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Hydrogeology, chemical characteristics, and water sources and pathways in the zone of contribution of a public-supply well in San Antonio, Texas

In 2001, the National Water-Quality Assessment (NAWQA) Program of the U.S. Geological Survey initiated a series of studies on the transport of anthropogenic and natural contaminants (TANC) to public-supply wells (PSWs). The main goal of the TANC project was to better understand the source, transport, and receptor factors that control contaminant movement to PSWs in representative aquifers of the United States. Regional- and local-scale study areas were selected from within existing NAWQA study units, including the south-central Texas Edwards aquifer. The local-scale TANC study area, nested within the regional-scale NAWQA study area, is representative of the regional Edwards aquifer. The PSW selected for study is within a well field of six production wells. Although a single PSW was initially selected, because of constraints of well-field operation, samples were collected from different wells within the well field for different components of the study. Data collected from all of the well-field wells were considered comparable because of similar well construction, hydrogeology, and geochemistry. An additional 38 PSWs (mostly completed in the confined part of the aquifer) were sampled throughout the regional aquifer to characterize water quality. Two monitoring well clusters, with wells completed at different depths, were installed to the east and west of the well field (the Zarzamora and Timberhill monitoring well clusters, respectively). One of the monitoring wells was completed in the overburden to evaluate potential hydrologic connectivity with the Edwards aquifer. Geophysical and flowmeter logs were collected from one of the well-field PSWs to determine zones of contribution to the wellbore. These contributing zones, associated with different hydrogeologic units, were used to select monitoring well completion depths and groundwater sample collection depths for depth-dependent sampling. Depth-dependent samples were collected from the PSW from three different depths and under three different pumping conditions. Additionally, selected monitoring wells and one of the well-field PSWs were sampled several times in response to a rainfall and recharge event to assess short-term (event-scale) temporal variations in water quality. For comparison purposes, groundwater samples were categorized as being from regional aquifer PSWs, from the well field (wellhead samples), from the monitoring wells (excluding the overburden well), from the overburden well, from the PSW depth-dependent sampling, and from temporal sampling. Groundwater samples were analyzed for inorganic, organic, isotopic, and age-dating tracers to characterize geochemical conditions in the aquifer and provide understanding of the mechanisms of mobilization and movement of selected constituents from source areas to a PSW. Sources, tracers, and conditions used to assess water quality and processes affecting the PSW and the aquifer system included (1) carbonate host rock composition; (2) physicochemical constituents; (3) major and trace element concentrations; (4) saturation indices with respect to minerals in aquifer rocks; (5) elemental ratios, such as magnesium to calcium ratios, that are indicative of water-rock interaction processes; (6) oxidation-reduction conditions; (7) nutrient concentrations, in particular nitrate concentrations; (8) the isotopic composition of nitrate, which can point to specific nitrate sources; (9) strontium isotopes; (10) stable isotopes of hydrogen and oxygen; (11) organic contaminant concentrations, including pesticides and volatile organic compounds; (12) age tracers, apparent-age distribution, and dissolved gas data used in age interpretations; (13) depth-dependent water chemistry collected from the PSW under different pumping conditions to assess zones of contribution; and (14) temporal variability in groundwater composition from the PSW and selected monitoring wells in response to an aquifer recharge event. Geochemical results indicate that the well-field and monitoring well samples were largely representative of groundwater in the regional confined aquifer. Constituents of concern in the Edwards aquifer for the long-term sustainability of the groundwater resource include the nutrient nitrate and anthropogenic organic contaminants. Nitrate concentrations (as nitrogen) for regional aquifer PSWs had a median value of 1.9 milligrams per liter, which is similar to previously reported values for the regional aquifer. Nitrate-isotope compositions for groundwater samples collected from the well-field PSWs and monitoring wells had a narrow range, with values indicative of natural soil organic values. A comparison with historical nitrate-isotope values, however, suggests that a component of nitrate in groundwater from biogenic sources might have increased over the last 30 years. Several organic contaminants (the pesticide atrazine, its degradate deethylatrazine, trichloromethane (chloroform; a drinking-water disinfection byproduct), and the solvent tetrachloroethene (PCE)) were widely distributed throughout the regional aquifer and in the local-scale TANC study area at low concentrations (less than 1 microgram per liter). Higher concentrations of PCE were detected in samples from the well-field PSWs and Zarzamora monitoring wells relative to the regional aquifer PSWs. The urban environment is a likely source of contaminants to the aquifer, and these results indicate that one or more local urban sources might be supplying PCE to the Zarzamora monitoring wells and the well-field wells. Samples from the well field also had high concentrations of chloroform relative to the monitoring wells and regional aquifer PSWs. For samples from the regional aquifer PSWs, the most frequently detected organic contaminants generally decreased in concentration with increasing well depth. Deeper wells might intercept longer regional flow paths with higher fractions of older water or water recharged in rural recharge areas in the western part of the aquifer that have been less affected by anthropogenic contaminants. A scenario of hypothetical contaminant loading was evaluated by using results from groundwater-flow-model particle tracking to assess the response of the aquifer to potential contamination. Results indicate that the aquifer responds quickly (less than 1 year to several years) to contaminant loading; however, it takes a relatively long time (decades) for concentrations to reach peak values. The aquifer also responds quickly (less than 1 year to several years) to the removal of contaminant loading; however, it also takes a relatively long time (decades) to reach near background concentrations. Interpretation of geochemical age tracers in this well-mixed karst system was complicated by contamination of a majority of measured tracers and complexities of extensive mixing. Age-tracer results generally indicated that groundwater samples were composed of young, recently recharged water with piston-flow model ages ranging from less than 1 to 41 years, with a median of 17 years. Although a piston-flow model is typically not valid for karst aquifers, the model ages provide a basis for comparing relative ages of different samples and a reference point for more complex hydrogeologic models for apparent-age interpretations. Young groundwater ages are consistent with particle-tracking results from hydrogeologic modeling for the local-scale TANC study area. Age-tracer results compared poorly with other geochemical indicators of groundwater residence time and anthropogenic effects on water quality, indicating that hydrogeologic conceptual models used in groundwater age interpretations might not adequately account for mixing in this karst system. Groundwater samples collected from the well field under a variety of pumping conditions were relatively homogeneous and well mixed for numerous geochemical constituents (with the notable exception of age tracers). Groundwater contributions to the PSW were dominated by well-mixed, relatively homogeneous groundwater, typical of the regional confined aquifer. Zones of preferential flow were determined for the PSW, but groundwater samples from different stratigraphic units were not geochemically distinct. Variations in chemical constituents in response to a rainfall and aquifer recharge event occurred but were relatively minor in the PSW and monitoring wells. This observation is consistent with the hypothesis that the response to individual recharge events in the confined aquifer, unless intersecting conduit flow paths, might be attenuated by mixing processes along regional flow paths. Results of this study are consistent with the existing conceptual understanding of aquifer processes in this karst system and are useful for water-resource development and management practices.

Texas

The integrated monarch monitoring program: From design to implementation

Steep declines in North American monarch butterfly ( Danaus plexippus ) populations have prompted continent-wide conservation efforts. While monarch monitoring efforts have existed for years, we lack a comprehensive approach to monitoring population vital rates integrated with habitat quality to inform adaptive management and effective conservation strategies. Building a geographically and ecologically representative dataset of monarchs and their habitat will improve these efforts. These data will help track long-term changes in the distribution and abundance of monarchs and their habitats, refine population and habitat models, and illuminate how conservation activities affect monarchs and their habitats. The Monarch Conservation Science Partnership developed the Integrated Monarch Monitoring Program (IMMP) to profile breeding habitats and their use by monarchs in North America. A spatially balanced random sampling framework guides site selection, while also allowing opportunistic inclusion of sites chosen by participants, such as conservation areas. The IMMP weaves new protocols together with those from existing monitoring programs to improve data compatibility for assessing milkweed (Asclepias spp.) density, nectar resources, monarch reproduction and survival, and adult monarch habitat use. Participants may select a protocol subset according to interests or local monitoring objectives, thereby maximizing contributions. Conservation partners, including public and private land managers, academic researchers, and citizen scientists contribute data to a national dataset available for analyses at multiple scales. We describe the program and its development, implementation elements that make the program robust and feasible, participation to date, and how IMMP data can advance research and conservation for monarchs, pollinators, and their habitats.

North America

Triangle area water supply monitoring project, October 1988 through September 2001, North Carolina -- description of the water-quality network, sampling and analysis methods, and quality-assurance practices

The Triangle Area Water Supply Monitoring Project was initiated in October 1988 to provide long-term water-quality data for six area water-supply reservoirs and their tributaries. In addition, the project provides data that can be used to determine the effectiveness of large-scale changes in water-resource management practices, document differences in water quality among water-supply types (large multiuse reservoir, small reservoir, run-of-river), and tributary-loading and in-lake data for water-quality modeling of Falls and Jordan Lakes. By September 2001, the project had progressed in four phases and included as many as 34 sites (in 1991). Most sites were sampled and analyzed by the U.S. Geological Survey. Some sites were already a part of the North Carolina Division of Water Quality statewide ambient water-quality monitoring network and were sampled by the Division of Water Quality. The network has provided data on streamflow, physical properties, and concentrations of nutrients, major ions, metals, trace elements, chlorophyll, total organic carbon, suspended sediment, and selected synthetic organic compounds. Project quality-assurance activities include written procedures for sample collection, record management and archive, collection of field quality-control samples (blank samples and replicate samples), and monitoring the quality of field supplies. In addition to project quality-assurance activities, the quality of laboratory analyses was assessed through laboratory quality-assurance practices and an independent laboratory quality-control assessment provided by the U.S. Geological Survey Branch of Quality Systems through the Blind Inorganic Sample Project and the Organic Blind Sample Project.

North Carolina

Management case study: Tampa Bay, Florida

Tampa Bay, Florida, USA, is a shallow, subtropical estuary that experienced severe cultural eutrophication between the 1940s and 1980s, a period when the human population of its watershed quadrupled. In response, citizen action led to the formation of a public- and private-sector partnership (the Tampa Bay Estuary Program), which adopted a number of management objectives to support the restoration and protection of the bay’s living resources. These included numeric chlorophyll a and water-clarity targets, as well as long-term goals addressing the spatial extent of seagrasses and other selected habitat types, to support estuarine-dependent faunal guilds. Over the past three decades, nitrogen controls involving sources such as wastewater treatment plants, stormwater conveyance systems, fertilizer manufacturing and shipping operations, and power plants have been undertaken to meet these and other management objectives. Cumulatively, these controls have resulted in a 60% reduction in annual total nitrogen (TN) loads relative to earlier worse-case (latter 1970s) conditions. As a result, annual water-clarity and chlorophyll a targets are currently met in most years, and seagrass cover measured in 2008 was the highest recorded since 1950. Factors that have contributed to the observed improvements in Tampa Bay over the past several decades include the following: (1) Development of numeric, science-based water-quality targets to meet a long-term goal of restoring seagrass acreage to 1950s levels. Empirical and mechanistic models found that annual average chlorophyll a concentrations were a primary manageable factor affecting light attenuation. The models also quantified relationships between TN loads, chlorophyll a concentrations, light attenuation, and fluctuations in seagrass cover. The availability of long-term monitoring data, and a systematic process for using the data to evaluate the effectiveness of management actions, has allowed managers to track progress and make adaptive changes when needed. (2) Citizen involvement, that is, the initial reductions in TN loads, which occurred in the late 1970s and early 1980s, was a result of state regulations that were developed in response to citizens’ call for action. Improved water clarity and better fishing and swimming conditions were identified as primary goals by citizens again in the early 1990s, and led to development of numeric water-quality targets and seagrass restoration goals. More recent citizen actions, from pet waste campaigns to support of reductions in residential fertilizer use, are important elements of the nitrogen management strategy. (3) Collaborative actions, that is, in addition to numerous other collaborative ventures that have benefitted Tampa Bay, the public/private Nitrogen Management Consortium, which includes more than 40 participating organizations, has implemented over 250 nutrient-reduction projects. These projects have addressed stormwater treatment, fertilizer manufacturing and shipping, agricultural practices, reclaimed water use, and atmospheric emissions from local power stations, providing more than 300 tons of TN load reductions since 1995. (4) State and federal regulatory programs, that is, regulatory requirements, such as state statutes and rules requiring compliance with advanced wastewater treatment standards by municipal sewerage works, have played a key role in Tampa Bay management efforts. The technical basis and implementation plan of the Tampa Bay nitrogen management strategy have been developed in cooperation with state and federal regulatory agencies, and the strategy has been recognized by them as an appropriate tool for meeting water-quality standards, including federally mandated total maximum daily loads. Subsequent management efforts have focused on maintaining and extending those improvements in Tampa Bay’s environmental resources by addressing water and sediment quality and habitat protection and restoration. Implementation of a collaborative, watershed-based management process, driven by an integrated science approach, has played a central role in supporting progress toward the achievement of science-based estuary management goals.

Florida

Strategies for ensuring global consistency/comparability of water-quality data

In the past 20 years the water quality of the United States has improved remarkably-the waters are safer for drinking, swimming, and fishing. However, despite many accomplishments, it is still difficult to answer such basic questions as: 'How clean is the water?' and 'How is it changing over time?' These same questions exist on a global scale as well. In order to focus water-data issues in the United States, a national Intergovernmental Task Force on Monitoring Water Quality (ITFM) was initiated for public and private organizations, whereby key elements involved in data collection, analysis, storage, and management could be made consistent and comparable. The ITFM recommended and its members are implementing a nationwide strategy to improve water-quality monitoring, assessment, and reporting activities. The intent of this paper is to suggest that a voluntary effort be initiated to ensure the comparability and utility of hydrological data on a global basis. Consistent, long-term data sets that are comparable are necessary in order to formulate ideas regarding regional and global trends in water quantity and quality. The author recommends that a voluntary effort similar to the ITFM effort be utilized. The strategy proposed would involve voluntary representation from countries and international organizations (e.g. World Health Organization) involved in drinking-water assessments and/or ambient water-quality monitoring. Voluntary partnerships such as this will improve curability to reduce health risks and achieve a better return on public and private investments in monitoring, environmental protection, and natural resource management, and result in a collaborative process that will save millions of dollars.In this work it is suggested that a voluntary effort be initiated to ensure the comparability and utility of hydrological data on a global basis. The strategy proposed would involve voluntary representation from countries and international organizations involved in drinking-water assessments and/or ambient water-quality monitoring.

Conference Paper

Potential for chemical transport beneath a storm-runoff recharge (retention) basin for an industrial catchment in Fresno, California

A wide variety of chemicals from urban runoff were found at elevated concentrations in sediment that accumulated in a storm-runoff recharge basin in an industrial part of the city of Fresno. The chemicals include as many as 20 inorganic elements and about the same number of organic compounds, primarily organochlorine pesticides and polycyclic aromatic hydrocarbons. Most of these contaminants were found to be sorbed to the upper 4 centimeters of sediment, which also is the maximum depth to which atmospheric lead-210 penetrated. None of the contaminants were detected above background concentrations in the sediment at depths greater than 16 centimeters. In shallow sediment, zinc is the inorganic element that showed the greatest enrichment; its concentration was 38 times higher in surface sediment (0-1 centimeter) than in deeper strata (below 16 centi- meters). Organic carbon enrichment in the surface sediment was nearly 1,000 times. Although batch- elutriation experiments demonstrated the potential for leaching of contaminants attached to sediments, a sharp decrease in concentrations with increasing sediment depth, and the extremely low level of contaminants in two monitor wells adjacent to the basin, confirmed the absence of contaminant transport to the water table. Continued long-term protection for ground water is afforded by an approximately 8-meter-thick unsaturated zone beneath the basin. On the basis of its hundredfold-higher concentration in the recharge pond then in ground water, zinc is indicated as the most sensitive surrogate for monitoring possible ground-water degradation by inorganic cations.

Water-Resources Investigations Report

Baseline water quality and preliminary effects of artificial recharge on ground water, south-central Kansas, 1995–98

To investigate the feasbility of artificial recharge as a method of meeting future water-supply needs and to protect the Equus Beds aquifer from saltwater intrusion from natural and anthropogenic sources to the west, the Equus Beds Ground-Water Recharge from Demonstration Project was begun in 1995. The project is a cooperative effort between the city of Wichita and the Bureau of Reclamation, U.S. Department of the Interior. During the project, high flows from the Little Arkansas River are captured and recharged into the Equus Beds aquifer through recharge basins, a trench, or a recharge well, located at two recharge sites near Halstead and Sedgwick, Kansas. To document baseline concentrations and compatibility of stream (recharge) and aquifer water, the U.S. Geological Survey collected water samples from February 1995 through August 1998. These samples were analyzed for dissolved solids, total and dissolved inorganic constituents, nutrients, organic and volatile organic compounds, radionuclides, and bacteria. Results of baseline sampling indicated that the primary constituents of concern for recharge were sodium, chloride, nitrite plus nitrate, iron and manganese, total coliform bacteria, and atrazine. Chloride and atrazine were of particular concern because concentrations of these constituents in water from the Little Arkansas River frequently exceeded regulatory criteria. The Little Arkansas River is used as the source water for recharge. The U.S. Environmental Protection Agency Secondary Maximum Contaminant Level for chloride is 250 mg/L (milligrams per liter), and the Maximum Contaminant Level for atrazine is 3.0 μg/L (micrograms per liter) as an annual mean. Baseline concentrations of chloride in surface water ranged from 8.0 to 400 μg/L. Baseline concentrations of atrazine in surface water ranged from less than 0.10 to 46 μg/L. Concentrations of chloride and atrazine have increased in water from some of the wells at both the Halstead and Sedgwick recharge sites after recharge began, although concentrations remained within the range of baseline values in the Equus Beds aquifer and are considerably less than U.S. Environmental Protection Agency drinking-water criteria. However, a substantial quantity of water has not been recharged at the Sedgwick site to determine the overall effects of artificial recharge on aquifer quality. Continued monitoring is necessary to determine long-term effects at both sites. Major ion and trace element concentrations in source water and receiving water were analyzed to determine the compatibility of recharge and receiving ground water for artificial recharge. Stiff diagrams of major ions were used to show the similarity or differences between source surface water and receiving ground water. The water from both sources, for the most part, was chemically compatible to the receiving aquifer water at both recharge sites. It may be possible to decrease the monitoring frequency at the Halstead recharge site because water-quality changes in receiving water at this site are very gradual. However, real-time water-quality monitoring of surrogates needs to be site specific for the determination of chloride and atrazine. Real-time water-quality monitoring potentially can be used to more effectively manage the artificial recharge process, enabling project officials to respond more rapidly to changes in water quality.

Water-Resources Investigations Report

Development of a grazing monitoring program for Great Sand Dunes National Park, Colorado

National parks in the United States face the difficult task of managing natural resources within park boundaries that are influenced to a large degree by historical land uses or by forces outside of the park’s protection and mandate. Among the many challenges faced by parks is management of wildlife populations that occupy larger landscapes than individual park units but that concentrate within park lands both seasonally and opportunistically. Great Sand Dunes National Park and Preserve in south-central Colorado is currently developing an Ungulate Management Plan to address management of elk and bison populations within the park. Execution of the Ungulate Management Plan will require monitoring and assessment of habitat conditions in areas that appear sensitive to ungulate use or heavily used by elk and bison. Several sources of information on the various habitats within the park and their use and response to foraging elk and bison exist from recent and on-going research in Great Sand Dunes National Park and Preserve as well as from studies in other regions of the Intermountain West. All of this data can be used to inform the planning process. This report provides background on vegetation types that make up the primary bison and elk ranges in Great Sand Dunes National Park and Preserve and on the potential effects of ungulate grazing and browsing in these specific vegetation communities (both locally and regionally). The report also provides a review of the elements necessary to develop a long-term monitoring program for Great Sand Dunes National Park and Preserve that addresses both the responses to ungulate herbivory seen in important habitats in the park and the amount and patterns of ungulate habitat use.

Colorado

Summary of information on synthetic organic compounds and trace elements in tissue of aquatic biota, Clark Fork-Pend Oreille and Spokane River basins, Montana, Idaho, and Washington, 1974-96

As part of the Northern Rockies Intermontane Basins study of the National Water-Quality Assessment Program, data collected between 1974 and 1996 were compiled to describe contaminants in tissue of riverine species. Tissue-contaminant data from 11 monitoring programs and studies representing 28 sites in the study area were summarized. Tissue-contaminant data for most streams generally were lacking. Many studies have focused on and around mining-affected areas on the Clark Fork and Coeur d'Alene Rivers and their major tributaries. DDT and PCBs and their metabolites and congeners were the synthetic organic contaminants most commonly detected in fish tissue. Fish collected from the Spokane River in Washington contained elevated concentrations of PCB arochlors, some of which exceeded guidelines for the protection of human health and predatory wildlife. Tissue samples of fish from the Flathead River watershed contained higher-than-expected concentrations of PCBs, which might have resulted from atmospheric transport. Trace element concentrations in fish and macroinvertebrates collected in and around mining areas were elevated compared with background concentrations. Some cadmium, copper, lead, and mercury concentrations in fish tissue were elevated compared with results from other studies, and some exceeded guidelines. Macroinvertebrates from the Coeur d'Alene River contained higher concentrations of cadmium, lead, and zinc than did macroinvertebrates from other river systems in mining-affected areas. A few sportfish fillet samples, most from the Spokane River in Washington, were collected to assess human health risk. Concentrations of PCBs in these fillets exceeded screening values for the protection of human health. At present, there is no coordinated, long-term fish tissue monitoring program for rivers in the study area, even though contaminants are present in fish at levels considered a threat to human health. Development of a coordinated, centralized national data base for contaminants in fish tissue is needed. The National Water-Quality Assessment Program can provide a framework for other agencies to evaluate tissue contaminants in the Northern Rockies Intermontane Basins study area. As of 1996, there are no fish consumption advisories or fishing restrictions as a result of elevated contaminants on any rivers within the study area.

Idaho, Montana, Washington

Benthic response to water quality and biotic pressures in lower south San Francisco Bay, Alviso Slough, and Coyote Creek

Benthic invertebrate communities are monitored because the composition of those communities can effect and be affected by the water quality of an aquatic system. Benthic communities use and sometimes regulate the cycling of essential elements (for example, carbon). Benthic invertebrate taxa may also indicate acutely and chronically stressful environments because they are mostly sessile, accumulate contaminants, and sometimes respond dramatically to oligotrophic as well as eutrophic conditions. Benthic communities can in turn affect water quality by grazing pelagic food resources and increasing the rate of nutrient regeneration through feeding and bioturbating the sediment. South San Francisco Bay is a system dependent on phytoplankton as the base to the food web. Despite abundant nutrients, south San Francisco Bay has had limited phytoplankton production in the last several decades owning to poor light conditions and high grazing losses from the water column by benthic invertebrates. The south San Francisco Bay achieves a balance of biogeochemical conditions in most springs to accommodate a short phytoplankton bloom. This balance has maintained the phytoplankton in south San Francisco Bay at low biomass levels relative to other high-nutrient urban estuaries. The role that benthic invertebrates play in this balance, in these episodic spring events, and in other seasons within the estuary remains of great interest to water-quality and biological resource managers. Our primary objective in this study is to quantify current (2014) benthic-community structure and function in the south San Francisco Bay sloughs and to compare those communities temporally over decadal time scales with a unique long-term dataset. The study area (fig. 1) is inclusive of the area south of the Dumbarton Bridge (DB) including Alviso and Guadalupe Sloughs and Coyote Creek. The following are results highlighted in this report: The benthic communities of Coyote Creek and Alviso, Guadalupe, and Artesian Sloughs were dominated by different organisms but similar functional groups in March, June, and September 2014. Coyote Creek stations (D3 and CC1) had a similar increase in Potamocorbula amurensis biomass followed by a decline in 2014, as was observed annually in the south San Francisco Bay since 1999. The lack of grazing pressure owing to the observed declines in these taxa in 2014 may allow the sloughs to become sources of phytoplankton in spring. Bivalve biomass is elevated in summer and fall relative to the spring and winter except in Artesian Slough, where bivalves did not establish a signifcant presence. Presence of certain species contributes to the prey value of the community to predators. Potamocorbula amurensis is a shallow-burrowing bivalve and hence is easy prey for bottom-feeding predators. In contrast, Macoma petalum is a deposit feeder and can burrow deeper into the substrate than Potamocorbula amurensis , making it harder to be preyed upon. The quantitative importance of such predator-prey relationships on phytoplankton dynamics requires further investigation. There were also more amphipods in the sloughs in March 2014; this group is another potential contributor to the benthic-pelagic biomass balance. There is no observed reason for Artesian Slough to have low bivalve biomass values and high amphipod abundances.

California

Water-quality trends for streams and reservoirs in the Research Triangle area of North Carolina, 1983-95

Water-quality and streamflow monitoring data, collected from 1983 to 1995, were analyzed for 34 stream and reservoir sites in a seven-county region within the upper Neuse and upper Cape Fear River Basins. Early data (1983-88) were compiled from U.S. Geological Survey water-quality studies and from the ambient water-quality monitoring network of the North Carolina Department of Environment, Health, and Natural Resources. Analyses of major ions, nutrients, metals, trace elements, and synthetic organic compounds were compiled from samples collected by the U.S. Geological Survey from 1988 to 1995 as part of a continuing project to monitor the water quality of surface-water supplies in the Research Triangle area of North Carolina, and from the North Carolina Department of Environment, Health, and Natural Resources ambient water-quality monitoring network. This report presents the results of analysis of consistently increasing or decreasing trends in concentrations of nitrogen and phosphorus species, suspended sediment, suspended solids, sodium, chloride, iron, manganese, zinc, and chlorophyll a from seasonal Kendall trend analysis on flow-adjusted concentrations for streams and concentrations in lakes. Total phosphorus concentrations also were tested for a step decrease in concentration (step trend) associated with the North Carolina phosphate-detergent ban of 1988. For some other constituents, insufficient data or values below laboratory detection limits precluded trend analysis. A regionwide decrease in total phosphorus, ranging from 25 to 81 percent, was observed that coincided with increased phosphorus removal efforts at municipal wastewater-treatment facilities in the region and the statewide phosphate-detergent ban. Most sites had stable or decreasing trends in nitrogen concentrations; however, increasing trends occurred in the Neuse River near Clayton and at Smithfield, both of which are downstream from the developing Raleigh-Durham area. Chlorophyll a concentrations have increased by 17 to 52 percent per year at monitored reservoirs, except at Cane Creek Reservoir and Lake Michie where there was no trend. No significant trends in suspended-sediment concentrations were observed. Long-term sodium concentrations were available for only a few sites. Of these, decreasing concentrations were observed in the Neuse River at Smithfield and Cane Creek near Orange Grove, and an increasing concentration was observed in University Lake. At most sites, concentrations of manganese, iron, and zinc were stable. Decreasing iron trends were observed in Little River and Cane Creek Reservoirs and Lake Michie. Cane Creek Reservoir also had a decreasing manganese trend. Seven sites, all downstream from wastewater-treatment facilities, were analyzed for zinc trends. A decreasing trend was observed in two of these--Knap of Reeds Creek and Little Lick Creek.

North Carolina

Review of Trace-Element Field-Blank Data Collected for the California Groundwater Ambient Monitoring and Assessment (GAMA) Program, May 2004-January 2008

Trace-element quality-control samples (for example, source-solution blanks, field blanks, and field replicates) were collected as part of a statewide investigation of groundwater quality in California, known as the Priority Basins Project of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA Priority Basins Project is being conducted by the U.S. Geological Survey (USGS) in cooperation with the California State Water Resources Control Board (SWRCB) to assess and monitor the quality of groundwater resources used for drinking-water supply and to improve public knowledge of groundwater quality in California. Trace-element field blanks were collected to evaluate potential bias in the corresponding environmental data. Bias in the environmental data could result from contamination in the field during sample collection, from the groundwater coming into contact with contaminants on equipment surfaces or from other sources, or from processing, shipping, or analyzing the samples. Bias affects the interpretation of environmental data, particularly if any constituents are present solely as a result of extrinsic contamination that would have otherwise been absent from the groundwater that was sampled. Field blanks were collected, analyzed, and reviewed to identify and quantify extrinsic contamination bias. Data derived from source-solution blanks and laboratory quality-control samples also were considered in evaluating potential contamination bias. Eighty-six field-blank samples collected from May 2004 to January 2008 were analyzed for the concentrations of 25 trace elements. Results from these field blanks were used to interpret the data for the 816 samples of untreated groundwater collected over the same period. Constituents analyzed were aluminum (Al), antimony (Sb), arsenic (As), barium (Ba), beryllium (Be), boron (B), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), lead (Pb), lithium (Li), manganese (Mn), mercury (Hg), molybdenum (Mo), nickel (Ni), selenium (Se), silver (Ag), strontium (Sr), thallium (Tl), tungsten (W), uranium (U), vanadium (V), and zinc (Zn). The detection frequency and the 90th percentile concentration at greater than 90 percent confidence were determined from the field-blank data for each trace element, and these results were compared to each constituent's long-term method detection level (LT-MDL) to determine whether a study reporting level (SRL) was necessary to ensure that no more than 10 percent of the detections in groundwater samples could be attributed solely to contamination bias. Only two of the trace elements analyzed, Li and Se, had zero detections in the 86 field blanks. Ten other trace elements (Sb, As, Be, B, Cd, Co, Mo, Ag, Tl, and U) were detected in fewer than 5 percent of the field blanks. The field-blank results for these constituents did not necessitate establishing SRLs. Of the 13 constituents that were detected in more than 5 percent of the field blanks, six (Al, Ba, Cr, Mn, Hg, and V) had field-blank results that indicated a need for SRLs that were at or below the highest laboratory reporting levels (LRL) used during the sampling period; these SRLs were needed for concentrations between the LT-MDLs and LRLs. The other seven constituents with detection frequencies above 5 percent (Cu, Fe, Pb, Ni, Sr, W, and Zn) had field-blank results that necessitated SRLs greater than the highest LRLs used during the study period. SRLs for these seven constituents, each set at the 90th percentile of their concentrations in the field blanks, were at least an order of magnitude below the regulatory thresholds established for drinking water for health or aesthetic purposes; therefore, reporting values below the SRLs as less than or equal to (=) the measured value would not prevent the identification of values greater than the drinking-water thresholds. The SRLs and drinking-water thresholds, respectively, for these 7 trace elements are Cu (1.7 ?g/L and 1,300

Scientific Investigations Report

Small watershed studies: Analytical approaches for understanding ecosystem response to environmental change

Biogeochemical studies in small watersheds provide an analytical approach to understand how ecosystems respond to natural climatic variations and human-induced environmental change. Small watersheds, usually less than 5 km2, are small enough to permit characterization and understanding of ecosystem processes within relatively simple, homogeneous biological and physical settings; yet they are large enough to incorporate more complex processes and element cycles than can be studied at plot scales. Watersheds comprise discrete hydrochemical environments allowing quantification of hydrologic, element, and energy budgets. Element budgets, or mass balances, can be quantified as the difference between the mass of a solute that enters a watershed in wet and dry deposition and leaves a watershed in streamflow. Element budgets are primary tools used to investigate biogeochemical processes. Monitoring various aspects of element budgets to assess ecosystem health and stability is analogous to measuring the pulse or blood chemistry of a patient. Monitoring streamwater chemistry, basic climate, soil, and biotic variables provide a means to integrate complex biogeochemical processes and evaluate trends in water quality. Small watershed studies provide a scientific basis to develop predictive models of watershed function. Major emphases of small watershed studies include investigation of hydrologic and chemical responses to natural climate variation, anthropogenic stressors, and alternate forest-management practices. The nature and significance of biogeochemical research in small watersheds is reviewed by Moldan and Cerny (1994). The U.S. Geological Survey, U.S. Department of Agriculture Forest Service, and other federal agencies support several long-term small watershed studies to provide insight into a variety of ecosystem processes. Long-term records are essential to distinguish trends resulting from natural climatic variations or other stressors. The following sites, with noted periods of records, are examples of intensively studied forested watersheds in eastern USA supported by federal agencies: ■ Coweeta Hydrologic Laboratory, North Carolina, (1939-present), Swank and Crossley (1988). ■ Hubbard Brook Experimental Forest, New Hampshire, (1956-present), Bormann and Likens (1979). ■ Sleepers River Research Watershed, Vermont, (1958-present), Shanley et al. (1995). ■ Walker Branch Watershed, Tennessee, (1967-present), Johnson and Van Hook (1989). ■ Catoctin Mountains Research Site, Maryland, (1982-present), Rice and Bricker (1995). ■ Catskill Stream Network, New York, (1983- present), Murdoch and Stoddard (1992). ■ Panola Mountain Research Watershed, Georgia, (1985-present), Huntington et al. (1993). Small watershed studies also provide essential baseline information for understanding variations in water quality and element cycling in "pristine" ecosystems that can be used as benchmarks to evaluate anthropogenic impacts and alternate watershed management practices. This paper provides examples of how analytical tools developed through watershed research provide insight into ecosystem processes and can contribute to the management of watershed resources.

Conference Paper

Water-resources-related information for the Milwaukee Metropolitan Sewerage District planning area, Wisconsin, 1970-2002

The Milwaukee Metropolitan Sewerage District (MMSD) Corridor Study is a three-phase project designed to improve the understanding of water resources in the stream corridors of the MMSD planning area by initially compiling existing data and using the compiled information to develop 3-year baseline and long-term monitoring plans. This report is one of the products of Phase I of the Corridor Study. A literature review of surface-water-quality, surface water- quantity, and ecology studies conducted from 1970 through 2001 was completed and is summarized in this report. An inventory of Geographic Information System spatial coverages available for the MMSD planning area has been assembled. A database of water, sediment, and tissue (fish, shellfish, and others) chemistry, macroinvertebrates, fish, algae, habitat, geomorphic, and other physical and ecological data was compiled from data sets from MMSD, U.S. Geological Survey, Wisconsin Department of Natural Resources, and the U.S. Environmental Protection Agency. More than 2.7 million results are available in the MMSD Corridor Study database and the compilation of multiple datasets allows for retrieving data from a central database rather than from each of the source datasets. Data for 1970 through 2002 were collected for the 420-square-mile planning area by various agencies using different field data-collection and laboratory analysis methods. Chemical constituents and ecological components that are important to an urban setting and well represented in the database were selected for further investigation. Each constituent or component is described in this report with some or all of the following: a text summary, map of sampling locations, and in some cases median concentrations, statistical distributions of concentrations by subwatershed, table of summary statistics by subwatershed, and graphs of temporal and (or) seasonal trends. Physical data presented in the report include streamflow, stream stage, and precipitation data. Chemical indicators of water quality presented in the report include field measurements and miscellaneous constituents (pH, alkalinity, specific conductance, hardness, dissolved oxygen, biochemical oxygen demand, and chloride), sediment (total suspended solids and suspended sediment), nutrients (total nitrogen, nitrate, Kjeldahl nitrogen, total phosphorus, and dissolved phosphorus), trace elements (cadmium, mercury, copper, lead, arsenic, chromium, nickel, and zinc), pesticides (historically used pesticides and pesticides still in use), and polychlorinated biphenyls. Ecological indicators of water quality discussed in the report include community surveys of macroinvertebrates and fish, chlorophyll a concentrations, habitat assessments and channel-measurement data, and fecal coliform and E. coli bacterial counts. In addition to the compilation of the database, a major purpose of this investigation was to identify additional sampling that should be conducted under the baseline monitoring phase, which will be the second phase of the Corridor Study. Additional sampling may include: • Some subwatersheds, such as those in the headwaters. • Emerging contaminants such as pharmaceuticals and personal care products (PPCPs), human hormones, organic wastewater contaminants, and other constituents that result from human activity. • E. coli, which can serve as an indicator of health risk to swimmers and other recreational water users. • Pesticides in all media. • PCBs. • Trace elements in water, bed sediment, and tissues (fish, shellfish, and others). • Samples during winter months or during early snowmelt episodes to address constituents such as chloride and some nutrients that have seasonal variability and that may be affected by factors such as road deicing during the winter. • Samples for macroinvertebrate and fish-community data and habitat assessments. • Physical data such as stream-channel cross-section profiles, bridge-scour assessments, flood-plain maps, structures, and shoreline conditions.

Wisconsin

Evaluating release alternatives for a long-lived bird species under uncertainty about long-term demographic rates

The release of animals to reestablish an extirpated population is a decision problem that is often attended by considerable uncertainty about the probability of success. Annual releases of captive-reared juvenile Whooping Cranes (Grus americana) were begun in 1993 in central Florida, USA, to establish a breeding, non-migratory population. Over a 12-year period, 286 birds were released, but by 2004, the introduced flock had produced only four wild-fledged birds. Consequently, releases were halted over managers' concerns about the performance of the released flock and uncertainty about the efficacy of further releases. We used data on marked, released birds to develop predictive models for addressing whether releases should be resumed, and if so, under what schedule. To examine the outcome of different release scenarios, we simulated the survival and productivity of individual female birds under a baseline model that recognized age and breeding-class structure and which incorporated empirically estimated stochastic elements. As data on wild-fledged birds from captive-reared parents were sparse, a key uncertainty that confronts release decision-making is whether captive-reared birds and their offspring share the same vital rates. Therefore, we used data on the only population of wild Whooping Cranes in existence to construct two alternatives to the baseline model. The probability of population persistence was highly sensitive to the choice of these three models. Under the baseline model, extirpation of the population was nearly certain under any scenario of resumed releases. In contrast, the model based on estimates from wild birds projected a high probability of persistence under any release scenario, including cessation of releases. Therefore, belief in either of these models suggests that further releases are an ineffective use of resources. In the third model, which simulated a population Allee effect, population persistence was sensitive to the release decision: high persistence probability was achieved only through the release of more birds, whereas extirpation was highly probable with cessation of releases. Despite substantial investment of time and effort in the release program, evidence collected to date does not favor one model over another; therefore, any decision about further releases must be made under considerable biological uncertainty. However, given an assignment of credibility weight to each model, a best, informed decision about releases can be made under uncertainty. Furthermore, if managers can periodically revisit the release decision and collect monitoring data to further inform the models, then managers have a basis for confronting uncertainty and adaptively managing releases through time.

Florida

The principal rare earth elements deposits of the United States: A summary of domestic deposits and a global perspective

The rare earth elements (REE) are fifteen elements with atomic numbers 57 through 71, from lanthanum to lutetium ('lanthanides'), plus yttrium (39), which is chemically similar to the lanthanide elements and thus typically included with the rare earth elements. Although industrial demand for these elements is relatively small in tonnage terms, they are essential for a diverse and expanding array of high-technology applications. REE-containing magnets, metal alloys for batteries and light-weight structures, and phosphors are essential for many current and emerging alternative energy technologies, such as electric vehicles, energy-efficient lighting, and wind power. REE are also critical for a number of key defense systems and other advanced materials. Section 843 of the National Defense Authorization Act for Fiscal Year 2010, Public Law 111-84, directs the Comptroller General to complete a report on REE materials in the defense supply chain. The Office of Industrial Policy, in collaboration with other U.S. Government agencies, has initiated (in addition to this report) a detailed study of REE. This latter study will assess the Department of Defense's use of REE, as well as the status and security of domestic and global supply chains. That study will also address vulnerabilities in the supply chain and recommend ways to mitigate any potential risks of supply disruption. To help conduct this study, the Office of Industrial Policy asked the U.S. Geological Survey (USGS) to report on domestic REE reserves and resources in a global context. To this end, the enclosed report is the initial USGS contribution to assessing and summarizing the domestic REE resources in a global perspective. In 2009, the Mineral Resources Program of the USGS organized a new project under the title Minerals at Risk and For Emerging Technologies in order to evaluate mineral resource and supply issues of rare metals that are of increasing importance to the national economy. Leaders and members of this project, with the assistance of the USGS National Minerals Information Center, prepared the enclosed USGS report on domestic REE resources. The USGS Mineral Resources Program has investigated domestic and selected foreign REE resources for many decades, and this report summarizes what has been learned from this research. The USGS National Minerals Information Center (formerly Minerals Information Team) has monitored global production, trade, and resources for an equally long period and is the principal source of statistics used in this report. The objective of this study is to provide a nontechnical overview of domestic reserves and resources of REE and possibilities for utilizing those resources. At the present time, the United States obtains its REE raw materials from foreign sources, almost exclusively from China. Import dependence upon a single country raises serious issues of supply security. In a global context, domestic REE resources are modest and of uncertain value; hence, available resources in traditional trading partners (such as Canada and Australia) are of great interest for diversifying sources of supply. This report restates basic geologic facts about REE relevant to assessing security of supply, followed by a review of current United States consumption and imports of REE, current knowledge of domestic resources, and possibilities for future domestic production. Further detail follows in a deposit-by-deposit review of the most significant domestic REE deposits (see index map). Necessary steps to develop domestic resources are discussed in a separate section, leading into a review of current domestic exploration and a discussion of the value of a future national mineral resource assessment of REE. The report also includes an overview of known global REE resources and discusses the reliability of alternative foreign sources of REE.

Scientific Investigations Report

Vertical gradients in water chemistry and age in the Northern High Plains Aquifer, Nebraska, 2003

The northern High Plains aquifer is the primary source of water used for domestic, industrial, and irrigation purposes in parts of Colorado, Kansas, Nebraska, South Dakota, and Wyoming. Despite the aquifer’s importance to the regional economy, fundamental ground-water characteristics, such as vertical gradients in water chemistry and age, remain poorly defined. As part of the U.S. Geological Survey’s National Water-Quality Assessment Program, water samples from nested, short-screen monitoring wells installed in the northern High Plains aquifer were analyzed for major ions, nutrients, trace elements, dissolved organic carbon, pesticides, stable and radioactive isotopes, dissolved gases, and other parameters to evaluate vertical gradients in water chemistry and age in the aquifer. Chemical data and tritium and radiocarbon ages show that water in the aquifer was chemically and temporally stratified in the study area, with a relatively thin zone of recently recharged water (less than 50 years) near the water table overlying a thicker zone of older water (1,800 to 15,600 radiocarbon years). In areas where irrigated agriculture was an important land use, the recently recharged ground water was characterized by elevated concentrations of major ions and nitrate and the detection of pesticide compounds. Below the zone of agricultural influence, major-ion concentrations exhibited small increases with depth and distance along flow paths because of rock/water interactions. The concentration increases were accounted for primarily by dissolved calcium, sodium, bicarbonate, sulfate, and silica. In general, the chemistry of ground water throughout the aquifer was of high quality. None of the approximately 90 chemical constituents analyzed in each sample exceeded primary drinking-water standards. Mass-balance models indicate that changes in groundwater chemistry along flow paths in the aquifer can be accounted for by small amounts of feldspar and calcite dissolution; goethite and clay-mineral precipitation; organic-carbon and pyrite oxidation; oxygen reduction and denitrification; and cation exchange. Mixing with surface water affected the chemistry of ground water in alluvial sediments of the Platte River Valley. Radiocarbon ages in the aquifer, adjusted for carbon mass transfers, ranged from 1,800 to 15,600 14C years before present. These results have important implications with respect to development of ground-water resources in the Sand Hills. Most of the water in the aquifer predates modern anthropogenic activity so excessive removal of water by pumping is not likely to be replenished by natural recharge in a meaningful timeframe. Vertical gradients in ground-water age were used to estimate long-term average recharge rates in the aquifer. In most areas, the recharge rates ranged from 0.02 to 0.05 foot per year. The recharge rate was 0.2 foot per year in one part of the aquifer characterized by large downward hydraulic gradients. Nitrite plus nitrate concentrations at the water table were 0.13 to 3.13 milligrams per liter as nitrogen, and concentrations substantially decreased with depth in the aquifer. Dissolved-gas and nitrogen-isotope data indicate that denitrification in the aquifer removed 0 to 97 percent (average = 50 percent) of the nitrate originally present in recharge. The average amount of nitrate removed by denitrification in the aquifer north of the Platte River (Sand Hills) was substantially greater than the amount removed south of the river (66 as opposed to 0 percent), and the extent of nitrate removal appears to be related to the presence of thick deposits of sediment on top of the Ogallala Group in the Sand Hills that contained electron donors, such as organic carbon and pyrite, to support denitrification. Apparent rates of dissolved-oxygen reduction and denitrification were estimated on the basis of decreases in dissolved-oxygen concentrations and increases in concentrations of excess nitrogen gas and ground-water ages along flow paths from the water table to deeper wells. Median rates of dissolved-oxygen reduction and denitrification south of the Platte River were at least 10 times smaller than the median rates north of the river in the Sand Hills. The relatively large denitrification rates in the Sand Hills indicate that the aquifer in that area may have a greater capacity to attenuate nitrate contamination than the aquifer south of the river, depending on rates of ground-water movement in the two areas. Small denitrification rates south of the river indicate that nitrate contamination in that part of the aquifer would likely persist for a longer period of time.

Nebraska

Possible sources of nitrate in ground water at swine licensed-managed feeding operations in Oklahoma, 2001

Samples collected and analyzed by the Oklahoma Department of Agriculture, Food, and Forestry from 1999 to 2001 determined that nitrate exceeded the U.S. Environmental Protection Agency maximum contaminant level for public drinking-water supplies of 10 milligrams per liter as nitrogen in 79 monitoring wells at 35 swine licensed-managed feeding operations (LMFO) in Oklahoma. The LMFOs are located in rural agricultural settings where long-term agriculture has potentially affected the ground-water quality in some areas. Land use prior to the construction of the LMFOs was assessed to evaluate the types of agricultural land use within a 500-meter radius of the sampled wells. Chemical and microbiological techniques were used to determine the possible sources of nitrate in water sampled from 10 wastewater lagoons and 79 wells. Samples were analyzed for dissolved major ions, dissolved trace elements, dissolved nutrients, nitrogen isotope ratios of nitrate and ammonia, wastewater organic compounds, and fecal coliform bacteria. Bacteria ribotyping analysis was done on selected samples to identify possible specific animal sources. A decision process was developed to identify the possible sources of nitrate. First, nitrogen isotope ratios were used to define sources as animal, mixed animal and fertilizer, or fertilizer. Second, wastewater organic compound detections, nitrogen-isotope ratios, fecal coliform bacteria detections, and ribotyping were used to refine the identification of possible sources as LFMO waste, fertilizer, or unidentified animal or mixtures of these sources. Additional evidence provided by ribotyping and wastewater organic compound data can, in some cases, specifically indicate the animal source. Detections of three or more wastewater organic compounds that are indicators of animal sources and detections of fecal coliform bacteria provided additional evidence of an animal source. LMFO waste was designated as a possible source of nitrate in water from 10 wells. The source of waste in water from five of those wells was determined through ribotyping, and the source of waste in water from the remaining five wells was determined by detections of three or more animal-waste compounds in the well samples. LMFO waste in the water from wells with unidentified animal source of nitrate does not indicate that LMFO waste was not the source, but indicated that multiple animal sources, including LMFO waste, may be the source of the nitrate.

Water-Resources Investigations Report