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Leaf litter breakdown, microbial respiration and shredder production in metal-polluted streams

1. If species disproportionately influence ecosystem functioning and also differ in their sensitivities to environmental conditions, the selective removal of species by anthropogenic stressors may lead to strong effects on ecosystem processes. We evaluated whether these circumstances held for several Colorado, U.S.A. streams stressed by Zn. 2. Benthic invertebrates and chemistry were sampled in five second-third order streams for 1 year. Study streams differed in dissolved metal concentrations, but were otherwise similar in chemical and physical characteristics. Secondary production of leaf-shredding insects was estimated using the increment summation and size-frequency methods. Leaf litter breakdown rates were estimated by retrieving litter-bags over a 171 day period. Microbial activity on leaf litter was measured in the laboratory using changes in oxygen concentration over a 48 h incubation period. 3. Dissolved Zn concentrations varied eightfold among two reference and three polluted streams. Total secondary production of shredders was negatively associated with metal contamination. Secondary production in reference streams was dominated by Taenionema pallidum. Results of previous studies and the current investigation demonstrate that this shredder is highly sensitive to metals in Colorado headwater streams. Leaf litter breakdown rates were similar between reference streams and declined significantly in the polluted streams. Microbial respiration at the most contaminated site was significantly lower than at reference sites. 4. Our results supported the hypothesis that some shredder species contribute disproportionately to leaf litter breakdown. Furthermore, the functionally dominant taxon was also the most sensitive to metal contamination. We conclude that leaf litter breakdown in our study streams lacked functional redundancy and was therefore highly sensitive to contaminant-induced alterations in community structure. We argue for the necessity of simultaneously measuring community structure and ecosystem function in anthropogenically stressed ecosystems.

Freshwater Biology

Geologic field-trip guide to Long Valley Caldera, California

This guide to the geology of Long Valley Caldera is presented in four parts: (1) An overview of the volcanic geology; (2) a chronological summary of the principal geologic events; (3) a road log with directions and descriptions for 38 field-trip stops; and (4) a summary of the geophysical unrest since 1978 and discussion of its causes. The sequence of stops is arranged as a four-day excursion for the quadrennial General Assembly of the International Association of Volcanology and Chemistry of the Earth’s Interior (IAVCEI), centered in Portland, Oregon, in August 2017. Most stops, however, are written freestanding, with directions that allow each one to be visited independently, in any order selected.

California

Evaluating the efficiency of environmental monitoring programs

Statistical uncertainty analyses can be used to improve the efficiency of environmental monitoring, allowing sampling designs to maximize information gained relative to resources required for data collection and analysis. In this paper, we illustrate four methods of data analysis appropriate to four types of environmental monitoring designs. To analyze a long-term record from a single site, we applied a general linear model to weekly stream chemistry data at Biscuit Brook, NY, to simulate the effects of reducing sampling effort and to evaluate statistical confidence in the detection of change over time. To illustrate a detectable difference analysis, we analyzed a one-time survey of mercury concentrations in loon tissues in lakes in the Adirondack Park, NY, demonstrating the effects of sampling intensity on statistical power and the selection of a resampling interval. To illustrate a bootstrapping method, we analyzed the plot-level sampling intensity of forest inventory at the Hubbard Brook Experimental Forest, NH, to quantify the sampling regime needed to achieve a desired confidence interval. Finally, to analyze time-series data from multiple sites, we assessed the number of lakes and the number of samples per year needed to monitor change over time in Adirondack lake chemistry using a repeated-measures mixed-effects model. Evaluations of time series and synoptic long-term monitoring data can help determine whether sampling should be re-allocated in space or time to optimize the use of financial and human resources.

Ecological Indicators

Groundwater chemistry and hexavalent chromium

Water samples collected by the U.S. Geological Survey from more than 100 wells between March 2015 and November 2017 in Hinkley and Water Valleys, in the Mojave Desert 80 miles northeast of Los Angeles, California, were analyzed for field parameters, major ions, nutrients, and selected trace elements, including hexavalent chromium, Cr(VI). Water from most wells was alkaline and oxic. The pH ranged from 6.9 in water-table wells near recharge areas along the Mojave River to 9.4 in deeper wells farther downgradient in the northern subarea. Hexavalent chromium concentrations measured by ion chromatography using U.S. Environmental Protection Agency Method 218.6 and a version of that method used for detection of Cr(VI) concentrations as low as 0.06 micrograms per liter (μg/L), produced results comparable to field speciation with subsequent analyses by graphite furnace atomic absorption spectroscopy (coefficient of determination, R 2 , of 0.97). Hexavalent chromium concentrations ranged from less than the study reporting level of 0.10 to 2,500 μg/L. The highest concentrations were within the October–December 2015 (Q4 2015) regulatory Cr(VI) plume downgradient from the Hinkley compressor station. Hexavalent chromium concentrations outside the Q4 2015 regulatory Cr(VI) plume were as high as 11 μg/L. Hexavalent chromium concentrations in water from most wells were distributed in a narrow redox potential and pH band within the overlapping chromate ion, CrO 4 2− (aqueous) , and manganese-3, Mn(III) (solid) , stability fields. The redox potential of water from some wells completed in carbonate-rich mudflat/playa deposits approached the more oxic manganese-4, Mn(IV) (solid) , stability field. However, Cr(VI) concentrations in porewater pressure-extracted from Mn(IV)-containing deposits in the eastern subarea did not exceed 3.3 μg/L, and porewater does not appear to be a source of Cr(VI) concentrations greater than this concentration in water from wells in the eastern subarea. On the basis of comparison with California-wide data, Cr(VI) concentrations at the measured pH were higher than expected for uncontaminated water from wells (1) within the Q4 2015 regulatory Cr(VI) plume, (2) within the eastern subarea nominally crossgradient from the Hinkley compressor station and upgradient from the Q4 2015 regulatory Cr(VI) plume, and (3) from shallow wells in the northern subarea downgradient from the leading edge of the Q4 2015 regulatory Cr(VI) plume. Hexavalent chromium concentrations in alkaline water from wells in the northern subarea of Hinkley Valley and in Water Valley were within ranges expected for uncontaminated water elsewhere in California given their pH and trace-element composition. Hexavalent chromium concentrations were higher than expected on the basis of selected trace-element concentrations that co-occur with Cr(VI) in water from wells within the Q4 2015 regulatory Cr(VI) plume and from wells in the eastern and northern subareas near the plume margins. Hexavalent chromium concentrations did not exceed 4 μg/L in water from domestic wells sampled in Hinkley and Water Valleys and were generally within ranges expected for uncontaminated groundwater given their pH and trace-element composition. Interpretations derived from Cr(VI) and pH, and from Cr(VI) and selected trace-element concentrations collected between March 2015 and November 2017 were used within a summative-scale analysis to determine the Cr(VI) plume extent (chapter G). However, Cr(VI) background concentrations (chapter G) were calculated from regulatory data collected from selected wells between April 2017 and January 2018.

California

Ground-water, surface-water, and water-chemistry data, Black Mesa area, northeastern Arizona—1999

The N aquifer is the major source of water in the 5,400-square-mile area of Black Mesa in northeastern Arizona. Availability of water is an important issue in this area because of continued industrial and municipal use, a growing population, and a precipitation of only about 6 to 12 inches per year. The monitoring program in Black Mesa has been operating since 1971 and is designed to determine the long-term effects of ground-water withdrawals from the N aquifer for industrial and municipal uses. The monitoring program includes measurements of (1) ground-water pumping, (2) ground-water levels, (3) spring discharge, (4) surface-water discharge, and (5) ground-water chemistry. In 1999, total ground-water withdrawals were 7,110 acre-feet, industrial use was 4,210 acre-feet, and municipal use was 2,900 acre-feet. From 1998 to 1999, total withdrawals increased by 0.7 percent, industrial use increased by 4 percent, and municipal use decreased by 4 percent. From 1998 to 1999, water levels declined in 11 of 15 wells in the unconfined part of the aquifer, and the median decline was 0.7 foot. Water levels declined in 14 of 16 wells in the confined part of the aquifer, and the median decline was 1.2 feet. From the prestress period (prior to 1965) to 1999, the median water-level decline in 31 wells was 10.6 feet. Median water-level changes were 0.0 foot for 15 wells in the unconfined part of the aquifer and a decline of 45.5 feet in 16 wells in the confined part. From 1998 to 1999, discharges were measured annually at four springs. Discharges declined 30 percent and 3 percent at 2 springs, did not change at 1 spring, and increased by 11 percent at 1 spring. For the past 10 years, discharges from the four springs have fluctuated; however, an increasing or decreasing trend was not observed. Continuous records of surface-water discharge have been collected from July 1976 to 1999 at Moenkopi Wash, July 1996 to 1999 at Laguna Creek, June 1993 to 1999 at Dinnebito Wash, and April 1994 to 1999 at Polacca Wash. Median flows for November, December, January, and February of each water year are used as an index of ground-water discharge to those streams. Increasing or decreasing trends are not apparent in these median winter flows for the periods of record. In 1999, water samples were collected from 12 wells and 4 springs and analyzed for selected chemical constituents. Dissolved-solids concentrations ranged from 91 to 630 milligrams per liter. Water samples from 10 of the wells and the 4 springs had less than 350 milligrams per liter of dissolved solids. Water-chemistry data are available for nine wells and four springs from about the mid-1980s. For that time period, the data from those sites have remained fairly stable. From 1987 to 1999, concentrations of dissolved solids, chloride, and sulfate may have increased slightly in samples from Moenkopi School Spring.

Arizona

Geochemical results from stream-water and stream-sediment samples collected in Colorado and New Mexico

Scientists from the U.S. Geological Survey are studying the relationship between watershed lithology and stream-water chemistry. As part of this effort, 60 stream-water samples and 43 corresponding stream-sediment samples were collected in 2010 and 2011 from locations in Colorado and New Mexico. Sample sites were selected from small to midsize watersheds composed of a high percentage of one rock type or geologic unit. Stream-water and stream-sediment samples were collected, processed, preserved, and analyzed in a consistent manner. This report releases geochemical data for this phase of the study.

Colorado;New Mexico

The influence of reagent type on the kinetics of ultrafine coal flotation

A kinetic study has been conducted to determine the influence of reagent type on flotation rates of ultrafine coal. Two ultrafine coal samples, the Illinois No. 5 (Springfield) and Pittsburgh No. 8, have been evaluated with various reagent types in order to derive the rate constants for coal (k c ), ash (k a ), and pyrite (k c ). The reagents used in the study include anionic surfactants, anionic surfactant—alcohol mixtures, and frothing alcohols. In general, the surfactant-alcohol mixtures tend to float ultrafine coal at a rate three to four times faster than either pure alcohols or pure anionic surfactants. Pine oil, a mixture of terpene alcohols and hydrocarbons, was an exception to this finding; it exhibited higher rate constants than the pure aliphatic alcohols or other pure anionic surfactants studied; this may be explained by the fact that the sample of pine oil used (70% alpha-terpineol) acted as a frother/collector system similar to alcohol/kerosene. The separation efficiencies of ash and pyrite from coal, as evidenced by the ratios of k c /k a or k c /k p , tend to indicate, however, that commercially available surfactant—alcohol mixtures are not as selective as pure alcohols such as 2-ethyl-1-hexanol or methylisobutylcarbinol. Some distinct differences in various rate constants, or their ratios, were noted between the two coals studied, and are possibly attributable to surface chemistry effects.

Powder Technology

Evaluation of the toxicity of sediments from the Anniston PCB Site to the mussel Lampsilis siliquoidea

The Anniston Polychlorinated Biphenyl (PCB) Site is located in the vicinity of the municipality of Anniston in Calhoun County, in the north-eastern portion of Alabama. Although there are a variety of land-use activities within the Choccolocco Creek watershed, environmental concerns in the area have focused mainly on releases of PCBs to aquatic and riparian habitats. PCBs were manufactured by Monsanto, Inc. at the Anniston facility from 1935 to 1971. The chemicals of potential concern (COPCs) in sediments at the Anniston PCB Site include: PCBs, mercury, metals, polycyclic aromatic hydrocarbons (PAHs), organochlorine and organophosphorous pesticides, volatile organic compounds (VOCs), semivolatile organic compounds (SVOCs), and polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/PCDFs). The purpose of this study was to evaluate the toxicity of PCB-contaminated sediments to the juvenile fatmucket mussel (Lampsilis siliquoidea) and to characterize relationships between sediment chemistry and the toxicity of sediment samples collected from the Anniston PCB Site using laboratory sediment testing. Samples were collected in August 2010 from OU-4 of the Anniston PCB Site, as well as from selected reference locations. A total of 32 samples were initially collected from six test sites and one reference site within the watershed. A total of 23 of these 32 samples were evaluated in 28-day whole-sediment toxicity tests conducted with juvenile mussels (L. siliquoidea). Physical and chemical characterization of whole sediment included grain size, total organic carbon (TOC), nutrients, PCBs, parent and alkylated PAHs, organochlorine pesticides, PCDD/PCDFs, total metals, simultaneously extracted metals (SEM), and acid volatile sulfide (AVS). Sediment collected from Snow Creek and Choccolocco Creek contained a variety of COPCs. Organic contaminants detected in sediment included PCBs, organochlorine pesticides, PCDDs/PCDFs, and PAHs. In general, the highest concentrations of PCBs were associated with the highest concentrations of PAHs, PCDDs/PCDFs, and organochlorine pesticides. Specifically, sediments 08, 18, and 19 exceeded probable effect concentration quotients (PEC-Qs) of 1.0 for all organic classes of contaminants. These three sediment samples also had high concentrations of mercury and lead, which were the only metals found at elevated concentrations (i.e., above the probable effect concentration [PEC]) in the samples collected. Many sediment samples were highly contaminated with mercury, based on comparisons to samples collected from reference locations. The whole-sediment laboratory toxicity tests conducted with L. siliquoidea met the test acceptability criteria (e.g., control survival was greater than or equal to 80%). Survival of mussels was high in most samples, with 4 of 23 samples (17%) classified as toxic based on the survival endpoint. Biomass and weight were more sensitive endpoints for the L. siliquoidea toxicity tests, with both endpoints classifying 52% of the samples as toxic. Samples 19 and 30 were most toxic to L. siliquoidea, as they were classified as toxic according to all four endpoints (survival, biomass, weight, and length). Mussels were less sensitive in toxicity tests conducted with sediments from the Anniston PCB Site than Hyalella azteca and Chironomus dilutus. Biomass of L. siliquoidea was less sensitive compared to biomass of H. azteca or biomass of larval C. dilutus. Based on the most sensitive endpoint for each species, 52% of the samples were toxic to L. siliquoidea, whereas 67% of sediments were toxic to H. azteca (based on reproduction) and 65% were toxic to C. dilutus (based on adult biomass). The low-risk toxicity threshold (TTLR) was higher for L. siliquoidea biomass (e.g., 20,400 µg/kg dry weight [DW]) compared to that for H. azteca reproduction (e.g., 499 µg/kg DW) or C. dilutus adult biomass (e.g., 1,140 µg/kg DW; MacDonald et al. 2014). While mussels such as L. sili

Alabama

Ground-water, surface-water, and water-chemistry data, Black Mesa Area, northeastern Arizona — 2000–2001, and performance and sensitivity of the 1988 USGS numerical model of the N aquifer

The N aquifer is the major source of water in the 5,400-square-mile area of Black Mesa in northeastern Arizona. Availability of water is an important issue in this area because of continued industrial and municipal use, a growing population, and precipitation of about 6 to 14 inches per year. The monitoring program in Black Mesa has been operating since 1971 and is designed to determine the long-term effects of ground-water withdrawals from the N aquifer for industrial and municipal uses. The monitoring program includes measurements of (1) ground-water pumping, (2) ground-water levels, (3) spring discharge, (4) surface-water discharge, and (5) ground-water chemistry. In 2000, total ground-water withdrawals were 7,740 acre-feet, industrial use was 4,490 acre-feet, and municipal use was 3,250 acre-feet. From 1999 to 2000, total withdrawals increased by 9 percent, industrial use increased by 7 percent, and municipal use increased by 12 percent. From 1999 to 2001, water levels declined in 10 of 15 wells in the unconfined part of the aquifer, and the median change was -0.4 foot. Water levels declined in 8 of 16 wells in the confined part of the aquifer, and the median change was -0.2 foot. From the prestress period (prior to 1965) to 2001, the median water-level change for 33 wells was -17.2 feet. Median water-level changes were -1.2 feet for 15 wells in the unconfined part of the aquifer and -31.0 feet for 18 wells in the confined part. Discharges were measured once in 1999 and once in 2001 at four springs. Discharges decreased by 5 percent and 33 percent at two springs and increased by 3 percent and 81 percent at two springs. For about the past 10 years, discharges did not significantly change in Burro Spring, the unnamed spring near Dennehotso, and Moenkopi School Spring. The record of discharge from a consistent measuring point for Pasture Canyon Spring is too short for statistical analysis of trends. Continuous records of surface-water discharge have been collected from July 1976 to 2000 at Moenkopi Wash, July 1996 to 2000 at Laguna Creek, June 1993 to 2000 at Dinnebito Wash, and April 1994 to 2000 at Polacca Wash. Median flows for November, December, January, and February of each water year were used as an index of ground-water discharge to those streams. There is no significant trend in the median winter flows for Moenkopi Wash from 1977 to 2000. The records for the other three streams are too short for a statistical analysis of trends. The median winter flows for Dinnebito Wash and Polacca Wash, however, appear to have decreased during the last 6 years. There is no apparent trend in the median winter flows for Laguna Creek since 1997. In 2001, water samples were collected from 12 wells and 4 springs and analyzed for selected chemical constituents. Dissolved-solids concentrations ranged from 102 to 628 milligrams per liter. Water samples from 9 of the wells and from the 4 springs had less than 350 milligrams per liter of dissolved solids. Water-chemistry data with sufficient years of record for a statistical analysis of trends over time are available from 7 wells and 4 springs. From about the mid-1980s or early 1990s to 2001 there are no significant trends in the concentrations of dissolved solids, chloride, and sulfate in water samples from 6 of the 7 wells. The concentration of one tested constituent (dissolved solids) in samples from Rocky Ridge PM3 significantly increased from 1990 to 2001. From the late 1980s to 2001, there are no significant trends in the concentrations of dissolved solids, chloride, and sulfate in water samples from Burro Spring, the unnamed spring near Dennehotso, and Pasture Canyon Spring. From 1987 to 2001, concentrations of chloride and sulfate significantly increased in water samples from Moenkopi School Spring and concentrations of dissolved solids did not significantly change. The performance and sensitivity of the 1988 USGS numerical model of the N aquifer were analyzed. The overall performance of the model in steady-state conditions is reasonable for residuals of heads (difference between observed and simulated steady-state heads); 80 percent of the absolute values of residuals are less than 38 feet. Simulated flows are about 40 percent different than estimated flows at two of three discharge areas; however, this comparison is only a rough approximation of performance because the accuracy of the estimated steady-state flows is uncertain. The overall performance of the model for transient conditions is fair for residuals of changes in head (difference between observed and simulated changes in head from steady state to 1999); 80 percent of the absolute values of residuals are less than 31 feet. The model is biased in two areas. In the Tuba City area, simulated changes in head are more negative than observed changes in head; all six residuals are positive, and three residuals are between 75 and 155 feet. In the confined area of the aquifer, observed changes in head are more negative than simulated changes in head; 12 of the 17 residuals are negative, and 8 residuals are between -57 and -20 feet. Analysis of model sensitivity indicates that recharge, transmissivity, and storage coefficient are the most important parameters for estimating heads, changes in heads, and flows. A strong correlation between recharge and transmissivity and a lack of independent and reliable estimates of recharge, transmissivity, and discharge create a uniqueness problem in model calibration. Several models could be constructed and calibrated with different values of recharge or transmissivity and still have similar fits to the observed data. Information from recent data and studies and more advanced modeling techniques could be used to develop a more representative and less uncertain model. Future data collection and studies should focus on obtaining a better definition of recharge, discharge, transmissivity, and storage coefficient.

Arizona

U/Th series radionuclides as coastal groundwater tracers

The study of coastal groundwater has recently surfaced as an active interdisciplinary area of research, driven foremost by its importance as a poorly quantified pathway for subsurface material transport into coastal ecosystems. Key issue in coastal groundwater research include a complete geochemical characterization of the groundwater(s); quantification of the kinetics of subsurface transport, including rock-water interactions; determination of groundwater ages; tracing of groundwater discharge into coastal waters using radiochemical fingerprints; and an assessment of the potential ecological impact of such subsurface flow to a reviving water body. For such applications, the isotopic systemics of select naturally occurring radionucludes in the U/Th series has proven to be particularly useful. These radionuclides (e.g., U, Th, Ram and Rn) are ubiquitous in all groundwaters ad are represented by several isotopes with widely different half-lives and chemistries (Figure 1). As a result, varied biogeochemical processes occurring over a broad range of time scales can be studied. In source rock, most U/Th series isotopes in secular equilibrium; that is, the rate of decay of a daughter isotope is equal to that of it radiogenic parent, and so will have equal activities (in this context, the specific activity is simply a measure of the amount of radioactivity per unit amount). In contrast, these nuclides exhibit strong fractionations within the surrounding groundwaters because of their respective physiochemical differences. Disequilibria in U/Th series radionuclides can thus be used to identify distinct water masses, quantify release rates from source rocks, assess groundwater migration rates, and assess groundwater discharge rates in coastal waters., Large isotopic variations also have the potential for providing precise fingerprints for groundwaters from specific aquifers and have been explored as a means for calculating groundwater ages and estuarine water mass transit times. The highly fractionated nature of U/Th series nuclides in groundwater is illustrated by the range in some measured activities. highest activities are typically observed for 222 Rn, reflecting the inert nature of this noble gas. Groundwater 222 Rn (t 1/2 =3.8) activities are thus controlled only by rapid in situ decay (Table 1) and production within host rocks, without the added complications of reversible removal via absorption or precipitation. Uranium, which is soluble as U(VI) in oxidizing waters, is present in intermediate activities in groundwaters that are moderated by redox-initiated removal onto aquifer rocks. The alkaline earth Ra and, to a greater extent, the less soluble actinide Th are readily removed from groundwater by water -- rock interactions and so are strongly depleted. Both of these elements have very short-lived as well as longer-lived isotopes, and so isotopes compositions reflect processes over a range of time scales. Many studies have evaluated and behavior of select radionuclides in groundwater and surface water systems. Recent advances in high-=precision mass spectrometry have opted new possibilities for more subtle interpretations in select long-lived U/Th series isotopes, such as U, Ra, Pa, and Th. However, these techniques have yet to be fully developed, ahns as a consequence, such data remain largely scarce and underutilized. Although many different approaches have been developed to study radionucluide behavior in groundwater, all are based on principles of radioactive production and decay and knowledge of source terms from weathering and recoil processes, as well as removal terms from the interaction with aquifer host rock surface by sorption and precipitation. This review is structured to present first a brief description of the background, driving forces, scales, and ecological significance of submarine groundwater discharge. Following this, a description of the geochemistry and behavior of select radionuclides in groundwater will be presented, and their application to tracing submarine groundwater discharge will be discussed.

Chemical Reviews

Design and methods of the Pacific Northwest Stream Quality Assessment (PNSQA), 2015

In 2015, the U.S. Geological Survey (USGS) National Water-Quality Assessment (NAWQA) project conducted the Pacific Northwest Stream Quality Assessment (PNSQA) to investigate stream quality across the western part of the Pacific Northwest. The goal of the PNSQA was to assess the health of streams in the region by characterizing multiple water-quality factors that are stressors to in-stream aquatic life and by evaluating the relation between these stressors and the condition of biological communities. The effects of urbanization and agriculture on stream quality for the Puget Lowland and Willamette Valley Level III Ecoregions were the focus of this regional study. Findings will help inform the public and policymakers about human and environmental factors that are the most critical in affecting stream quality and, thus, provide insights into possible strategies to protect or improve the health of streams in the region. Land-use data were used in the study to identify and select sites within the region that ranged in levels of urban and agricultural development. A total of 88 sites were selected across the region—69 were on streams that explicitly spanned a range of urban land use in their watersheds, 8 were on streams in agricultural watersheds, and 11 were reference sites with little or no development in their watersheds. Depending on the type of land use, sites were sampled for contaminants, nutrients, and sediment for either a 4- or 10-week period during April, May, and June 2015. This water-quality “index period” was immediately followed with an ecological survey of all sites that included stream habitat, benthic algae, benthic macroinvertebrates, and fish. Additionally, streambed sediment was collected during the ecological survey for analysis of sediment chemistry and toxicity testing. This report provides a detailed description of the specific study components and methods of the PNSQA, including (1) surveys of stream habitat and aquatic biota, (2) discrete water sampling, (3) deployment of passive polar organic chemical integrative samplers for pesticides and pharmaceuticals, and (4) sampling of streambed sediment. At selected study sites, toxicity testing of streambed sediment, continuous water-quality monitoring, and daily pesticide sampling also were conducted and are described.

Oregon, Washington

Rodent repellents, preparation and properties of thiouronium compounds and cyclic imides

Syntheses and bioassays of cyclic imides and thiouronium compounds were carried out as part of a search for materials capable of preventing rodent damage to packaged commodities. Previous studies had shown that repellent activity was associated with functional groups containing nitrogen and sulfur, and was enhanced by the presence of ionic linkages. Twenty-seven thiouronium compounds and 40 imides, including 1 0 compounds not described previously, were prepared for these tests. Ten imides and 26 thiouronium compounds were repellent under the conditions of test. Information obtained in these studies will be utilized in the development and selection of more effective materials for prevention of rodent damage to foods and other commodities.

Journal of Agricultural and Food Chemistry

Streamflow gain and loss and water quality in the upper Nueces River Basin, south-central Texas, 2008-10

The U.S. Geological Survey-in cooperation with the U.S. Army Corps of Engineers, The Nature Conservancy, the Real Edwards Conservation and Reclamation District, and the Texas Parks and Wildlife Department-investigated streamflow gain and loss and water quality in the upper Nueces River Basin, south-central Texas, specifically in the watersheds of the West Nueces, Nueces, Dry Frio, Frio, and Sabinal Rivers upstream from the Edwards aquifer outcrop. Streamflow in these rivers is sustained by groundwater contributions (for example, from springs) and storm runoff from rainfall events. To date (2012), there are few data available that describe streamflow and water-quality conditions of the rivers within the upper Nueces River Basin. This report describes streamflow gain-loss characteristics from three reconnaissance-level synoptic measurement surveys (hereinafter referred to as "surveys") during 2008-10 in the upper Nueces River Basin. To help characterize the hydrology, groundwater-level measurements were made, and water-quality samples were collected from both surface-water and groundwater sites in the study area from two surveys during 2009-10. The hydrologic (streamflow, springflow, and groundwater) measurements were made during three reconnaissance-level synoptic measurement surveys occurring in July 21-23, 2008; August 8-18, 2009; and March 22-24, 2010. These survey periods were selected to represent different hydrologic conditions. Streamflow gains and losses were based on streamflow and springflow measurements made at 74 sites in the study area, although not all sites were measured during each survey. Possible water chemistry relations among sample types (streamflow, springflow, or groundwater), between surveys, and among watersheds were examined using water-quality samples collected from as many as 20 sites in the study area. During the three surveys, reaches of gaining, losing, or no verifiable change in streamflow were observed in the watersheds in the study area. Reaches of generally consistent gaining or losing streamflow were identified in the Nueces, Frio, and Sabinal River watersheds. The water-quality data indicate that the streamflow, springflow, and groundwater have similar major ion chemical characteristics and generally can be categorized as a calcium-carbonate water type. Those data also indicate that the major ion chemistry was similar during the 2009 and 2010 surveys. Graphical comparisons among ratios of major ions, trace elements, and isotopes (for example, magnesium/calcium ratios to strontium isotopic ratios) indicate that samples collected from each watershed generally clustered together. Determining the source areas and other possible contributors on the basis of these data is not possible because of the small sample size of the water-quality dataset (both in number of samples and spatial distribution of samples). The different relations among the water-quality data indicate that the surface water in the different watersheds is likely influenced by differences in source areas, geochemical evolution, groundwater flow paths and residence time, local stratigraphy, or some combination thereof.

Texas

Guidelines and standard procedures for studies of ground-water quality; selection and installation of wells, and supporting documentation

This is the first of a two-part report to document guidelines and standard procedures of the U.S. Geological Survey for the acquisition of data in ground-water-quality studies. This report provides guidelines and procedures for the selection and installation of wells for water-quality studies/*, and the required or recommended supporting documentation of these activities. Topics include (1) documentation needed for well files, field folders, and electronic files; (2) criteria and information needed for the selection of water-supply and observation wells, including site inventory and data collection during field reconnaissance; and (3) criteria and preparation for installation of monitoring wells, including the effects of equipment and materials on the chemistry of ground-water samples, a summary of drilling and coring methods, and information concerning well completion, development, and disposition.

Water-Resources Investigations Report

Ground-water, surface-water, and water-chemistry data, Black Mesa area, northeastern Arizona— 2005-06

The N aquifer is the major source of water 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 and the needs of a growing population. Precipitation in the Black Mesa area averages about 6 to 14 inches per year. The water monitoring program in the Black Mesa area began in 1971 and is designed to provide information about the long-term effects of ground-water withdrawals from the N aquifer for industrial and municipal uses. This report presents results of data collected for the monitoring program in the Black Mesa area from January 2005 to September 2006. The monitoring program includes measurements of (1) ground-water pumping, (2) ground-water levels, (3) spring discharge, (4) surface-water discharge, (5) ground-water chemistry, and (6) periodic testing of ground-water withdrawal meters. In 2005, ground-water withdrawals in the Black Mesa area totaled 7,330 acre-feet, including ground-water withdrawals for industrial (4,480 acre-feet) and municipal (2,850 acre-feet) uses. From 2004 to 2005, total withdrawals increased by less than 2 percent, industrial withdrawals increased by approximately 3 percent, and total municipal withdrawals increased by 0.35 percent. From 2005 to 2006, annually measured water levels in the Black Mesa area declined in 10 of 13 wells in the unconfined areas of the N aquifer, and the median change was -0.5 foot. Measurements indicated that water levels declined in 12 of 15 wells in the confined area of the aquifer, and the median change was -1.4 feet. From the prestress period (prior to 1965) to 2006, the median water-level change for 29 wells was -8.5 feet. Median water-level changes were -0.2 foot for 13 wells in the unconfined areas and -46.6 feet for 16 wells in the confined area. Ground-water discharges were measured once in 2005 and once in 2006 at Moenkopi School Spring and Burro Spring. Discharge decreased by 3.5 percent at Moenkopi School Spring and by 15 percent at Burro Spring. During the period of record at each spring, discharges fluctuated; a decreasing trend was apparent. Continuous records of surface-water discharge in the Black Mesa area have been collected from streamflow gages at the following sites: Moenkopi Wash (1976 to 2005), Dinnebito Wash (1993 to 2005), Polacca Wash (1994 to 2005), Pasture Canyon Spring (August 2004 to December 2005), and Laguna Creek (1996 to 2005). Median flows during November, December, January, and February of each water year were used as an index of the amount of ground-water discharge to the above named sites. For the period of record at each streamflow-gaging station, the median winter flows have decreased for Moenkopi Wash, Dinnebito Wash, and Polacca Wash. There is not a long enough period of record for Pasture Canyon Spring and Laguna Creek was discontinued at the end of December 2005. In 2006, water samples were collected from 6 wells and 2 springs in the Black Mesa area and analyzed for selected chemical constituents. Dissolved-solids concentrations ranged from 111 to 588 milligrams per liter. Water samples from 5 of the wells and both of the springs had less than 500 milligrams per liter of dissolved solids. Trends in the chemistry of water samples from the 6 wells show the Pi?on NTUA 1 and Peabody 9 wells increasing in dissolved solids, Forest Lake NTUA 1 and Peabody 2 wells decreasing in dissolved solids, and Kykotsmovi PM2 and Keams Canyon PM2 wells show a steady trend. Increasing trends in dissolved-solids, chloride, and sulfate concentrations were evident from the more than 11 years of data for the 2 springs.

Arizona

Ground-water quality data in the Kern County Subbasin study unit, 2006— Results from the California GAMA Program

Ground-water quality in the approximately 3,000 square-mile Kern County Subbasin study unit (KERN) was investigated from January to March, 2006, as part of the Priority Basin Assessment Project of the 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 California State Water Resources Control Board (SWRCB) in collaboration with the U.S. Geological Survey (USGS) and the Lawrence Livermore National Laboratory (LLNL). The Kern County Subbasin study was designed to provide a spatially unbiased assessment of raw (untreated) ground-water quality within KERN, as well as a statistically consistent basis for comparing water quality throughout California. Samples were collected from 50 wells within the San Joaquin Valley portion of Kern County. Forty-seven of the wells were selected using a randomized grid-based method to provide a statistical representation of the ground-water resources within the study unit. Three additional wells were sampled to aid in the evaluation of changes in water chemistry along regional ground-water flow paths. The ground-water samples were analyzed for a large number of man-made organic constituents (volatile organic compounds [VOCs], pesticides, and pesticide degradates), constituents of special interest (perchlorate, N-nitrosodimethylamine [NDMA], and 1,2,3-trichloropropane [1,2,3-TCP]), naturally occurring inorganic constituents (nutrients, major and minor ions, and trace elements), radioactive constituents, and microbial indicators. Naturally occurring isotopes (tritium, carbon-14, and stable isotopes of hydrogen, oxygen, nitrogen, and carbon) and dissolved noble gases also were measured to help identify the source and age of the sampled ground water. Quality-control samples (blanks, replicates, and laboratory matrix spikes) were collected and analyzed at approximately 10 percent of the wells, and the results for these samples were used to evaluate the quality of the data from the ground-water samples. Assessment of the quality-control information resulted in censoring of less than 0.4 percent of the data collected for ground-water samples. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, raw ground water typically is treated, disinfected, or blended with other waters to maintain acceptable water quality. Regulatory thresholds apply, not to the raw ground water, but to treated water that is served to the consumer. 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 the California Department of Public Health (CDPH), and as well as with thresholds established for aesthetic concerns (secondary maximum contaminant levels, SMCL-CA) by CDPH. VOCs and pesticides each were detected in approximately 60 percent of the grid wells, and detections of all compounds but one were below health-based thresholds. The fumigant, 1,2-dibromo-3-chloropropane (DBCP), was detected above the USEPA maximum contaminant level (MCL-US) in one sample. Detections of most inorganic constituents were also below health-based thresholds. Constituents detected above health-based thresholds include: nitrate, (MCL-US, 2 samples), arsenic (MCL-US, 2 samples), and vanadium (California notification level, NL-CA, 1 sample). All detections of radioactive constituents were below health-based thresholds, although nine samples had activities of radon-222 above the lower proposed MCL-US. Most of the samples from KERN wells had concentrations of major elements, total dissolved solids, and trace elements below the non-enforceable thresholds set for aesthetic concerns.

California

Effects of selective forest clearing fertilization, and liming on the hydrology and water quality of a small tributary to the Quabbin Reservoir, central Massachusetts

Effects of selective forest clearing on water yield and water quality were investigated in a 308-hectare basin that drains to Quabbin Reservoir Watershed in central Massachusetts. The experimental basin and a nearby 280-hectare control basin were studied together for comparison. Streamflow was measured continuously and water-quality samples were collected biweekly in both basins from February 1985 through September 1989. During the same period, measurements of precipitation quantity and ground- water levels were made and samples were collected for determination of precipitation and ground-water quality. After an initial monitoring period to establish baseline hydrology and water quality in both basins, an area of red pine and white pine forest in the experimental basin was cleared. From October 1986 until April 1987, 23.8 percent of the total basal area was removed by clearcutting and thinning. Part of the cleared area was converted to rye and other field grasses, and the remainder was allowed to regrow naturally. Fertilizer and lime were applied to part of the cleared area. An additional 8.3 percent of basal area was cleared in fall 1988. Despite differences in bedrock geology, topography, and amount of wetland area, pre- treatment hydrology and chemistry of the two basins were similar. Biogeochemical reactions of the dilute mixture of sulfuric and nitric acids in precipitation with soils and rocks in the basins resulted in moderately buffered calcium-magnesium bicarbonate-type streamwater. During high flows, sulfate concentrations increased and alkalinity decreased. Selective forest clearing resulted in a slight increase in water yield during the year in which the clearing took place, particularly during the spring high-flow period, but flows returned to normal thereafter. Concurrent increases in solute flux were primarily a function of the increased water flux. No major alterations to biogeochemical processes were induced by the forest clearing, nor were any effects from the fertilizer or liming activity observed. The minimal effect observed from the clearing was attributed primarily to the limited area that was cleared, and the location of the cleared area in the headwaters of the basin (away from the riparian zone).

Massachusetts

Selected Physical, Chemical, and Biological Data for 30 Urbanizing Streams in the North Carolina Piedmont Ecoregion, 2002-2003

This report provides summarized physical, chemical, and biological data collected during a study of the effects of urbanization on stream ecosystems as part of the U.S. Geological Survey's National Water-Quality Assessment study. The purpose of this study was to examine differences in biological, chemical, and physical characteristics of streams across a gradient of urban intensity. Thirty sites were selected along an urbanization gradient that represents conditions in the North Carolina Piedmont ecoregion, including the cities of Raleigh, Durham, Cary, Greensboro, Winston-Salem, High Point, Asheboro, and Oxford. Data collected included streamflow variability, stream temperature, instream chemistry, instream aquatic habitat, and collections of the algal, macroinvertebrate, and fish communities. In addition, ancillary data describing land use, socioeconomic conditions, and urban infrastructure were compiled for each basin using a geographic information system analysis. All data were processed and summarized for analytical use and are presented in downloadable data tables, along with the methods of data collection and processing.

North Carolina