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Groundwater, surface-water, and water-chemistry data from C-aquifer monitoring program, northeastern Arizona, 2005-11

The C aquifer is a regionally extensive multiple-aquifer system supplying water for municipal, agricultural, and industrial use in northeastern Arizona, northwestern New Mexico, and southeastern Utah. An increase in groundwater withdrawals from the C aquifer coupled with ongoing drought conditions in the study area increase the potential for drawdown within the aquifer. A decrease in the water table and potentiometric surface of C aquifer is illustrated locally by the drying up of Obed Meadows, a natural peat deposit, and Hugo Meadows, a natural wetland, both south of Joseph City, Arizona. Continual increase in water use from the C aquifer, including a planned increase in pumpage by the City of Flagstaff, is justification for continued monitoring of the C-aquifer system in order to quantify physical and chemical responses to pumping stresses. Fifteen of the 35 C-aquifer wells analyzed had water-level data sufficient for percentage difference calculation for 2005–11. Change in water level as a percentage of the initial water-level measurement for these 15 wells ranged from about -0.2 to about -0.5 percent. For historical water-level data, changes in water levels were greatest around pumping centers, as indicated by a -97.0 feet (percentage difference of -16.5 percent) change over the period of record (1962–2005) for the Lake Mary 1 Well near Flagstaff, Arizona. In more rural areas of the C aquifer, water levels showed less change for both the temporal focus of this report (2005–11) and for historical values. Continuous records of surface-water discharge from 2005 to 2007 for three discontinued streamflow-gaging stations (Clear Creek near Winslow, AZ, 09399000; Clear Creek below McHood Lake near Winslow, AZ, 09399100; and Chevelon Creek near Winslow, AZ, 09398000) were tabulated. For the period of record, Clear Creek near Winslow, AZ, and Chevelon Creek near Winslow, AZ, showed seasonal discharge distributions indicative of natural streams in the southwestern United States. Clear Creek below McHood Lake near Winslow, AZ, showed discharge distribution indicative of perennial spring flow with little variation annually. Physical and chemical data collected during four baseflow investigations (summer 2005, summer 2006, summer 2008, and winter 2010) conducted on Clear Creek, Chevelon Creek, and a portion of the Little Colorado River were compiled and analyzed. Data from 7 sampling sites established on the Little Colorado River, 11 sites along Chevelon Creek, and 14 sites along Clear Creek were included. For the four baseflow investigations presented, a 2,000–3,000 microsiemens per centimeter increase in specific conductance was measured in Chevelon Creek from near its headwaters to the confluence with the Little Colorado River because of the contribution of highly conductive spring discharge. Clear Creek showed a less consistent pattern of increase in specific conductance with distance, but still exhibited changes on the order of 5,000 microsiemens per centimeter over just a few river miles. Water-chemistry data for selected wells and baseflow investigations sites are presented. No well samples analyzed exceeded the U.S. Environmental Protection Agency Maximum Contaminant Level standards for drinking water, but several samples exceeded Secondary Maximum Contaminant Level standards for chloride, fluoride, sulfate, iron, and total dissolved solids.

Arizona

Effectiveness of an alluvial wetland on improving ground-water quality in a municipal well field, Cedar Rapids, Iowa, 1998-2006

Nutrients and pesticides are water-quality topics of concern in Iowa. Nitrate concentrations in the Cedar River and other streams in Iowa are among the highest in the Nation. A 12-mile reach of the Cedar River upstream from Cedar Rapids, Iowa, is identified on the Total Maximum Daily Load list for nitrate impairment by the U.S. Environmental Protection Agency. In addition, pesticide concentrations in water samples from alluvial aquifers in Iowa have been ranked as some of the largest in the Nation. The Cedar River, like many rivers with alluvium, affects the alluvial aquifer that is used as a municipal water supply for Cedar Rapids, Iowa. A continuing challenge for the Cedar Rapids Water Department is to provide drinking water that meets all drinking-water regulations; this is made more of a challenge because of the high (often over 10 milligrams per liter) nitrate concentrations in the Cedar River and the presence of other potential chemicals of concern, such as pesticides. An alluvial wetland proved useful in improving water quality. Samples from observation wells completed in the alluvial wetland near the municipal well field had nitrate concentrations that were four to six times lower when compared to river or upland sites; however, iron and manganese concentrations in samples from observation wells in the wetland areas were an order of magnitude higher when compared to the river or an upgradient well. Biological and chemical reduction processes were determined to mobilize inorganic constituents in accordance with physical chemistry principles. Generally, selected pesticides and two pesticide degradates of atrazine that were sampled for in alluvial wetland wells remained relatively unchanged, and indicated only a slight decrease in concentration compared to the Cedar River water samples. Pesticides were not detected above regulatory limits in any of the observation wells; however, one sample from the Cedar River had an atrazine detection at 4.5 micrograms per liter, which is above the maximum contaminant level of 3.0 micrograms per liter for drinking-water regulations for that compound. Results indicate that alluvial wetlands may provide substantial reductions of nitrate concentrations in ground water, and may be a useful strategy for the reduction of nitrate for municipal wells. Results for reducing pesticides were less dramatic than for nitrate, as pesticide concentrations were reduced slightly from the river to the wetland.

Iowa

Hydrological conditions and evaluation of sustainable groundwater use in the Sierra Vista Subwatershed, Upper San Pedro Basin, southeastern Arizona

This study assessed progress toward achieving sustainable groundwater use in the Sierra Vista Subwatershed of the Upper San Pedro Basin, Arizona, through evaluation of 14 indicators of sustainable use. Sustainable use of groundwater in the Sierra Vista Subwatershed requires, at a minimum, a stable rate of groundwater discharge to, and thus base flow in, the San Pedro River. Many of the 14 indicators are therefore related to long-term or short-term effects on base flow and provide us with a means to evaluate groundwater discharge to and base flow in the San Pedro River. The indicators were based primarily on 10 to 20 years of data monitoring in the subwatershed, ending in 2012, and included subwatershedwide indicators, riparian-system indicators, San Pedro River indicators, and springs indicators. Groundwater management actions including voluntary retirement of irrigation pumping in the subwatershed resulted in about a 5,100 acre-feet (acre-ft) reduction in net human use from 2002 to 2012. Subwatershed population increased more than 10,000 during the same period. Most of the reduction occurred during 2002–07 and included reductions in groundwater pumping and increases in managed recharge; net human use varied annually by a few hundred acre-ft during 2007–12. The groundwater budget for 2012 showed a deficit of about 5,000 acre-ft, although the total water-budget uncertainty was about 5,500 acre-ft. In the vicinity of the U.S. Army’s Fort Huachuca, regional-aquifer water levels were in steady decline beginning in at least the mid-1990s (in older wells since at least the early-1970s), as the cone of depression centered on the Sierra Vista and Fort Huachuca pumping centers continued to deepen. This was evident in the individual water levels on Fort Huachuca, as well as from the horizontal hydraulic gradients that extend from the pumping centers toward the San Pedro and Babocomari Rivers. Basin water levels in wells southeast of Sierra Vista, away from the river, were also experiencing declines, while some water levels closer to the river were rising. Near-stream vertical gradients along the San Pedro River showed no clear increasing or decreasing trends that would indicate a shift in the direction of subsurface flow between the riverbed and the alluvial aquifer, or a trend in the magnitude of groundwater/surface-water exchange. Annual streamflow permanence data showed no clear change in streamflow permanence trends in any of the river reaches, other than those related to precipitation trends. Similarly, the single-day, dry-season, wet-dry streamflow analysis of all subwatershed river reaches indicated no change in condition over the past 14 years, with the exception of the Hereford reach, which has seen a statistically significant increase in wetted length. Dry-season, alluvial-aquifer water levels in the Hereford reach also showed a statistically significant increase. These improvements are attributed to the end of irrigation pumping in the area. Although data indicate that the length of the Fairbank North wetted reach may be in decline, it is not yet statistically significant. Stable-isotope data indicated reduced groundwater discharge to the Babocomari River in the vicinity of the Babocomari River near Tombstone gaging station and to the San Pedro River near the San Pedro River at Palominas gaging station and near the Lewis Springs DCP stage recorder. The Babocomari River near Tombstone gaging station is downgradient of the major pumping centers. The change in isotopic signature at the Lewis Springs stage recorder could have been the result of alterations in groundwater/surface-water interactions there caused by beaver damming of the river. Base flow in the San Pedro River declined over the periods of record at the three San Pedro River gaging stations in the subwatershed (Palominas, Charleston, and Tombstone), as well as at the Babocomari River near Tombstone gaging station. Precipitation declined slightly from the 1990s to the 2000s, although there is no statistically significant trend in subwatershed precipitation from 1991 to 2012. The occurrence of large winter discharge events appeared to decline and that of large summer discharge events appeared to increase over this same period. Data for physical parameters, general chemistry, nutrient species, select trace elements, and suspended sediment were collected at San Pedro River at Charleston stream-gaging station. These data were summarized over time and analyzed in relation to discharge and season as a means to assess trends over the period of analysis. Federal and State of Arizona drinking-water and human-contact standards were all met and few exceedances occurred for the ecological thresholds investigated. Several constituents showed a significant trend over the period of analysis, but only concentration and flux data for total phosphate, orthophosphate, total nitrogen, suspended sediment, and sulfate were suitable to be used in a weighted regression analysis that statistically accounted for time, discharge, and season. Sulfate concentrations and flux showed a significant downward trend over the period of analysis, whereas total phosphorus and ortho-phosphate showed a relatively small magnitude upward trend relative to standards. Suspended sediment concentrations and flux both showed a significant downward trend in the 1980s, an effect attributed to reduction of cattle in the subwatershed at about this time, and (or) increased cottonwood ( Populus fremontii ) and willow ( Salix goodingii ) recruitment, and (or) the curtailment of sand and gravel mining adjacent to the San Pedro River with the designation of the San Pedro Riparian National Conservation Area in 1988. A spike in sediment flux in 2006 may be attributable to the more than 100 debris flows in the Huachuca Mountains during the summer monsoon of that year. Spring discharge along the San Pedro River generally increased at three sites proximate to the Sierra Vista treated effluent recharge facility and varied somewhat with climate at two other sites. Median annual discharge at the recharge facility peaked in 2006, and at Murray Springs and Horsethief Spring, downgradient of the recharge facility, in 2009. Sampling for trace organic compounds in flow from springs was carried out using both discrete sampling and passive sampling methods. Spring samples thus collected showed the presence of trace-organic compounds. Lewis Springs (background site) had the least number of detections, whereas Murray Springs, located directly downgradient of the City of Sierra Vista’s treated effluent recharge facility, had the greatest number of detections of all the springs. Discrete samples from the recharge facility had more than twice the detections found in discrete samples from Murray Spring and at much higher concentrations. Few similar trace-organic compounds were detected at both the springs and the treated effluent recharge facility, and the number of detections did not increase during the collection period. Limitations of the study prevented the determination of trace-organic concentration in passive samplers and also prevented linking trace organic compounds detected at the treated effluent recharge facility with compounds detected from the springs. In particular, trace organic compounds could also derive from other sources such as septic systems. Looking at the subwatershed as a whole, base flow was in decline along the entire river reach, but determination of the specific cause of the decline was beyond the scope of this report. Conditions in the area from the municipal pumping center of Sierra Vista and Fort Huachuca northeast to the river (from about the Charleston to Tombstone gaging stations) were more commonly in decline than in regions further south. Both long-term indicators, such as regional aquifer groundwater levels and horizontal gradients, and the isotope analysis indicated that groundwater discharge to the river and thus base flow may continue to decline in that area. South of Charleston, indicators were more mixed. Some indicators in the Hereford reach suggest groundwater discharge to the San Pedro River may be increasing there, whereas some indicators in the Palominas reach suggest groundwater discharge to the river there may be declining.

Arizona

Synthesis of nearshore recovery following the 1989 Exxon Valdez oil spill: sea otter liver pathology and survival in Western Prince William Sound, 2001 – 2008

We examined livers and liver biopsies collected from captured sea otters in WPWS, 2001–2008, to determine whether indicators of liver health correlated with history of oil contamination from the 1989 Exxon Valdez oil spill. Sea otters captured in oiled areas had a significantly higher proportion of livers with gross pathological change, based on visual inspection at the time of capture, than those from unoiled areas. Of the 10 histopathology variables scored on liver biopsies, only two (vacuolar change and pigment) differed between animals from oiled and unoiled areas, and neither correlated with gross pathology scores. Vacuolar change indicates physiological disturbance, which is consistent with potential effects from oil exposure but also could be influenced by a number of other factors. We concluded that, as of 2008, some differences in liver health were evident between sea otters from oiled and unoiled areas; these differences were consistent with, but not specific to, effects that might be expected with sublethal exposure to lingering Exxon Valdez oil. We also quantified variation in survival of radiomarked sea otters within oiled areas of WPWS in relation to age, sex, body condition, selected blood serum chemistry variables, and histological scores indicative of liver health. Of the variables considered, only the serum enzyme aspartate aminotransferase (AST) and the ratio of serum proteins albumin and globulin (A/G) were correlated with survival, with higher levels of AST and lower levels of A/G associated with increased likelihood of mortality. High AST and low A/G both may be indicative of liver disease. Taken together, results reported here suggest that liver health of sea otters in oiled areas was slightly poorer than those from unoiled areas and, ifurther, that this may have translated to poorer survival through 2008, nearly 2 decades after the spill. More recently collected information indicated that mortality patterns and abundance had returned to pre-spill conditions between 2010 and 2013, suggesting that the effects that we detected through 2008 may have represented the end of effects related to exposure to lingering oil.

Alaska

Effects of selective handling of pyritic, acid-forming materials on the chemistry of pore gas and ground water at a reclaimed surface coal mine in Clarion County, PA, USA

A change from dragline to “selective handling” mining methods at a reclaimed surface coal mine in western Pennsylvania did not significantly affect concentrations of metals in ground water because oxidation of pyrite and dissolution of siderite were not abated. Throughout the mine, placement of pyritic material near the land surface facilitated the oxidation of pyrite, causing the consumption of oxygen (O 2 ) and release of acid, iron, and sulfate ions. Locally in the unsaturated zone, water sampled within or near pyritic zones was acidic, with concentrations of sulfate exceeding 3,000 milligrams per liter (mg/L). However, acidic conditions generally did not persist below the water table because of neutralization by carbonate minerals. Dissolution of calcite, dolomite, and siderite in unsaturated and saturated zones produced elevated concentrations of carbon dioxide (CO 2 ), alkalinity, calcium, magnesium, iron, and manganese. Alkalinity concentrations of 600 to 800 mg/L as CaCO 3 were common in water samples from the unsaturated zone in spoil, and alkalinities of 100 to 400 mg/L as CaCO 3 were common in ground-water samples from the underlying saturated zone in spoil and bedrock. Saturation indices indicated that siderite could dissolve in water throughout the spoil, but that calcite dissolution or precipitation could occur locally. Calcite dissolution could be promoted as a result of pyrite oxidation, gypsum precipitation, and calcium ion exchange for sodium. Calcite precipitation could be promoted by evapotranspiration and siderite dissolution, and corresponding increases in concentrations of alkalinity and other solutes. Partial pressures of O 2 (Po 2 ) and CO 2 (Pco 2 ) in spoil pore gas indicated that oxidation of pyrite and precipitation of ferric hydroxide, coupled with dissolution of calcite, dolomite, and siderite were the primary reactions affecting water quality. Highest vertical gradients in Po 2 , particularly in the near-surface zone (0-1 m), did not correlate with concentrations of total sulfur in spoil. This lack of correlation could indicate that total sulfur concentrations in spoil do not reflect the amount of reactive pyrite or that oxidation rates can be controlled more by rates of O 2 diffusion than the amount of pyrite. Hence, if placed in O 2 -rich zones near the land surface, even small amounts of disseminated pyritic material can be relatively significant sources of acid and mineralized water.

Pennsylvania

Response of Stream Chemistry During Base Flow to Gradients of Urbanization in Selected Locations Across the Conterminous United States, 2002-04

During 2002-2004, the U.S. Geological Survey's National Water-Quality Assessment Program conducted a study to determine the effects of urbanization on stream water quality and aquatic communities in six environmentally heterogeneous areas of the conterminous United States--Atlanta, Georgia; Raleigh-Durham, North Carolina; Milwaukee-Green Bay, Wisconsin; Dallas-Fort Worth, Texas; Denver, Colorado; and Portland, Oregon. This report compares and contrasts the response of stream chemistry during base flow to urbanization in different environmental settings and examines the relation between the exceedance of water-quality benchmarks and the level of urbanization in these areas. Chemical characteristics studied included concentrations of nutrients, dissolved pesticides, suspended sediment, sulfate, and chloride in base flow. In three study areas where the background land cover in minimally urbanized basins was predominantly forested (Atlanta, Raleigh-Durham, and Portland), urban development was associated with increased concentrations of nitrogen and total herbicides in streams. In Portland, there was evidence of mixed agricultural and urban influences at sites with 20 to 50 percent urban land cover. In two study areas where agriculture was the predominant background land cover (Milwaukee-Green Bay and Dallas-Fort Worth), concentrations of nitrogen and herbicides were flat or decreasing as urbanization increased. In Denver, which had predominantly shrub/grass as background land cover, nitrogen concentrations were only weakly related to urbanization, and total herbicide concentrations did not show any clear pattern relative to land cover - perhaps because of extensive water management in the study area. In contrast, total insecticide concentrations increased with increasing urbanization in all six study areas, likely due to high use of insecticides in urban applications and, for some study areas, the proximity of urban land cover to the sampling sites. Phosphorus concentrations increased with urbanization only in Portland; in Atlanta and Raleigh-Durham, leachate from septic tanks may have increased phosphorus concentrations in basins with minimal urban development. Concentrations of suspended sediment were only weakly associated with urbanization, probably because this study analyzed only base-flow samples, and the bulk of sediment loads to streams is transported in storm runoff rather than base flow. Sulfate and chloride concentrations increased with increasing urbanization in four study areas (Atlanta, Raleigh-Durham, Milwaukee-Green Bay, and Portland), likely due to increasing contributions from urban sources of these constituents. The weak relation between sulfate and chloride concentrations and urbanization in Dallas-Fort Worth and Denver was likely due in part to high sulfate and chloride concentrations in ground-water inflow, which would have obscured any pattern of increasing concentration with urbanization. Pesticides often were detected at multiple sites within a study area, so that the pesticide 'signature' for a given study area - the mixtures of pesticides detected, and their relative concentrations, at streams within the study area - tended to show some pesticides as dominant. The type and concentrations of the dominant pesticides varied markedly among sites within a study area. There were differences between pesticide signatures during high and low base-flow conditions in five of the six study areas. Normalization of absolute pesticide concentrations by the pesticide toxicity index (a relative index indicating potential toxicity to aquatic organisms) dramatically changed the pesticide signatures, indicating that the pesticides with the greatest potential to adversely affect cladocerans or fish were not necessarily the pesticides detected at the highest concentrations. In a screening-level assessment, measured contaminant concentrations in individual base-flow water samples were compared with various water-qual

Scientific Investigations Report

Chemistry and origin of minor and trace elements in selected vitrinite concentrates from bituminous and anthracitic coals

Organic and inorganic affinities were determined by comparing the elemental concentrations in the vitrinite concentrates to the concentrations in the companion whole coals. The ratios of these concentrations for 33 selected elements are shown in Figure 1. Ratios greater than 1 indicate organic affinity, and ratios less than 1 indicate inorganic affinity. Br and W generally showed organic affinity in all samples in this study. In the nine samples from the eastern United States (Fig. 1A-C) less than one-fourth of the trace elements show organic affinity compared to nearly one-half for the three English and Australian samples (Fig. 1D). The elements that generally show organic affinity in the non-U.S.A. samples studied include As, Cs, Hf, and Ni, which have generally inorganic affinities in the U.S.A. samples, and Cr, Sb, Se, and U, which have mixed (both organic and inorganic) affinities, in the U.S.A. coals studied, has an inorganic affinity in the English coals studied. B shows organic affinity in the samples from the Illinois basin (Fig. 1C). For the samples studied, Ba shows organic affinity in the Appalachian basin bituminous coals (Fig. 1B), inorganic affinity in the Illinois basin coals, and overall mixed affinities. In all the samples studied, Cu, Mn, Na, Sr, Ta, V, and Zn show mixed affinities, and A1, Co, Eu, Fe, Ga, K, La, Mg, Sc, Si, Th, Ti, and Ub have generally inorganic affinity.

International Journal of Coal Geology

Geologic, water-chemistry, and hydrologic data from multiple-well monitoring sites and selected water-supply wells in the Santa Clara Valley, California, 1999-2003

To better identify the three-dimensional geohydrologic framework of the Santa Clara Valley, lithologic, geologic, geophysical, geomechanical, hydraulic, and water-chemistry data were collected from eight ground-water multiple-well monitoring sites constructed in Santa Clara County, California, as part of a series of cooperative studies between the U.S. Geological Survey and the Santa Clara Valley Water District. The data are being used to update and improve the three-dimensional geohydrologic framework of the basin and to address issues related to water supply, water chemistry, sequence stratigraphy, geology, and geological hazards. This report represents a compilation of data collected from 1999 to 2003, including location and design of the monitoring sites, cone penetrometer borings, geologic logs, lithologic logs, geophysical logs, core analysis, water-chemistry analysis, ground-water-level measurements, and hydraulic and geomechanical properties from wells and core samples. Exploratory cone penetrometer borings taken in the upper 17 to 130 feet at six of the monitoring sites identified the base of Holocene as no deeper than 75 feet in the central confined area and no deeper than 35 feet in the southern unconfined areas of the valley. Generalized lithologic characterization from the monitoring sites indicates about four to six different aquifer units separated by relatively fine-grained units occur within the alluvial deposits shallower than 860 feet deep. Analysis of geophysical logs indicates that coarse-grained units varied in thickness between 10 and 25 feet in the southeastern unconfined area of the valley and between 50 and 200 feet in the south-central and southwestern areas of the valley. Deviations from temperature-gradient logs indicate that the majority of horizontal ground-water flow occurs above a depth of 775 feet in the south central and above 510 feet in the southeastern areas of the valley. Bulk physical properties from more than 1,150 feet of core samples indicate an average primary-wave velocity of about 5,515 feet per second, a bimodal distribution of density between 2.19 and 2.32 grams per cubic centimeter with an average of 2.16 grams per cubic centimeter, and a magnetic susceptibility that generally ranged between 9 and 40 with an average of 22. Water-chemistry data indicate that the ground water in the alluvial aquifers generally is low in total dissolved solids and chloride and of good quality. Isotopic data indicate that water from artificial recharge is present throughout the shallower parts of the aquifer system but may not be present toward the center of the valley. The percentage of water from artificial recharge present in ground water ranges from 0 to 61 percent for water-supply wells. The age of most shallow ground water is less than 2,000 years before present, and the age of deeper ground water is as much as 39,900 years before present, as determined from carbon age dates. Initial water-level data from the multiple-well monitoring sites indicate seasonal water-level fluctuations as great as 60 feet and water-level differences between aquifers as great as 10 feet. The water-level hydrographs indicate different water-level changes and relations between aquifers in different parts of the basin. However, most of these hydrographs indicate the potential for downward water-level gradients, with lower hydraulic heads in the deeper monitoring wells. Hydraulic properties of selected new monitoring wells indicate that horizontal hydraulic conductivities range from 0.1 to 583 feet per day. Hydraulic testing of selected core samples yielded vertical hydraulic conductivity values ranging from 8 x 10-4 to 0.3 feet per day, and effective porosity values ranging from 0.21 to 0.4. Geomechanical properties estimated from one-dimensional consolidation tests of selected core samples resulted in geometric mean inelastic and elastic specific storage values of 1.5 x 10-

Scientific Investigations Report

Hydrogeologic characterization, groundwater chemistry, and vulnerability assessment, Ute Mountain Ute Reservation, Colorado and Utah

The U.S. Geological Survey, in cooperation with the Ute Mountain Ute Tribe (UMUT), initiated a study in 2016 to increase understanding of the hydrogeology and chemistry of groundwater within select areas of the Ute Mountain Ute Reservation (UMUR) in Colorado and Utah, identify vulnerabilities to the system and other natural resources, and outline information needs to aid in the understanding and protection of groundwater resources. The results presented for this study can be used to support the UMUT’s goal of protecting their vital groundwater resources on the UMUR. Hydrogeologic conditions were characterized for the surficial aquifer contained in Quaternary-age unconsolidated surficial deposits and the Dakota aquifer contained in the Cretaceous-age Dakota Sandstone. In the surficial aquifer, median depth to water ranges from about 5.4 to 17.2 feet below land surface in the Farm and Ranch Enterprise area and 11 to 34 feet below land surface in the Towaoc area, and the water table slopes generally southwest or south. A map of depth to the top of the Dakota Sandstone was constructed from existing well data. Depths range from zero in outcrop areas to more than 3,000 feet below land surface on mesas in the southeastern part of the UMUR. Groundwater-chemistry data were collected by the UMUT from 13 springs and 31 wells from 1996 through 2017. Specific conductance was much lower for samples from springs than from wells; median values were 512 and 6,024 microsiemens per centimeter at 25 degrees Celsius, respectively. Spring samples were well oxygenated. A few well samples were anoxic (dissolved oxygen concentrations less than 0.5 milligrams per liter [mg/L]), indicating reducing conditions in the aquifer. About 75 percent of spring samples had fresh water (total dissolved solids concentrations less than 1,000 mg/L), and about 85 percent of well samples had brackish or highly saline water (total dissolved solids concentrations greater than 1,000 mg/L). Water type for springs on the Ute Mountains was calcium bicarbonate. Lower-altitude springs had a calcium-sulfate water type. Most well samples had sodium as the dominant cation, and sulfate, bicarbonate, and chloride as the dominant anions. Fluoride concentrations in about 45 percent of well samples were greater than an agricultural-use standard of 2 mg/L. Nitrate plus nitrite concentrations in most spring and well samples were less than about 1.6 mg/L per liter. Concentrations in samples from wells in the irrigated agricultural area were elevated; the maximum concentration was 78.5 mg/L. About one-half of the trace-element samples had concentrations that were less than laboratory reporting limits. Only aluminum, arsenic, and selenium in spring samples, and boron and selenium in well samples, were detected at concentrations greater than surface-water standards or water-quality standards for agricultural use of groundwater. Only three organic compounds, the pesticides alachlor and atrazine and the volatile organic compound di(2-ethylhexyl) phthalate, were detected in well samples. The Escherichia coli bacteria was detected in 47 and 23 percent of samples from wells and springs, respectively. The E. coli detections included samples from three culturally significant springs, which did not meet the UMUT cultural-use standard of total absence of E. coli. Tritium and carbon-14 were the primary environmental tracers used for interpreting groundwater ages for Lopez 2 Spring and five wells (AP–1, 5000 Block, Cottonwood Spring, Goodknight, and SE Toe). Water from the AP–1 well contained a mixture of pre- and post-1950s recharge. Tritium and carbon-14 recharge ages for Lopez 2 Spring (post-1950s in age), Goodknight and SE Toe wells (pre-1950s in age), and Cottonwood Spring well (primarily pre-1950s in age) are supported by helium-4 data. The helium-4 data for the 5000 Block well are inconsistent with the tritium and carbon-14 age of pre-1950s recharge because of interference caused by high methane concentrations in the water. Springs and surficial deposits are more vulnerable to contamination from anthropogenic chemicals than deeper bedrock wells. Bedrock aquifers are vulnerable in areas where the geologic formations containing the aquifers are exposed at the land surface. Groundwater in deep bedrock aquifers is likely thousands of years old and is not currently affected by present-day land uses. Both shallow and deep groundwater are vulnerable to naturally occurring salts and minerals, such as of total dissolved solids, major ions, nitrate, and trace elements. Effects of a changing climate on water resources and other ecological characteristics of the UMUR could include changes in evapotranspiration, a decrease in snowpack, decreased aquifer recharge and flow of springs, a decrease in soil moisture, and increased occurrence of wildfires and forest mortality. Of particular interest for the UMUT are possible effects of a changing climate on medicinal and culturally important plants and springs Several information needs were identified during this study that would aid in the understanding and protection of groundwater resources on the UMUR. These include well-completion information for bedrock wells, the collection of environmental tracer data at additional wells, the addition of methane and hydrocarbon analysis to well sampling plans, and the resampling of springs and wells that were last sampled in 2002 or earlier.

Colorado

Impacts of temporal revisit designs on the power to detect trend with a linear mixed model: An application to long-term monitoring of Sierra Nevada lakes

Long-term ecological monitoring programs often use linear mixed models to estimate trend in an ecological indicator sampled across large landscapes. A linear mixed model is versatile for estimating a linear trend in time as well as components of spatial and temporal variationin the case of unbalanced data structures , which are common in complex monitoring designs where limited sampling effort must be optimized over time and space. A power analysis was used to inform a lake chemistry monitoring design, including selecting the most appropriate temporal revisit design. Pilot data from surveys of lakes across large wilderness national parks (Sequoia, Kings Canyon, and Yosemite national parks) were used to obtain variance components for a Monte Carlo power simulation. Using a linear mixed model for a range of temporal revisit designs, sample sizes, and trend magnitudes, we evaluated the power to detect trend, the trend test size, and the relative bias of trend coefficient estimates for four continuous and normally distributed indicators. Contrary to prior research based on large-sample approximations that identified a single panel of sites visited annually as the revisit design generating the highest power, we found that the power to detect a 12-year trend based on the Wald t-test from a linear mixed model may be optimized by obtaining unbalanced data sets with limited to no annual replication. We emphasize the importance of examining variance composition, sample size, and the power and size of the trend test with Monte Carlo simulation when allocating sampling effort over time and space.

Ecological Indicators

Water-Chemistry and On-Site Sulfur-Speciation Data for Selected Springs in Yellowstone National Park, Wyoming, 1996-1998

Fifty-eight water analyses are reported for samples collected from 19 hot springs and their overflow drainages and one ambient-temperature acid stream in Yellowstone National Park (YNP) during 1996-98. These water samples were collected and analyzed as part of research investigations on microbially mediated sulfur oxidation in stream waters and sulfur redox speciation in hot springs in YNP and chemical changes in overflow drainages that affect major ions, redox species, and trace elements. The research on sulfur redox speciation in hot springs is a collaboration with the State University of New York at Stony Brook, Northern Arizona University, and the U.S. Geological Survey (USGS). One ambient-temperature acidic stream system, Alluvium Creek and its tributaries in Brimstone Basin, was studied in detail. Analyses were performed adjacent to the sampling site, in an on-site mobile laboratory truck, or later in a USGS laboratory, depending on stability and preservability of the constituent. Water temperature, specific conductance, pH, Eh, dissolved oxygen (D.O.), and dissolved H2S were determined on-site at the time of sampling. Alkalinity and F were determined within a few days of sample collection by titration and by ion-selective electrode, respectively. Concentrations of S2O3 and SxO6 were determined as soon as possible (minutes to hours later) by ion chromatography (IC). Concentrations of Cl, SO4, and Br were determined by IC within a few days of sample collection. Concentrations of Fe(II) and Fe(total) were determined by ultraviolet/visible spectrophotometry within a few days of sample collection. Densities were determined later in the USGS laboratory. Concentrations of Li, Na, and K were determined by flame atomic absorption (Li) and emission (Na, K) spectrometry. Concentrations of Al, As(total), B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe(total), Mg, Mn, Ni, Pb, Si, Sr, V, and Zn were determined by inductively-coupled plasma optical emission spectrometry. Trace concentrations of Cd, Se, As(total), Ni, and Pb were determined by Zeeman-corrected graphite-furnace atomic-absorption spectrometry. Trace concentrations of As(total) and As(III) were determined by hydride generation using a flow-injection analysis system.

Open-File Report

Water-chemistry and on-site sulfur-speciation data for selected springs in Yellowstone National Park, Wyoming, 1994-1995

Forty-two water analyses are reported for samples collected at 8 hot springs and their overflow drainages, two geysers, and two ambient-temperature acid streams in Yellowstone National Park during 1994-95. These water samples were collected and analyzed as part of the initial research investigations on sulfur redox speciation in the hot springs of Yellowstone and to document chemical changes in overflows that affect major ions, redox species, and trace elements. The sulfur redox speciation research is a collaboration between the State University of New York (SUNY) at Stony Brook and the U.S. Geological Survey (USGS). Four hot springs, Ojo Caliente, Azure, Frying Pan, and Angel Terrace, were studied in detail. Analyses were performed adjacent to the sampling site or in an on-site mobile lab truck constructed by the USGS, or later in a USGS laboratory. Water temperature, specific conductance, pH, Eh, D.O., and dissolved H2S were determined adjacent to the sample source at the time of sampling. Alkalinity and F- were determined on-site on the day of sample collection. Thiosulfate and polythionates were determined as soon as possible (minutes to hours later) by ion chromatography (IC). Other major anions (Cl-, SO4 2-, Br-) also were determined on-site by IC within two days of sample collection. Ammonium, Fe(II), and Fe(total) were determined on-site by ultraviolet/visible spectrophotometry within two days of sample collection. Later in the USGS laboratory, densities were determined. Concentrations of Ca, Mg, Li, Na, and K were determined by flame atomic absorption and emission (Na, K) spectrometry. Concentrations of Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe(total), K, Mg, Mn, Na, Ni, Pb, Si, Sr, V, and Zn were determined by inductively-coupled plasma optical emission spectrometry. Trace concentrations of Al and Mg were determined by Zeeman-corrected graphite furnace atomic absorption spectrometry. Three important conclusions from the sampling and analyses are: (1) variability in H2S concentrations can be caused as much by sampling and preservation artifacts as by actual variations in water composition over time, (2) historical determinations of S2O3 2- were subject to overestimation, most likely because of inadequate preservation leading to H2S oxidation, and (3) S2O3 2- is a common constituent of hot spring waters.

Wyoming

Temporal trends in water-quality constituent concentrations and annual loads of chemical constituents in Michigan watersheds, 1998–2013

In 1998, the Michigan Department of Environmental Quality and the U.S. Geological Survey began the Water Chemistry Monitoring Program for select streams in the State of Michigan. Objectives of this program were to provide assistance with (1) statewide water-quality assessments, (2) the National Pollutant Discharge Elimination System permitting process, and (3) water-resource management decisions. As part of this program, water-quality data collected from 1998 to 2013 were analyzed to identify potential trends for select constituents that were sampled. Sixteen water-quality constituents were analyzed at 32 stations throughout Michigan. Trend analysis on the various water-quality data was done using either the uncensored Seasonal Kendall test or through Tobit regression. In total, 79 trends were detected in the constituents analyzed for 32 river stations sampled for the study period—53 downward trends and 26 upward trends were detected. The most prevalent trend detected throughout the State was for ammonia, with 11 downward trends and 1 upward trend estimated. In addition to trends, constituent loads were estimated for 31 stations from 2002 to 2013 for stations that were sampled 12 times per year. Loads were computed using the Autobeale load computation program, which used the Beale ratio estimator approach to estimate an annual load. Constituent loads were the largest in large watershed streams with the highest annual flows such as the Saginaw and Grand Rivers. Likewise, constituent loads were the smallest in smaller tributaries that were sampled as part of this program such as the Boardman and Thunder Bay Rivers.

Michigan

Ground-water quality data in the middle Sacramento Valley study unit, 2006— Results from the California GAMA program

Ground-water quality in the approximately 3,340 mi 2 Middle Sacramento Valley study unit (MSACV) was investigated from June through September, 2006, as part of the California Groundwater Ambient Monitoring and Assessment (GAMA) program. The GAMA Priority Basin Assessment project was developed in response to the Groundwater Quality Monitoring Act of 2001 and is being conducted by the U.S. Geological Survey (USGS) in cooperation with the California State Water Resources Control Board (SWRCB). The Middle Sacramento Valley study was designed to provide a spatially unbiased assessment of raw ground-water quality within MSACV, as well as a statistically consistent basis for comparing water quality throughout California. Samples were collected from 108 wells in Butte, Colusa, Glenn, Sutter, Tehama, Yolo, and Yuba Counties. Seventy-one wells were selected using a randomized grid-based method to provide statistical representation of the study unit (grid wells), 15 wells were selected to evaluate changes in water chemistry along ground-water flow paths (flow-path wells), and 22 were shallow monitoring wells selected to assess the effects of rice agriculture, a major land use in the study unit, on ground-water chemistry (RICE wells). The ground-water samples were analyzed for a large number of synthetic organic constituents (volatile organic compounds [VOCs], gasoline oxygenates and degradates, pesticides and pesticide degradates, and pharmaceutical compounds), constituents of special interest (perchlorate, N-nitrosodimethylamine [NDMA], and 1,2,3-trichloropropane [1,2,3-TCP]), inorganic constituents (nutrients, major and minor ions, and trace elements), radioactive constituents, and microbial indicators. Naturally occurring isotopes (tritium, and carbon-14, and stable isotopes of hydrogen, oxygen, nitrogen, and carbon), and dissolved noble gases also were measured to help identify the sources and ages of the sampled ground water. Quality-control samples (blanks, replicates, laboratory matrix spikes) were collected at approximately 10 percent of the wells, and the results for these samples were used to evaluate the quality of the data for the ground-water samples. Field blanks rarely contained detectable concentrations of any constituent, suggesting that contamination was not a noticeable source of bias in the data for the ground-water samples. Differences between replicate samples were within acceptable ranges, indicating acceptably low variability. Matrix spike recoveries were within acceptable ranges for most constituents. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, water typically is treated, disinfected, or blended with other waters to maintain acceptable water quality. Regulatory thresholds apply to treated water that is served to the consumer, not to raw ground water. However, to provide some context for the results, concentrations of constituents measured in the raw ground water were compared with health-based thresholds established by the U.S. Environmental Protection Agency (USEPA) and California Department of Public Health (CDPH) and thresholds established for aesthetic concerns (secondary maximum contaminant levels, SMCL-CA) by CDPH. Comparisons between data collected for this study and drinking-water thresholds are for illustrative purposes only and are not indicative of compliance or noncompliance with regulatory thresholds. Most constituents that were detected in ground-water samples were found at concentrations below drinking-water thresholds. VOCs were detected in less than one-third and pesticides and pesticide degradates in just over one-half of the grid wells, and all detections of these constituents in samples from all wells of the MSACV study unit were below health-based thresholds. All detections of trace elements in samples from MSACV grid wells were below health-based thresholds, with the exceptions of arsenic and boron. Arsenic concentrations were above the USEPA maximum contaminant level (MCL-US) threshold in eight grid wells, and boron concentrations were above the CDPH notification level (NL-CA) in two grid wells. Arsenic was detected above the MCL-US in two flow-path wells. Arsenic, barium, boron, molybdenum, strontium, and vanadium were detected above health-based thresholds in a few of the RICE wells; these wells are not used to supply drinking water. All detections of radioactive constituents were below health-based thresholds, although six samples had activities of radon-222 above the lower proposed MCL-US threshold. Most of the samples from the MSACV wells had concentrations of major elements, total dissolved solids, and trace elements below the non-enforceable thresholds set for aesthetic concerns. Chloride and sulfate concentrations exceeded SMCL-CA thresholds in two and one grid well, respectively. Iron, manganese, and total dissolved solids concentrations were above the SMCL-CA thresholds in 1, 12, and 6 grid wells, respectively. Nitrate (nitrite plus nitrate, as dissolved nitrogen) concentrations from two grid wells were above the MCL-US threshold. There were no detections of microbial indicators in MSACV.

California

Application of a multipurpose unequal probability stream survey in the Mid-Atlantic Coastal Plain

A stratified, spatially balanced sample with unequal probability selection was used to design a multipurpose survey of headwater streams in the Mid-Atlantic Coastal Plain. Objectives for the survey include unbiased estimates of regional stream conditions, and adequate coverage of unusual but significant environmental settings to support empirical modeling of the factors affecting those conditions. The design and field application of the survey are discussed in light of these multiple objectives. A probability (random) sample of 175 first-order nontidal streams was selected for synoptic sampling of water chemistry and benthic and riparian ecology during late winter and spring 2000. Twenty-five streams were selected within each of seven hydrogeologic subregions (strata) that were delineated on the basis of physiography and surficial geology. In each subregion, unequal inclusion probabilities were used to provide an approximately even distribution of streams along a gradient of forested to developed (agricultural or urban) land in the contributing watershed. Alternate streams were also selected. Alternates were included in groups of five in each subregion when field reconnaissance demonstrated that primary streams were inaccessible or otherwise unusable. Despite the rejection and replacement of a considerable number of primary streams during reconnaissance (up to 40 percent in one subregion), the desired land use distribution was maintained within each hydrogeologic subregion without sacrificing the probabilistic design.

Journal of the American Water Resources Associatio

Fish communities of benchmark streams in agricultural areas of eastern Wisconsin

Fish communities were surveyed at 20 stream sites in agricultural areas in eastern Wisconsin in 1993 and 1995 as part of the National Water-Quality Assessment (NAWQA) Program. These streams, designated "benchmark streams," were selected for study because of their potential use as regional references for healthy streams in agricultural areas, based on aquatic communities, habitat, and water chemistry. The agricultural benchmark streams were selected from four physical settings, or relatively homogeneous units (RHU's), that differ in bedrock type, texture of surficial deposits, and land use. Additional data were collected along with the fish-community data, including measures of habitat, water chemistry, and population surveys of algae and benthic invertebrates. Of the 20 sites, 19 are classified as trout (salmonid) streams. Fish species that require cold or cool water were the most commonly collected. At least one species of trout was collected at 18 sites, and trout were the most abundant species at 13 sites. The species with the greatest collective abundance, and collected at 18 of the 20 sites, were mottled sculpin (Cottus bairdi), a coldwater species. The next most abundant species were brown trout (Salmo trutta), followed by brook trout (Salvelinusfontinalis), creek chub (Semotilus atromaculatus), and longnose dace (Rhinichthys cataractae). In all, 31 species of fish were collected. The number of species per stream ranged from 2 to 14, and the number of individuals collected ranged from 19 to 264. According to Index of Biotic Integrity (IBI) scores, 5 sites were rated excellent, 10 sites rated good, 4 rated fair, and 1 rated poor. The ratings of the five sites in the fair to poor range were low for various reasons. Two sites appeared to have more warmwater species than was ideal for a high-quality coldwater stream. One was sampled during high flow and the results may not be valid for periods of normal flow; the other may have been populated by migrating warmwater species. Two sites had insufficient deep-water habitat to support large numbers offish, especially top carnivores. Finally, one stream may be too cool to support enough warmwater species and too warm to support trout. In general, two methods of evaluating site habitat indicate that habitat is not a limiting factor for fish communities. However, two sites were rated as fair according to both habitat evaluation methods due to low base flow. Two sites rated below good according to one habitat evaluation method but rated good or excellent according to the other. Detrended correspondence analysis (DCA) of data for 17 sites showed three station groupings. These groupings fell along RHU divisions and each group was associated with one of three trout species. A species-richness gradient was evident on the station-ordination diagram. Intolerant species were associated with each grouping, a reflection of the generally high water quality at the sites. However, no significant differences were found between IBI scores or habitat indices among the site groupings. The DCA axis 1 and 2 scores correlated with average velocity and percent pool as well as RHU factors percent sandy surficial deposits, percent wetland, percent agriculture, and bedrock. Average velocity was highest at three sites which also had among the highest measured flow and largest drainage areas. Percent pool was generally lower at sites with smaller percentages of sandy surficial deposits, with one exception. The usefulness of ordination methods in conjunction with more traditional methods of defining biotic integrity (IB I) has been noted in previous studies. In this study, however, perhaps because of the relative homogeneity of the benchmark streams, the IBI did not correlate with the same kinds of factors as the DCA axis scores did.

Wisconsin

Temporal analysis of water chemistry and smallmouth bass (Micropterus dolomieu) health at two sites with divergent land use in the Susquehanna River watershed, Pennsylvania, USA

Monitoring wild fish health and exposure effects in impacted rivers and streams with differing land use has become a valuable research tool. Smallmouth bass ( Micropterus dolomieu ) are a sensitive, indicator species that exhibit signs of immunosuppression and endocrine disruption in response to water quality changes and contaminant exposure. To determine the impact of agriculture and development on smallmouth bass health, two sites (a developed/agriculture site and a forested site) in the Susquehanna River watershed, Pennsylvania were selected where bass and water chemistry were sampled from 2015 to 2019. Smallmouth bass were sampled for histopathology to assess parasite and macrophage aggregate density in the liver and spleen, condition factor (Ktl), hepatic gene transcript abundance, hepatosomatic index (HSI), and a health assessment index (HAI). Land use at the developed/agriculture site included greater pesticide application rates and phytoestrogen crop cover and more detections and higher concentrations of pesticides, wastewater-associated contaminants, hormones, phytoestrogens, and mycotoxins than at the forested site. Additionally, at the developed/agriculture site, indicators of molecular changes, including oxidative stress, immune/inflammation, and lipid metabolism-related hepatic gene transcripts, were associated with more contaminants and land use variables. At both sites, there were multiple associations of contaminants with liver and/or spleen macrophage aggregate density, indicating that changes at the molecular level seemed to be a better indicator of exposures unique to each site. The findings illustrate the importance of timing for land management practices, the complex mixtures aquatic animals are exposed to, and the temporal changes in contaminant concentration. Agricultural practices that affect hepatic gene transcripts associated with immune function and disease resistance were demonstrated which could negatively affect smallmouth bass populations.

Pennsylvania

Subchronic mercury exposure in coturnix and a method of hazard evaluation

The sublethal toxicity of inorganic (HgCl 2 ) and organic (CH 3 HgCl) mercury chloride was studied in coturnix ( Coturnix japonica ) by feeding them mercuric compounds (CH 3 HgCl at concentrations of 0.125,0.5,2 and 8 ppm; HgCl 2 at 0.5, 2, 8 and 32 ppm) in ad libitum diets from hatching to adulthood. Differences of response to the mercurials were compared on the basis of selected indicator enzymes and plasma chemistries. Comparisons of response to equivalent concentrations of the two mercurials and dose-response relationships were made at 1,3,5,7 and 9 weeks. Changes of activity were detected for brain acetylcholinesterase (AChE) and the plasma enzymes aspartate aminotransferase (ASAT), butyrylcholinesterase (BChE), lactate dehydrogenase (LDH) and ornithine carbamoyl transferase (OCT). Changes of ASAT, LDH and OCT were then quantified by probit analysis and the mercurials were compared through their median effective concentrations (EC 50 ). This quantal procedure was based on the establishment of normal control values for each enzyme and then classifying mercury-treated outliers (more than ± 2 SD) as respondents. The EC 50 values at 9 weeks for ASAT, LDH and OCT, respectively, were 9, 3 and 63 ppm for HgCl 2 , and 5, 1 and 4 ppm for CH 3 HgCl. These results provided the basis for two hazard indices that were calculated by dividing the EC 50 into the oral LD 50 and the 5-d dietary LC 50 . Mercury also had contradictory effects on gonadal maturation in both sexes.

Environmental Toxicology and Chemistry