level changes were -1.6 feet for 16 wells measured in the unconfined areas and -36.7 feet for 18 wells measured in the confined area. Spring flow was measured at three springs in 2009. 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 constant since it was first measured in 1998. 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 2008), Dinnebito Wash near Sand Springs 09401110 (1993 to 2008), Polacca Wash near Second Mesa 09400568 (1994 to 2008), and Pasture Canyon Springs 09401265 (August 2004 to 2008). 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 2009, water samples collected from 6 wells and 3 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 6 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 trend in those data. Concentrations of dissolved solids, chloride, and sulfate at Burro Spring have varied for the period of record, but there is no trend in the data.

Arizona

Groundwater, surface–water, and water-chemistry data, Black Mesa area, northeastern Arizona—2007-2008

The 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, which is typically about 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 2007 to September 2008. The monitoring program includes measurements of (1) groundwater withdrawals, (2) groundwater levels, (3) spring discharge, (4) surface-water discharge, and (5) groundwater chemistry. In 2007, total groundwater withdrawals were 4,270 acre-feet, industrial withdrawals were 1,170 acre-ft, and municipal withdrawals were 3,100 acre-ft. Total withdrawals during 2007 were about 41 percent less than total withdrawals in 2005. From 2006 to 2007, however, total withdrawals increased by 4 percent, industrial withdrawals decreased by approximately 2 percent, and total municipal withdrawals increased by 7 percent. From 2007 to 2008, annually measured water levels in the Black Mesa area declined in 6 of 11 wells measured in the unconfined areas of the N aquifer, and the median change was -0.2 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 -0.2 feet. From the prestress period (prior to 1965) to 2008, the median water-level change for 33 wells in both the confined and unconfined area was -12.9 feet. Median water-level changes were -1.0 feet for 15 wells measured in the unconfined areas and -33.2 feet for 18 wells measured in the confined area. Spring flow was measured at two springs in 2008. Flow decreased at both Moenkopi School Spring and Pasture Canyon Spring from previous years. Flow fluctuated during the period of record, but a decreasing trend was apparent. 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 2007), Dinnebito Wash near Sand Springs 09401110 (1993 to 2007), Polacca Wash near Second Mesa 09400568 (1994 to 2007), and Pasture Canyon Springs 09401265 (August 2004 to 2007). 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. The period of record is too short to determine if there is a trend at Pasture Canyon Spring. In 2008, water samples collected from 6 wells and 2 springs in the Black Mesa area were analyzed for selected chemical constituents and the results compared with previous analyses. Concentrations of dissolved solids, chloride, and sulfate have varied at all 6 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 trend in those data.

Arizona

Diel changes in water chemistry in an arsenic-rich stream and treatment-pond system

Arsenic concentrations are elevated in surface waters of the Warm Springs Ponds Operable Unit (WSPOU), located at the head of the upper Clark Fork River Superfund site, Montana, USA. Arsenic is derived from historical deposition of smelter emissions (Mill and Willow Creeks) and historical mining and milling wastes (Silver Bow Creek). Although long-term monitoring has characterized the general seasonal and flow-related trends in As concentrations in these streams and the pond system used to treat Silver Bow Creek water, little is known about solubility controls and sorption processes that influence diel cycles in As concentrations. Diel (24-h) sampling was conducted in July 2004 and August 2005 at the outlet of the treatment ponds, at two locations along a nearby reconstructed stream channel that diverts tributary water around the ponds, and at Silver Bow Creek 2 km below the ponds. Dissolved As concentration increased up to 51% during the day at most of the stream sites, whereas little or no diel change was displayed at the treatment-pond outlet. The strong cycle in streams is explained by pH- and temperature-dependent sorption of As onto hydrous metal oxides or biofilms on the streambed. Concentrations of dissolved Ca 2+ and HCO 3 − at the stream sites showed a diel temporal pattern opposite to that of As, and geochemical modeling supports the hypothesis that the concentrations of Ca 2+ and HCO 3 − were controlled by precipitation of calcite during the warm afternoon hours when pH rose above 9.0. Nightly increases in dissolved Mn and Fe(II) concentrations were out of phase with concentrations of other divalent cations and are more likely explained by redox phenomena.

Montana