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Radium accumulation in carbonate river sediments at oil and gas produced water discharges: Implications for beneficial use as disposal management

In the western U.S., produced water from oil and gas wells discharged to surface water augments downstream supplies used for irrigation and livestock watering. Here we investigate six permitted discharges on three neighboring tributary systems in Wyoming. During 2013-16, we evaluated radium activities of the permitted discharges and the potential for radium accumulation in associated stream sediments. Radium activities of the sediments at the points of discharge ranged from approximately 200-3600 Bq/kg with elevated activities above the background of 74 Bq/kg over 30 km downstream of one permitted discharge. Sediment as deep as 30 cm near the point of discharge had radium activities elevated above background. X-ray diffraction and targeted sequential extraction of radium in sediments indicate that radium is likely coprecipitated with carbonate, and to a lesser extent sulfate minerals. PHREEQC modeling predicts radium coprecipitation with aragonite and barite, but over-estimates the latter compared to observations of downstream sediment, where carbonate predominates. Mass-balance calculations indicate over 3 billion Bq of radium activity (226Ra+228Ra) is discharged each year from five of the discharges, combined, with only 5 percent of the annual load retained in stream sediments within 100m of the effluent discharges; the remaining 95 percent of the radium is transported farther downstream as sediment-associated and aqueous species

Environmental Science

Geochemical and mineralogical controls on trace element release from the Penn Mine base-metal slag dump, California

Base-metal slag deposits at the Penn Mine in Calaveras County, California, are a source of environmental contamination through leaching of potentially toxic elements. Historical Cu smelting at Penn Mine (1865-1919) generated approximately 200,000 m3 of slag. The slag deposits, which are flooded annually by a reservoir used for drinking water and irrigation, also may be in contact with acidic ground waters (pH < 4) from the adjacent mine area. Slags vary from grey to black, are glassy to crystalline, and range in size from coarse sand to large (0.6 ?? 0.7 ?? 1.5 m), tub-shaped casts. Metals are hosted by a variety of minerals and two glass phases. On the basis of mineralogy, slags are characterized by 4 main types: fayalite-rich, glassy, willemite-rich, and sulfide-rich. The ranges in metal and metalloid concentrations of 17 slag samples are: As, 0.0004-0.92; Ba, 0.13-2.9; Cd, 0.0014-1.4; Cu, 0.18-6.4; Pb, 0.02-11; and Zn, 3.2-28 wt.%. Leachates from Toxicity Characteristic Leaching Procedure tests (acetic acid buffered at pH 4.93) on two wiltemite-rich slags contained Cd and Pb concentrations (up to 2.5 and 30 mg/l, respectively) in excess of US Environmental Protection Agency (USEPA) regulatory limits. Analyses of filtered (0.45 ??m) water, collected within the flooded slag dump during reservoir drawdown, reveal concentrations of Cd (1.7 ??g/l), Cu (35 ??g/l), and Zn (250 ??g/l) that exceed USEPA chronic toxicity guidelines for the protection of aquatic life. Data from field and laboratory studies were used to develop geochemical models with the program EQ3/6 that simulate irreversible mass-transfer between slag deposits and reservoir waters. These models include kinetic rate laws for abiotic sulfide oxidation and surface-controlled dissolution of silicates, oxides, and glass. Calculations demonstrate that the main processes controlling dissolved metal concentrations are (1) dissolution of fayalite, willemite, and glass; (2) sulfide oxidation; and (3) secondary phase precipitation. Close agreement between model results and measured concentrations of Al, Ba, Cu, Fe, SiO2, and SO4 in the slag dump pore waters suggests that the dissolved concentrations of these elements are controlled by solubility equilibrium with secondary phases. Differences between predicted and measured Cd and Pb concentrations imply that field weathering rates of glass and sulfides are approximately two orders of magnitude lower than laboratory rates. Overprediction of Pb release may also reflect other attenuation processes in the natural system, such as sorption or coprecipitation. ?? 2001 Elsevier Science Ltd. All rights reserved.

Applied Geochemistry

Study and interpretation of the chemical characteristics of natural water

The chemical composition of natural water is derived from many different sources of solutes, including gases and aerosols from the atmosphere, weathering and erosion of rocks and soil, solution or precipitation reactions occurring below the land surface, and cultural effects resulting from activities of man. Some of the processes of solution or precipitation of minerals can be closely evaluated by means of principles of chemical equilibrium including the law of mass action and the Nernst equation. Other processes are irreversible and require consideration of reaction mechanisms and rates. The chemical composition of the crustal rocks of the earth and the composition of the ocean and the atmosphere are significant in evaluating sources of solutes in natural fresh water. The ways in which solutes are taken up or precipitated and the amounts present in solution are influenced by many environmental factors, especially climate, structure and position: of rock strata, and biochemical effects associated with life cycles of plants and animals, both microscopic and macroscopic. Taken all together and in application with the further influence of the general circulation of all water in the hydrologic cycle, the chemical principles and environmental factors form a basis for the developing science of natural-water chemistry. Fundamental data used in the determination of water quality are obtained by the chemical analysis of water samples in the laboratory or onsite sensing of chemical properties in the field. Sampling is complicated by changes in composition of moving water and the effects of particulate suspended material. Most of the constituents determined are reported in gravimetric units, usually milligrams per liter or milliequivalents per liter. More than 60 constituents and properties are included in water analyses frequently enough to provide a basis for consideration of the sources from which each is generally derived, most probable forms of elements and ions in solution, solubility controls, expected concentration ranges and other chemical factors. Concentrations of elements that are commonly present in amounts less than a few tens of micrograms per liter cannot always be easily explained, but present information suggests many are controlled by solubility of hydroxide or carbonate or by sorption on solid particles. Chemical analyses may be grouped and statistically evaluated by averages, frequency distributions, or ion correlations to summarize large volumes of data. Graphing of analyses or of groups of analyses aids in showing chemical relationships among waters, probable sources of solutes, areal water-quality regimen, and water-resources evaluation. Graphs may show water type based on chemical composition, relationships among ions, or groups of ions in individual waters or many waters considered simultaneously. The relationships of water quality to hydrologic parameters, such as stream discharge rate or ground-water flow patterns, can be shown by mathematical equations, graphs, and maps. About 75 water analyses selected from the literature are tabulated to illustrate the relationships described, and some of these, along with many others that are not tabulated, are also utilized in demonstrating graphing and mapping techniques. Relationships of water composition to source rock type are illustrated by graphs of some of the tabulated analyses. Activities of man may modify water composition extensively through direct effects of pollution and indirect results of water development, such as intrusion of sea water in ground-water aquifiers. Water-quality standards for domestic, agricultural, and industrial use have been published by various agencies. Irrigation project requirements for water quality are particularly intricate. Fundamental knowledge of processes that control natural water composition is required for rational management of water quality.

Water Supply Paper

Study and interpretation of the chemical characteristics of natural water

The chemical composition of natural water is derived from many different sources of solutes, including gases and aerosols from the atmosphere, weathering and erosion of rocks and soil, solution or precipitation reactions occurring below the land surface, and cultural effects resulting from activities of man. Some of the processes of solution or precipitation of minerals can be closely evaluated by means of principles of chemical equilibrium including the law of mass action and the Nernst equation. Other processes are irreversible and require consideration of reaction mechanisms and rates. The chemical composition of the crustal rocks of the earth and the composition of the ocean and the atmosphere are significant in evaluating sources of solutes in natural fresh water. The ways in which solutes are taken up or precipitated and the amounts present in solution are influenced by many environmental factors, especially climate, structure and position: of rock strata, and biochemical effects associated with life cycles of plants and animals, both microscopic and macroscopic. Taken all together and in application with the further influence of the general circulation of all water in the hydrologic cycle, the chemical principles and environmental factors form a basis for the developing science of natural-water chemistry. Fundamental data used in the determination of water quality are obtained by the chemical analysis of water samples in the laboratory or onsite sensing of chemical properties in the field. Sampling is complicated by changes in composition of moving water and the effects of particulate suspended material. Most of the constituents determined are reported in gravimetric units, usually milligrams per liter or milliequivalents per liter. More than 60 constituents and properties are included in water analyses frequently enough to provide a basis for consideration of the sources from which each is generally derived, most probable forms of elements and ions in solution, solubility controls, expected concentration ranges and other chemical factors. Concentrations of elements that are commonly present in amounts less than a few tens of micrograms per liter cannot always be easily explained, but present information suggests many are controlled by solubility of hydroxide or carbonate or by sorption on solid particles. Chemical analyses may be grouped and statistically evaluated by averages, frequency distributions, or ion correlations to summarize large volumes of data. Graphing of analyses or of groups of analyses aids in showing chemical relationships among waters, probable sources of solutes, areal water-quality regimen, and water-resources evaluation. Graphs may show water type based on chemical composition, relationships among ions, or groups of ions in individual waters or many waters considered simultaneously. The relationships of water quality to hydrologic parameters, such as stream discharge rate or ground-water flow patterns, can be shown by mathematical equations, graphs, and maps. About 75 water analyses selected from the literature are tabulated to illustrate the relationships described, and some of these, along with many others that are not tabulated, are also utilized in demonstrating graphing and mapping techniques. Relationships of water composition to source rock type are illustrated by graphs of some of the tabulated analyses. Activities of man may modify water composition extensively through direct effects of pollution and indirect results of water development, such as intrusion of sea water in ground-water aquifiers. Water-quality standards for domestic, agricultural, and industrial use have been published by various agencies. Irrigation project requirements for water quality are particularly intricate. Fundamental knowledge of processes that control natural water composition is required for rational management of water quality.

Water Supply Paper

Selenium accumulation in mammals exposed to contaminated California irrigation drainwater

In May 1984, 332 mammals of 10 species were collected at Kesterson Reservoir (San Joaquin Valley, Merced Co., CA), which had received selenium-laden irrigation drainwater, and at the nearby Volta Wildlife Area, which had not. The study concentrated on the California vole ( Microtus californicus ); 88 were taken at Kesterson, 89 at Volta. Mean selenium concentrations in livers were as much as 522 times higher at Kesterson. There were species-to-species differences at Kesterson; higher selenium concentrations occurred in carnivorous species and/or species that feed on foods closely linked to pond water. There were also pond-to-pond differences at Kesterson; drainwater historically was delivered to Ponds 1 and 2, where concentrations in 1984 were higher, with subsequent flow to other ponds, where they were lower. Whereas none of 50 adult female voles from Kesterson was pregnant, 12 of 41 (29%) from Volta were pregnant. However, this cessation of reproductive activity at Kesterson was probably not due to selenium toxicity but could have resulted because drying conditions at Kesterson forced voles to a seed diet earlier than at Volta. One malformation was found among five embryonic litters of three species from Kesterson. Mammals seem much less susceptible to selenium-induced embryonic abnormalities than birds. No adverse impacts of selenium on wild mammals were demonstrated; however, some sensitive species might have been extirpated from Kesterson before this study began. In addition, high concentrations in small mammal species at Kesterson may threaten predatory birds and mammals that feed on them, with the endangered San Joaquin kit fox ( Vulpes macrotis mutica ) of particular concern.

Science of the Total Environment

Water availability and land subsidence in the Central Valley, California, USA

The Central Valley in California (USA) covers about 52,000 km 2 and is one of the most productive agricultural regions in the world. This agriculture relies heavily on surface-water diversions and groundwater pumpage to meet irrigation water demand. Because the valley is semi-arid and surface-water availability varies substantially, agriculture relies heavily on local groundwater. In the southern two thirds of the valley, the San Joaquin Valley, historic and recent groundwater pumpage has caused significant and extensive drawdowns, aquifer-system compaction and subsidence. During recent drought periods (2007&ndash;2009 and 2012-present), groundwater pumping has increased owing to a combination of decreased surface-water availability and land-use changes. Declining groundwater levels, approaching or surpassing historical low levels, have caused accelerated and renewed compaction and subsidence that likely is mostly permanent. The subsidence has caused operational, maintenance, and construction-design problems for water-delivery and flood-control canals in the San Joaquin Valley. Planning for the effects of continued subsidence in the area is important for water agencies. As land use, managed aquifer recharge, and surface-water availability continue to vary, long-term groundwater-level and subsidence monitoring and modelling are critical to understanding the dynamics of historical and continued groundwater use resulting in additional water-level and groundwater storage declines, and associated subsidence. Modeling tools such as the Central Valley Hydrologic Model, can be used in the evaluation of management strategies to mitigate adverse impacts due to subsidence while also optimizing water availability. This knowledge will be critical for successful implementation of recent legislation aimed toward sustainable groundwater use.

California

Study and interpretation of the chemical characteristics of natural water

The chemical composition of natural water is derived from many different sources of solutes, including gases and aerosols from the atmosphere, weathering and erosion of rocks and soil, solution or precipitation reactions occurring below the land surface, and cultural effects resulting from human activities. Broad interrelationships among these processes and their effects can be discerned by application of principles of chemical thermodynamics. Some of the processes of solution or precipitation of minerals can be closely evaluated by means of principles of chemical equilibrium, including the law of mass action and the Nernst equation. Other processes are irreversible and require consideration of reaction mechanisms and rates. The chemical composition of the crustal rocks of the Earth and the composition of the ocean and the atmosphere are significant in evaluating sources of solutes in natural freshwater. The ways in which solutes are taken up or precipitated and the amounts present in solution are influenced by many environmental factors, especially climate, structure and position of rock strata, and biochemical effects associated with life cycles of plants and animals, both microscopic and macroscopic. Taken together and in application with the further influence of the general circulation of all water in the hydrologic cycle, the chemical principles and environmental factors form a basis for the developing science of natural-water chemistry. Fundamental data used in the determination of water quality are obtained by the chemical analysis of water samples in the laboratory or onsite sensing of chemical properties in the field. Sampling is complicated by changes in the composition of moving water and by the effects of particulate suspended material. Some constituents are unstable and require onsite determination or sample preservation. Most of the constituents determined are reported in gravimetric units, usually milligrams per liter or milliequivalents per liter. More than 60 constituents and properties are included in water analyses frequently enough to provide a basis for consideration of the sources from which each is generally derived, the most probable forms of elements and ions in solution, solubilitycontrols, expected concentration ranges, and other chemical factors. Mechanisms that control concentrations of elements commonly present in amounts less than a few tens of micrograms per liter cannot always be easily ascertained, but present information suggests that many are controlled by solubility of their hydroxides or carbonates or by sorption on solid particles. Many dissolved organic compounds can now be specifically determined. Chemical analyses may be grouped and statistically evaluated by means, medians, frequency distributions, or ion correlations to summarize large volumes of data. Graphing of analyses or of groups of analyses aids in showing chemical relationships among water, probable sources of solutes, areal water-quality regimen, temporal and spatial variation, and water-resources evaluation. Graphs may show water type based on chemical composition, relationships among ions, or groups of ions in individual waters or many waters considered simultaneously. The relationships of water quality to hydrogeologic characteristics, such as stream discharge rate or ground-water flow patterns, can be shown by mathematical equations, graphs, and maps. About 80 water analyses selected from the literature are tabulated to illustrate the relationships described, and some of these, along with many others that are not tabulated, are also used in demonstrating graphing and mapping techniques. Relationships of water composition to source rock type are illustrated by graphs of some of the tabulated analyses. Human activities may modify water composition extensively through direct effects of pollution and indirect results of water development, such as intrusion of seawater in groundwater aquifers. Water-quality standards for domestic, agricultural, and industrial use have been published by various agencies. Irrigation project requirements for water quality are particularly intricate. Fundamental knowledge of processes that control natural-water composition is required for rational management of water quality.

Water Supply Paper

Meeting ecological and societal needs for freshwater

Human society has used freshwater from rivers, lakes, groundwater, and wetlands for many different urban, agricultural, and industrial activities, but in doing so has overlooked its value in supporting ecosystems. Freshwater is vital to human life and societal well-being, and thus its utilization for consumption, irrigation, and transport has long taken precedence over other commodities and services provided by freshwater ecosystems. However, there is growing recognition that functionally intact and biologically complex aquatic ecosystems provide many economically valuable services and long-term benefits to society. The short-term benefits include ecosystem goods and services, such as food supply, flood control, purification of human and industrial wastes, and habitat for plant and animal life—and these are costly, if not impossible, to replace. Long-term benefits include the sustained provision of those goods and services, as well as the adaptive capacity of aquatic ecosystems to respond to future environmental alterations, such as climate change. Thus, maintenance of the processes and properties that support freshwater ecosystem integrity should be included in debates over sustainable water resource allocation. The purpose of this report is to explain how the integrity of freshwater ecosystems depends upon adequate quantity, quality, timing, and temporal variability of water flow. Defining these requirements in a comprehensive but general manner provides a better foundation for their inclusion in current and future debates about allocation of water resources. In this way the needs of freshwater ecosystems can be legitimately recognized and addressed. We also recommend ways in which freshwater ecosystems can be protected, maintained, and restored. Freshwater ecosystem structure and function are tightly linked to the watershed or catchment of which they are a part. Because riverine networks, lakes, wetlands, and their connecting groundwaters, are literally the “sinks” into which landscapes drain, they are greatly influenced by terrestrial processes, including many human uses or modifications of land and water. Freshwater ecosystems, whether lakes, wetlands, or rivers, have specific requirements in terms of quantity, quality, and seasonality of their water supplies. Sustainability normally requires these systems to fluctuate within a natural range of variation. Flow regime, sediment and organic matter inputs, thermal and light characteristics, chemical and nutrient characteristics, and biotic assemblages are fundamental defining attributes of freshwater ecosystems. These attributes impart relatively unique characteristics of productivity and biodiversity to each ecosystem. The natural range of variation in each of these attributes is critical to maintaining the integrity and dynamic potential of aquatic ecosystems; therefore, management should allow for dynamic change. Piecemeal approaches cannot solve the problems confronting freshwater ecosystems. Scientific definitions of the requirements to protect and maintain aquatic ecosystems are necessary but insufficient for establishing the appropriate distribution between societal and ecosystem water needs. For scientific knowledge to be implemented science must be connected to a political agenda for sustainable development. We offer these recommendations as a beginning to redress how water is viewed and managed in the United States: (1) Frame national and regional water management policies to explicitly incorporate freshwater ecosystem needs, particularly those related to naturally variable flow regimes and to the linking of water quality with water quantity; (2) Define water resources to include watersheds, so that freshwaters are viewed within a landscape, or systems context; (3) Increase communication and education across disciplines, especially among engineers, hydrologists, economists, and ecologists to facilitate an integrated view of freshwater resources; (4) Increase restoration efforts, using well-grounded ecological principles as guidelines; (5) Maintain and protect the remaining freshwater ecosystems that have high integrity; and (6) Recognize the dependence of human society on naturally functioning ecosystems.

Ecological Applications

Chemically enhanced treatment wetland to improve water quality and mitigate land subsidence in the Sacramento-San Joaquin Delta: Cost and design considerations

Water quality impairment and land surface subsidence threaten the viability of the Sacramento-San Joaquin Delta (Delta), a critical component of California’s water conveyance system. Current day irrigation drainage through Delta island peat soils impacts drinking water treatment and is linked to mercury transport, potentially posing both ecological and public health concerns. Hybrid coagulation-treatment wetland systems, termed Chemically Enhanced Treatment Wetlands (CETWs), were studied as a means to cost-effectively treat agricultural drainage water from subsided Delta islands to reduce the export of drinking water quality constituents of concern and mitigate land subsidence through accretion. We provide cost estimates and design recommendations to aid broader implementation of this technology. Over a 20-year horizon using a Total Annualized Cost analysis, we estimate treatment costs of $602 – $747 per acre-foot (ac-ft) water treated and $36 – $70 per kg dissolved organic carbon (DOC) removed depending upon source water DOC concentrations for a small 3-acre CETW system. For larger CETW systems scaled for island sizes of 3,500 – 14,000 acres, costs decrease to $108 – $239 per ac-ft water treated and $11 – $14 per kg DOC removed. The footprints of CETW systems were estimated to be approximately 3% of the area being treated for 4-day hydraulic retention time systems but would decrease to less than 1% for 1-day hydraulic retention time systems. CETWs ultimately address several of the Delta’s key internal issues while keeping water treatment costs competitive with other currently available treatment technologies at similar scales on a per carbon removed basis. CETWs offer a reliable system to reduce out-going DOC and mercury loads and they provide the additional benefit of sediment accretion. System costs and treatment efficacy are highly dependent on inflow source water conditions, land availability and other practical matters. To keep costs low and removal efficacy high, wetland design features will need site-specific evaluation.

California

Groundwater quality of aquifers overlying the Oxnard Oil Field, Ventura County, California

Groundwater samples collected from irrigation, monitoring, and municipal supply wells near the Oxnard Oil Field were analyzed for chemical and isotopic tracers to evaluate if thermogenic gas or water from hydrocarbon-bearing formations have mixed with surrounding groundwater. New and historical data show no evidence of water from hydrocarbon-bearing formations in groundwater overlying the field. However, thermogenic gas mixed with microbial methane was detected in 5 wells at concentrations ranging from 0.011–9.1 mg/L. The presence of these gases at concentrations <10 mg/L do not indicate degraded water quality posing a known health risk. Analysis of carbon isotopes (δ 13 C-CH 4 ) and hydrogen isotopes (δ 2 H-CH 4 ) of methane and ratios of methane to heavier hydrocarbon gases were used to differentiate sources of methane between a) microbial, b) thermogenic or c) mixed sources. Results indicate that microbial-sourced methane is widespread in the study area, and concentrations overlap with those from thermogenic sources. The highest concentrations of thermogenic gas were observed in proximity to relatively high density of oil wells, large injection volumes of water disposal and cyclic steam, shallow oil development, and hydrocarbon shows in sediments overlying the producing oil reservoirs. Depths of water wells containing thermogenic gas were within approximately 200 m of the top of the Vaca Tar Sand production zone (approximately 600 m below land surface). Due to the limited sampling density, the source and pathways of thermogenic gas detected in groundwater could not be conclusively determined. Thermogenic gas detected in the absence of co-occurring water from hydrocarbon-bearing formations may result from natural gas migration over geologic time from the Vaca Tar Sand or deeper formations, hydrocarbon shows in sediments overlying producing zones, and/or gas leaking from oil-field infrastructure. Denser sampling of groundwater, potential end-members, and pressure monitoring could help better distinguish pathways of thermogenic gases.

California

Combined impacts of current and future dust deposition and regional warming on Colorado River Basin snow dynamics and hydrology

The Colorado River provides water to 40 million people in seven western states and two countries and to 5.5 million irrigated acres. The river has long been overallocated. Climate models project runoff losses of 5&ndash;20% from the basin by mid-21st century due to human-induced climate change. Recent work has shown that decreased snow albedo from anthropogenic dust loading to the CO mountains shortens the duration of snow cover by several weeks relative to conditions prior to western expansion of the US in the mid-1800s, and advances peak runoff at Lees Ferry, Arizona, by an average of 3 weeks. Increases in evapotranspiration from earlier exposure of soils and germination of plants have been estimated to decrease annual runoff by more than 1.0 billion cubic meters, or ~5% of the annual average. This prior work was based on observed dust loadings during 2005&ndash;2008; however, 2009 and 2010 saw unprecedented levels of dust loading on snowpacks in the Upper Colorado River Basin (UCRB), being on the order of 5 times the 2005&ndash;2008 loading. Building on our prior work, we developed a new snow albedo decay parameterization based on observations in 2009/10 to mimic the radiative forcing of extreme dust deposition. We convolve low, moderate, and extreme dust/snow albedos with both historic climate forcing and two future climate scenarios via a delta method perturbation of historic records. Compared to moderate dust, extreme dust absorbs 2&times; to 4&times; the solar radiation, and shifts peak snowmelt an additional 3 weeks earlier to a total of 6 weeks earlier than pre-disturbance. The extreme dust scenario reduces annual flow volume an additional 1% (6% compared to pre-disturbance), a smaller difference than from low to moderate dust scenarios due to melt season shifting into a season of lower evaporative demand. The sensitivity of flow timing to dust radiative forcing of snow albedo is maintained under future climate scenarios, but the sensitivity of flow volume reductions decreases with increased climate forcing. These results have implications for water management and suggest that dust abatement efforts could be an important component of any climate adaptation strategies in the UCRB.

Arizona, Colorado, New Mexico, Utah, Wyoming

Population and habitat analyses for greater sage-grouse (Centrocercus urophasianus) in the bi-state distinct population segment—2018 update

Executive Summary The Bi-State Distinct Population Segment (Bi-State DPS) of greater sage-grouse ( Centrocercus urophasianus , hereinafter “sage-grouse”) represents a genetically distinct and geographically isolated population that straddles the border between Nevada and California. The primary threat to these sage-grouse populations is the expansion of single-leaf pinyon ( Pinus monophylla ) and Utah juniper ( Juniperus osteosperma ) into sagebrush ecosystems, which fragments and reduces population connectivity and survival. Other important threats include low water availability during brood-rearing, particularly during drought, and increased predation by common ravens ( Corvus corax ), a generalist predator often associated with anthropogenic resource subsidies. Although the Bi-State DPS occurs at high elevations relative to sage-grouse range-wide, changes in historical wildfire cycles and the conversion of native shrubs to invasive annual grasslands still threaten these populations. The Bi-State DPS has undergone multiple federal status assessments and associated litigation. For example, in October of 2013, the Bi-State DPS was proposed for listing as threatened under the Endangered Species Act of 1973 by the U.S. Fish and Wildlife Service (USFWS), then withdrawn in April 2015. The withdrawal decision was challenged, and in May 2018, a Federal district court ordered the withdrawal decision to be vacated, and USFWS was required to re-open the October 2013 listing evaluation. In response, the U.S. Geological Survey (USGS), with State and Federal collaborators, embarked on a multipronged analysis to provide current and best available science regarding population status of sage-grouse within the Bi-State DPS. Using data from a long-term monitoring program, we carried out four analytical study objectives, and here, we provide preliminary results of these analyses. First, we used integrated population modeling (IPM) to predict annual population abundance and annual finite rate of population change for the Bi-State DPS, as a whole, and for each subpopulation between 1995 and 2018. Because sage-grouse exhibit population cycles (periodic increases and decreases in abundance across approximately 6- to 10-year wavelengths), we estimated trends across three nested temporal scales that represent one (11 years), two (18 years), and three (24 years) complete population cycles. These estimates of relatively long-term averaged population change account for temporal (that is, interannual) variation. Our model predicted population abundance for the Bi-State DPS during 2018 at 3,305 individuals (2,247–4,683), with the majority occupying Bodie Hills and Long Valley. The model also predicted cyclic dynamics in abundance through time with evidence of 24-year population growth and slight trends of decline over the past 18 years. Specifically, across the Bi-State DPS as a whole, we estimated annual average at 0.99, 0.99, and 1.02 over the one, two, and three population cycles, which equated to a 10.5 percent, 16.6 percent decrease, and 60.0 percent increase in abundance over the 11-, 18-, and 24-year cycles. Estimated abundance in 2018 had not reached numbers lower than those predicted during 1995. However, we found spatial variation in population trends across the three cycles. Bodie Hills subpopulation comprised the greatest (1,521) and exhibited average annual greater than 1.0 across all periods resulting in average annual increases of 7 percent. This relatively large subpopulation has grown 5 times larger than what was predicted in 1995 while experiencing cyclical dynamics within that period. Conversely, other smaller subpopulations within the Bi-State DPS exhibited average annual equal to or less than 1.0 resulting in estimated 10-year risks of extirpation ranging from 2.0 to 76.1 percent. In general, evidence of decline among smaller subpopulations was greatest for the most recent period (2008–18) compared to a period that encompassed three full population cycles (24-year). This difference coincides with an intense period of drought that began in 2012. For comparative purposes as part of this first objective, we conducted a similar analysis for populations of sage-grouse within Nevada and California but outside the Bi-State DPS. We developed a region-wide and distance-weighted IPM using lek count from Nevada Department of Wildlife (NDOW) and California Department of Fish and Wildlife (CDFW) databases and with telemetry data collected by USGS across 12 sage-grouse subpopulations. Our models predicted similar patterns in population cycling outside the Bi-State DPS but with much stronger evidence of long-term declines across 24 years. Specifically, median averaged across each year of the 11-, 18-, and 24-year periods resulted in average annual values of 0.94, 0.97, and 0.99, respectively. These values equate to 41.0 percent, 38.5 percent, and 21.3 percent declines over the corresponding periods. Second, we used lek count data in a state-space modeling framework to compare trends in population abundance across different spatial scales (that is, leks versus Bi-State DPS). This hierarchical framework allowed us to disentangle declines associated with climate conditions as opposed to other local level factors that might signal the need for management intervention. Specifically, we identified 7 leks that were both declining and recently decoupled from larger spatial scale trends, typically governed by climatic conditions (referred to as soft or hard signals). The goal of this analysis was to provide an early warning system that might have implications for conservation actions at local scales. Third, we developed phenological (spring, summer–fall, and winter) and reproductive life stage (nesting, early brood-rearing, and late-brood rearing) based resource selection functions using various environmental covariates. We report rankings of variable importance for each season and life stage, developed maps of habitat selection indices (HSI), binned categories representing low, moderate, and high classes of quality (where any category greater than or equal to low indicated selected habitat) for each phenological season and life stage, and produced composite maps by selected phenological and reproductive stage to estimate annual habitat. Fourth, we used for each lek within the Bi-State DPS to carry out a spatial analysis that quantified substantial changes in the distribution of occupied habitat across long- (24-year) and short- (11-year) term periods. Owing to differences among available datasets, the long-term analysis primarily reflected spatial shifts among subpopulations comprising the majority of the Bi-State DPS (that is, Bodie Hills and Long Valley) while the short-term analysis also quantified changes among subpopulations along the periphery. Over long and short-term periods, the overall distribution of occupied habitat (as measured by 99 percent utilization distributions intersecting any quantified habitat) was reduced by 20,573 ha and 55,492 ha, respectively. Occupied core areas (as measured by 50 percent utilization distributions intersecting any quantified habitat) over long-term periods were solely located in Bodie Hills and Long Valley. Although nearly all subpopulations experienced contractions in occupied overall and core distribution, Bodie Hills experienced spatial expansion that occurred with concomitant spatial contraction at Long Valley over both periods. Subpopulations at the northern (Pine Nuts), central (Sagehen) and southern (White-Mountains) extents of the Bi-State DPS also experienced spatial contraction over the short-term period. These findings, coupled with those of population trends, indicate long-term patterns in redistribution of sage-grouse from Long Valley and peripheral subpopulations to Bodie Hills. That is, sage-grouse subpopulations at the periphery are declining while the largest population at the core is increasing, which could have meaningful impacts on overall metapopulation persistence. We provide evidence for loss of occupied habitat (reduced distribution) given local extirpation of subpopulations. Fifth, we calculated percentages of selected phenological, life stage, and annual habitat that each subpopulation contributed to the Bi-State DPS. We then intersected these maps with a composite estimate of occupied habitat from the fourth objective and calculated percentages of selected habitat likely occupied by sage-grouse that each subpopulation contributed to the Bi-State DPS. These values provide evidence for loss of occupied habitat and subsequent reductions in spatial distribution given reductions in abundance and, in some cases, extirpation of leks within subpopulations. Lastly, we carried out an initial in-depth analysis of selection for irrigated pastures and wet meadows during the brood-rearing stage for the Long Valley subpopulation. We chose this subpopulation because it represents a population core, representing 26.5 percent of total sage-grouse within the Bi-State DPS, and has exhibited long-term declines in abundance and distribution. This subpopulation is highly sensitive to precipitation and other factors that influence water availability. Models predicted higher use of the interior portions of irrigated pastures and wet meadows during late brood-rearing period, which represented a potentially risky use of habitat that was exacerbated during periods of low moisture (for example, drought, reduced water delivery, or both). Sage-grouse typically used edges of riparian areas and pastures, largely because the interior of these mesic areas consisted of considerably less overhead concealment cover (for example, shrubs) that likely resulted in a higher risk of mortality. We found that a lack of water delivery to pastures in the form of overwinter precipitation or diversion ditches increased the movements of sage-grouse to the interior of pastures. Although further investigation of water delivery impacts on chick survival are warrented, our initial findings regarding resource selection may explain recent declines in population growth at Long Valley.

California, Nevada

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

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

Colorado