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Water-quality characteristics and trend analyses for the Tongue, Powder, Cheyenne, and Belle Fourche River drainage basins, Wyoming and Montana, for selected periods, water years 1991 through 2010

The Powder River structural basin in northeastern Wyoming and southeastern Montana is an area of ongoing coalbed natural gas (CBNG) development. Waters produced during CBNG development are managed with a variety of techniques, including surface impoundments and discharges into stream drainages. The interaction of CBNG-produced waters with the atmosphere and the semiarid soils of the Powder River structural basin can affect water chemistry in several ways. Specific conductance and sodium adsorption ratios (SAR) of CBNG-produced waters that are discharged to streams have been of particular concern because they have the potential to affect the use of the water for irrigation. Water-quality monitoring has been conducted since 2001 at main-stem and tributary sites in the Tongue, Powder, Cheyenne, and Belle Fourche River drainage basins in response to concerns about CBNG effects. A study was conducted to summarize characteristics of stream-water quality for water years 2001–10 (October 1, 2000, to September 30, 2010) and examine trends in specific conductance, SAR, and primary constituents that contribute to specific conductance and SAR for changes through time (water years 1991–2010) that may have occurred as a result of CBNG development. Specific conductance and SAR are the focus characteristics of this report. Dissolved calcium, magnesium, and sodium, which are primary contributors to specific conductance and SAR, as well as dissolved alkalinity, chloride, and sulfate, which are other primary contributors to specific conductance, also are described. Stream-water quality in the Tongue, Powder, Cheyenne, and Belle Fourche River drainage basins was variable during water years 2001–10, in part because of variations in streamflow. In general, annual runoff was less than average during water years 2001–06 and near or above average during water years 2007–10. Stream water of the Tongue River had the smallest specific conductance values, sodium adsorption ratios, and major ion concentrations of the main-stem streams. Sites in the Tongue River drainage basin typically had the smallest range of specific conductance and SAR values. The water chemistry of sites in the Powder River drainage basin generally was the most variable as a result of diverse characteristics of that basin. Plains tributaries in the Powder River drainage basin had the largest range of specific conductance and SAR values, in part due to the many tributaries that receive CBNG-produced waters. Trends were analyzed using the seasonal Kendall test with flow-adjusted concentrations to determine changes to water quality through time at sites in the Tongue, Powder, Cheyenne, and Belle Fourche River drainage basins. Trends were evaluated for water years 2001–10 for 17 sites, which generally were on the main-stem streams and primary tributaries. Trends were evaluated for water years 2005–10 for 26 sites to increase the spatial coverage of sites. Trends were evaluated for water years 1991–2010 for eight sites to include water-quality data collected prior to widespread CBNG development and expand the temporal context of trends. Consistent patterns were not observed in trend results for water years 2001–10 for flow-adjusted specific conductance and SAR values in the Tongue, Powder, and Belle Fourche River drainage basins. Significant (p-values less than 0.05) upward trends in flow-adjusted specific conductance values were determined for 3 sites, a downward trend was determined for 1 site, and no significant (p-value greater than 0.05) trends were determined for 13 sites. One of the sites with a significant upward trend was the Tongue River at the Wyoming-Montana State line. No trend in flow-adjusted specific conductance values was determined for the Powder River at Moorhead, Mont. Significant upward trends in flow-adjusted SAR values were determined for 2 sites and no significant trends were determined for 15 sites. No trends in flow-adjusted SAR values were determined for the Tongue River at the Wyoming-Montana State line or for the Powder River at Moorhead, Mont. One of the sites with a significant upward trend in flow-adjusted SAR values was the Powder River at Arvada, Wyo. For water years 2005–10, significant upward trends in flow-adjusted specific conductance values were determined no significant trends were determined for 13 sites. A significant upward trend was determined for flow-adjusted specific conductance values for the Tongue River at the Wyoming-Montana State line. No trend in flow-adjusted specific conductance values was determined for the Powder River at Moorhead, Mont. Significant upward trends in flow-adjusted SAR values were determined for 4 sites, downward trends were determined for 5 sites, and no significant trend was determined for 17 sites. No trends in flow-adjusted SAR values were determined for the Tongue River at the Wyoming-Montana State line or for the Powder River at Moorhead, Mont. Results of the seasonal Kendall test applied to flow-adjusted specific conductance values for water years 1991–2010 indicated no significant trend for eight sites in the Tongue, Powder, and Belle Fourche River drainage basins. No significant trend in flow-adjusted specific conductance was determined for the Tongue River at the Wyoming-Montana State line or the Powder River at Moorhead, Mont. Results of the seasonal Kendall test applied to flow-adjusted SAR values for water years 1991–2010 indicated an upward trend for one site and no significant trend for four sites in the Powder and Belle Fourche River drainage basins. The significant upward trend in flow-adjusted SAR values was determined for the Powder River at Arvada, Wyo., for water years 1991–2010. Results indicate that CBNG development in the Powder River structural basin may have contributed to some trends, such as the upward trend in flow-adjusted SAR for the Powder River at Arvada, Wyo., for water years 1991–2010. An upward trend in flow-adjusted alkalinity concentrations for water years 2001–10 also was determined for the Powder River at Arvada, Wyo. Trend results are consistent with changes that can occur from the addition of sodium and bicarbonate associated with CBNG-produced waters to the Powder River. Upward trends in constituents at other sites, including the Belle Fourche River, may be the result of declining CBNG development, indicating that CBNG-produced waters may have had a dilution effect on some streams. The factors affecting other trends could not be determined because multiple factors could have been affecting the stream-water quality or because trends were observed at sites upstream from CBNG development that may have affected water-quality trends at sites downstream.

Wyoming;Montana

Quality of groundwater at and near an aquifer storage and recovery site, Bexar, Atascosa, and Wilson Counties, Texas, June 2004-August 2008

The U.S. Geological Survey, in cooperation with the San Antonio Water System, did a study during 2004–08 to characterize the quality of native groundwater from the Edwards aquifer and pre- and post-injection water from the Carrizo aquifer at and near an aquifer storage and recovery (ASR) site in Bexar, Atascosa, and Wilson Counties, Texas. Groundwater samples were collected and analyzed for selected physical properties and constituents to characterize the quality of native groundwater from the Edwards aquifer and pre- and post-injection water from the Carrizo aquifer at and near the ASR site. Geochemical and isotope data indicated no substantial changes in major-ion, trace-element, and isotope chemistry occurred as the water from the Edwards aquifer was transferred through a 38-mile pipeline to the aquifer storage and recovery site. The samples collected from the four ASR recovery wells were similar in major-ion and stable isotope chemistry compared to the samples collected from the Edwards aquifer source wells and the ASR injection well. The similarity could indicate that as Edwards aquifer water was injected, it displaced native Carrizo aquifer water, or, alternatively, if mixing of Edwards and Carrizo aquifer waters was occurring, the major-ion and stable isotope signatures for the Carrizo aquifer water might have been obscured by the signatures of the injected Edwards aquifer water. Differences in the dissolved iron and dissolved manganese concentrations indicate that either minor amounts of mixing occurred between the waters from the two aquifers, or as Edwards aquifer water displaced Carrizo aquifer water it dissolved the iron and manganese directly from the Carrizo Sand. Concentrations of radium-226 in the samples collected at the ASR recovery wells were smaller than the concentrations in samples collected from the Edwards aquifer source wells and from the ASR injection well. The smaller radium-226 concentrations in the samples collected from the ASR recovery wells likely indicate some degree of mixing of the two waters occurred rather than continued decay of radium-226 in the injected water. Geochemical and isotope data measured in samples collected in May 2005 from two Carrizo aquifer monitoring wells and in July 2008 from the three ASR production-only wells in the northern section of the ASR site indicate that injected Edwards aquifer water had not migrated to these five sites. Geochemical and isotope data measured in samples collected from Carrizo aquifer wells in 2004, 2005, and 2008 were graphically analyzed to determine if changes in chemistry could be detected. Major-ion, trace element, and isotope chemistry varied spatially in the samples collected from the Carrizo aquifer. With the exception of a few samples, major-ion concentrations measured in samples collected in Carrizo aquifer wells in 2004, 2005, and 2008 were similar. A slightly larger sulfate con­centration and a slightly smaller bicarbonate concentration were measured in samples collected in 2005 and 2008 from well NC1 compared to samples collected at well NC1 in 2004. Larger sodium concentrations and smaller calcium, magnesium, bicarbonate, and sulfate concentrations were measured in samples collected in 2008 from well WC1 than in samples collected at this well in 2004 and 2005. Larger calcium and magnesium concentrations and a smaller sodium concentration were measured in the samples collected in 2008 at well EC2 compared to samples collected at this well in 2004 and 2005. While in some cases the computed percent differences (compared to concentrations from June 2004) in dissolved iron and dissolved manganese concentrations in 11 wells sampled in the Carrizo aquifer in 2005 and 2008 were quite large, no trends that might have been caused by migration of injected Edwards aquifer water were observed. Because of the natural variation in geochemical data in the Carrizo aquifer and the small data set collected for this study, differences in major-ion and trace element data among the samples collected in 2004, 2005 and 2008 cannot be directly attributed to the ASR site operations. When the data were analyzed graphically, no appreciable differences in isotope concentrations were observed between samples collected in 2004 and 2008 from Carrizo aquifer wells, indicating that the Edwards aquifer source water might not have affected the isotope chemistry of the native Carrizo aquifer water near the sampled Carrizo wells by July 2008.

Texas

Chemical constituents in groundwater from multiple zones in the eastern Snake River Plain aquifer, Idaho National Laboratory, Idaho, 2009-13

From 2009 to 2013, the U.S. Geological Survey’s (USGS) Idaho National Laboratory (INL) Project office, in cooperation with the U.S. Department of Energy, collected water-quality samples from multiple water-bearing zones in the eastern Snake River Plain aquifer. Water samples were collected from 11 monitoring wells completed in about 250–750 feet of the upper part of the aquifer, and samples were analyzed for selected major ions, trace elements, nutrients, radiochemical constituents, and stable isotopes. Each well was equipped with a multilevel monitoring system containing four to seven sampling ports that were each isolated by permanent packer systems. The sampling ports were installed in aquifer zones that were highly transmissive and that represented the water chemistry of the top three to five model layers of a steady-state and transient groundwater‑flow model. The groundwater-flow model and water chemistry are being used to better define movement of wastewater constituents in the aquifer. The water-chemistry composition of all sampled zones for the five new multilevel wells is calcium plus magnesium bicarbonate. One of the zones in well USGS 131A has a slightly different chemistry from the rest of the zones and wells and the difference is attributed to more wastewater influence from the Idaho Nuclear Technology and Engineering Center. One well, USGS 135, was not influenced by wastewater disposal and consisted of mostly older water in all of its zones. Tritium concentrations in relation to basaltic flow units indicate the presence of wastewater influence in multiple basalt flow groups; however, tritium is most abundant in the South Late Matuyama flow group in the southern boundary wells. The concentrations of wastewater constituents in deep zones in wells Middle 2051, USGS 132, USGS 105, and USGS 103 support the concept of groundwater flow deepening in the southwestern corner of the INL, as indicated by the INL groundwater-flow model.

Idaho

Managing salinity in Upper Colorado River Basin streams: Selecting catchments for sediment control efforts using watershed characteristics and random forests models

Elevated concentrations of dissolved-solids (salinity) including calcium, sodium, sulfate, and chloride, among others, in the Colorado River cause substantial problems for its water users. Previous efforts to reduce dissolved solids in upper Colorado River basin (UCRB) streams often focused on reducing suspended-sediment transport to streams, but few studies have investigated the relationship between suspended sediment and salinity, or evaluated which watershed characteristics might be associated with this relationship. Are there catchment properties that may help in identifying areas where control of suspended sediment will also reduce salinity transport to streams? A random forests classification analysis was performed on topographic, climate, land cover, geology, rock chemistry, soil, and hydrologic information in 163 UCRB catchments. Two random forests models were developed in this study: one for exploring stream and catchment characteristics associated with stream sites where dissolved solids increase with increasing suspended-sediment concentration, and the other for predicting where these sites are located in unmonitored reaches. Results of variable importance from the exploratory random forests models indicate that no simple source, geochemical process, or transport mechanism can easily explain the relationship between dissolved solids and suspended sediment concentrations at UCRB monitoring sites. Among the most important watershed characteristics in both models were measures of soil hydraulic conductivity, soil erodibility, minimum catchment elevation, catchment area, and the silt component of soil in the catchment. Predictions at key locations in the basin were combined with observations from selected monitoring sites, and presented in map-form to give a complete understanding of where catchment sediment control practices would also benefit control of dissolved solids in streams.

Upper Colorado River Basin

Design and methods of the Southeast Stream Quality Assessment (SESQA), 2014

During 2014, the U.S. Geological Survey (USGS) National Water-Quality Assessment Program (NAWQA) assessed stream quality across the Piedmont and southern Appalachian Mountain regions of the southeastern United States. This Southeast Stream Quality Assessment (SESQA) simultaneously characterized watershed and stream-reach water-quality stressors along with instream biological conditions, in order to better understand regional stressor-effects relations. The goal of SESQA is to provide communities and policymakers with information about those human and environmental factors that have the greatest impact on stream quality across the region. The SESQA design focused on hydrologic alteration and urbanization because of their importance as ecological stressors of particular concern to Southeast region resource managers. Streamflow and land-use data were used to identify and select sites representing gradients in urbanization and streamflow alteration across the region. One hundred fifteen sites were selected and sampled for as many as 10 weeks during April, May, and June 2014 for contaminants, nutrients, and sediment. This water-quality “index” period culminated with an ecological survey of habitat, periphyton, benthic macroinvertebrates, and fish at all sites. Sediment was collected during the ecological survey for analysis of sediment chemistry and toxicity testing. Of the 115 sites, 59 were on streams in watersheds with varying degrees of urban land use, 5 were on streams with multiple confined animal feeding operations, and 13 were reference sites with little or no development in their watersheds. The remaining 38 “hydro” sites were on streams in watersheds with relatively little agricultural or urban development but with hydrologic alteration, such as a dam or reservoir. This report provides a detailed description of the SESQA study components, including surveys of ecological conditions, routine water sampling, deployment of passive polar organic compound integrative samplers for pesticides and contaminants of emerging concern, and synoptic sediment sampling and toxicity testing at all urban, confined animal feeding operation, and reference sites. Continuous water-quality monitoring and daily pesticide sampling efforts conducted at a subset of urban sites are also described.

Alabama, Georgia, North Carolina, South Carolina,

Prioritizing High-Temperature Geothermal Resources in Utah

The Utah Geological Survey and the Utah Energy Office recently released geothermal resource information for Utah as a "digital atlas." We are now expanding this project to include economic analyses of selected geothermal sites and previously unavailable resource information. The enhancements to the digital atlas will include new resource, demographic, regulatory, economic, and other information to allow analyses of economic factors for comparing and ranking geothermal resource sites in Utah for potential electric power development. New resource information includes temperature gradient and fluid chemistry data, which was previously proprietary. Economic analyses are based upon a project evaluation model to assess capital and operating expenses for a variety of geothermal powerplant configuration scenarios. A review of legal and institutional issues regarding geothermal development coupled with water development will also be included.

Conference Paper

Ground-water and stream-water interaction in the Owl Creek basin, Wyoming

Understanding of the interaction of ground-water and surface-water resources is vital to water management when water availability is limited.Inflow of ground water is the primary source ofwater during stream base flow. The water chemistry of streams may substantially be affected by that inflow of ground water. This report is part of a study to examine ground-water and surface-water interaction in the Owl Creek Basin, Wyoming, completed by the U.S. Geological Survey incooperation with the Northern Arapaho Tribe and the Shoshone Tribe. During a low flow period between November\x1113 - 17, 1991, streamflowmeasurements and water-quality samples were collected at 16 selected sites along major streams and tributaries in the Owl Creek Basin,Wyoming. The data were used to identify stream reaches receiving ground-water inflow and to examine causes of changes in stream chemistry.Streamflow measurements, radon-222 activity load, and dissolved solids load were used to identified stream reaches receiving ground-water inflow.Streamflow measurements identified three stream reaches receiving ground-water inflow. Analysis of radon-222 activity load identified five stream reaches receiving ground-water inflow. Dissolvedsolids load identified six stream reaches receiving ground-water inflow. When these three methods were combined, stream reaches in two areas, theEmbar Area and the Thermopolis Anticline Area, were identified as receiving ground-water inflow.The Embar Area and the Thermopolis Anticline Area were then evaluated to determine the source of increased chemical load in stream water. Three potential sources were analyzed: tributary inflow, surficial geology, and anticlines. Two sources,tributary inflow and surficial geology, were related to changes in isotopic ratios and chemical load in the Embar Area. In two reaches in the Embar Area, isotopic ratios of 18O/16O, D/H, and 34S/32S indicated that tributary inflow affected stream-water chemistry. Increased chemical load of dissolved solids and dissolved sulfate in North Fork andSouth Fork Owl Creek appear to be related to the percentage of unconsolidated Quaternary deposits and of Cretaceous-Jurassic deposits in the drainage area. In the Thermopolis Anticline Area, changes in water chemistry in Owl Creek were not related to tributary inflow, surficial geology, or anticlines.The three tributaries that flow into Owl Creek in the Thermopolis Anticline Area did not substantially affect the isotopic ratios or contribute to the chemical load. Changes in the chemical load were not associated with changes in the surficial geologybetween the stream-water sampling sites. Water levels and chemical ratios indicate no ground-water inflow from the Thermopolis Anticline geothermal system to Owl Creek.

Water-Resources Investigations Report

Statistical summary of selected physical, chemical, and microbial characteristics, and estimates of constituent loads in urban stormwater, Maricopa County, Arizona

Stormwater and streamflow in the Phoenix, Arizona, area were monitored to determine the physical, chemical, and microbial characteristics of storm- water from areas having different land uses; to describe the characteristics of streamflow in a river that receives urban stormwater; and to estimate constituent loads in stormwater from unmonitored areas in Maricopa County, Arizona. Land use affects urban stormwater chemistry mostly because the percentage of impervious area controls the suspended-solids concentrations and varies with the type of land use. Urban activities also seem to concentrate cadmium, lead, and zinc in sediments. Urban stormwater had larger concentrations of chemical oxygen demand and biological oxygen demand, oil and grease, and higher counts of fecal bacteria than streamflow and could degrade the quality of the Salt River. Most regression equations for estimating constituent loads require three explanatory variables (total rainfall, drainage area, and per- centage of impervious area) and had standard errors that were from 65 to 266 percent. Localized areas that appear to contribute a large proportion of the constituent loads typically have 40 percent or more impervious area and are associated with industrial, commercial, and high-density residential land uses. The use of the mean value of the event-mean constituent concentrations measured in stormwater may be the best way of estimating constituent concentrations.

Arizona

Spatial and temporal variation of stream chemistry associated with contrasting geology and land-use patterns in the Chesapeake Bay watershed—Summary of results from Smith Creek, Virginia; Upper Chester River, Maryland; Conewago Creek, Pennsylvania; and Difficult Run, Virginia, 2010–2013

Despite widespread and ongoing implementation of conservation practices throughout the Chesapeake Bay watershed, water quality continues to be degraded by excess sediment and nutrient inputs. While the Chesapeake Bay Program has developed and maintains a large-scale and long-term monitoring network to detect improvements in water quality throughout the watershed, fewer resources have been allocated for monitoring smaller watersheds, even though water-quality improvements that may result from the implementation of conservation practices are likely to be first detected at smaller watershed scales. In 2010, the U.S. Geological Survey partnered with the U.S. Environmental Protection Agency and the U.S. Department of Agriculture to initiate water-quality monitoring in four selected small watersheds that were targeted for increased implementation of conservation practices. Smith Creek watershed is an agricultural watershed in the Shenandoah Valley of Virginia that is dominated by cattle and poultry production, and the Upper Chester River watershed is an agricultural watershed on the Eastern Shore of Maryland that is dominated by row-cropping activities. The Conewago Creek watershed is an agricultural watershed in southeastern Pennsylvania that is characterized by mixed agricultural activities. The fourth watershed, Difficult Run, is a suburban watershed in northern Virginia that is dominated by medium density residential development. The objective of this study was to investigate spatial and temporal variations in water chemistry and suspended sediment in these four relatively small watersheds that represent a range of land-use patterns and underlying geology to (1) characterize current water-quality conditions in these watersheds, and (2) identify the dominant sources, sinks, and transport processes in each watershed. The general study design involved two components. The first included intensive routine water-quality monitoring at an existing streamgage within each study area (including continuous water-quality monitoring as well as discrete water-quality sampling) to develop a detailed understanding of the temporal and hydrologic variability in stream chemistry and sediment transport in each watershed. The second component involved extensive water-quality monitoring at various sites throughout each watershed to develop a detailed understanding of spatial patterns. Both components were used to improve understanding of sources and transport processes affecting stream chemistry, including nutrients and suspended sediments, and their implications for detecting long-term trends related to best management practices. This report summarizes the results of monitoring that was performed from April 2010 through September 2013. Individual Small Watershed Summaries Summaries for each of the four small watersheds are presented below. Each watershed has a more descriptive and detailed section in the report, but these summaries may be particularly useful for some watershed managers and stakeholders desiring slightly less technical detail. Smith Creek Smith Creek is a 105.39-mi 2 watershed within the Shenandoah Valley that drains to the North Fork Shenandoah River. The long-term Smith Creek base-flow index is 72.3 percent, indicating that on average, approximately 72 percent of Smith Creek flow was base flow, which suggests that Smith Creek streamflow is dominated by groundwater discharge rather than stormwater runoff. A series of cluster and principal components analyses demonstrated that the majority of the variability in Smith Creek water quality could be attributed to hydrologic and seasonal variability. Statistically significant positive correlations with flow were observed for turbidity, suspended sediments, total nitrogen, ammonium, orthophosphate, iron, total phosphorus, and the ratio of calcium to magnesium. Statistically significant inverse correlations with flow were observed for specific conductance, magnesium, δ 15 N of nitrate, pH, bicarbonate, calcium, and δ 18 O of nitrate. Of particular note, flow and nitrate were not statistically significantly correlated, likely because of the relatively complex concentration-discharge relationship observed in continuous and discrete datasets. Statistically significant seasonal patterns were observed for numerous water-quality constituents: water temperature, turbidity, orthophosphate, total phosphorus, suspended-sediment concentration, and silica were higher during the warm season, but pH, dissolved oxygen, and sulfate were higher during the cool season. Surrogate regression models were developed to compute sediment and nutrient loads in Smith Creek using the continuous water-quality monitors. The mean Smith Creek in-stream sediment load was approximately 6,900 tons per year, with nearly 90 percent of the sediment load over the 3-year study period contributed during the eight largest storm events during that period. The Smith Creek total phosphorus load was approximately 21,000 pounds of phosphorus per year, with the majority of the load contributed during stormflow periods, although a substantial phosphorus load still occurs during base-flow conditions. The Smith Creek total nitrogen load was approximately 400,000 pounds per year, with total nitrogen accumulation less dominated by stormflow contributions (as was the case for sediment and total phosphorus) and strongly affected by base-flow export of nitrogen from the basin. Extensive water-quality monitoring throughout the Smith Creek watershed revealed how the complex geology and hydrology interacted to result in variable water chemistry. During relatively dry and low base-flow periods, much of the discharge in Smith Creek was contributed by a single dominant spring—Lacey Spring. During wetter base-flow periods, the flows in Smith Creek were largely generated by a mixture of headwater springs and forested mountain tributaries with very different geochemical composition. The headwater springs generally issued from limestone bedrock and were characterized as having relatively high nitrate, specific conductance, calcium, and magnesium, as well as relatively low concentrations of phosphorus, ammonium, iron, and manganese. The undeveloped, high-gradient, forested mountain sites were generally characterized by low ionic strength waters with low nutrient concentrations. Nitrate isotope data from the limestone springs generally were consistent with manure-derived nitrogen sources (such as cattle and poultry), although the possibility of other mixed sources cannot be excluded. Nitrate isotope data from the undeveloped, high-gradient forested mountain sites were more consistent with nitrogen from undisturbed soils, atmospheric deposition, or nitrogen fixation. Regardless of the nitrogen source, oxygen isotope data indicate that the nitrate was largely a result of nitrification. Land-use data indicate that manure sources of nitrogen dominated watershed nitrogen inputs. Phosphorus sources were less well studied. The presence of a single point-source discharge near the town of New Market contributed the majority of the phosphorus to Smith Creek under base-flow conditions, but nonpoint sources of phosphorus dominated the loading to Smith Creek during stormflow periods. Implementation of conservation practices increased in the Smith Creek watershed during the study period, and even though a broad range of practice types was implemented, the most common practices included stream fencing (for cattle exclusion), the development of nutrient management plans, conservation crop rotation, and the planting of cover crops. While the implementation of these conservation practices is encouraging, results indicate small increases in nitrate concentrations at the streamgage over the last 29 years, concurrent with small decreases in nitrate fluxes. It will likely be years before the cumulative effect of these practices can be detected in the Smith Creek water quality, and the magnitude of the effect of these conservation practices detected in Smith Creek will depend largely on whether nutrient loading (of manure and commercial fertilizer) is reduced over time. Upper Chester River The Upper Chester River watershed includes the 36-square-mile (mi 2 ) watershed area around several nontidal tributaries that drain into the tidal Chester River. The streamgage is on Chesterville Branch, the largest nontidal tributary (approximately 6.12 mi 2 ) and is the site for continuous water-quality monitoring for this project. The base-flow index at Chesterville Branch is about 72 percent and indicates that, as in most of the Coastal Plain, groundwater is the greatest contributor to streamflow. As such, more than 90 percent of the nitrogen in the stream is in the form of nitrate from groundwater. Continuous and discrete data collected at Chesterville Branch show the effects of streamflow and season on water quality. Significantly positive correlations with flow were observed for ammonium, dissolved and total phosphorus, sediment, and turbidity as runoff carried these constituents from the land surface into Chesterville Branch. Other constituents that increased significantly with flow include potassium, sulfate, iron, and manganese, which are likely contributed from near-stream areas and ponds with high organic-matter content. Total nitrogen, pH, and specific conductance, along with chemical constituents associated with groundwater inputs including nitrate, calcium, ratio of calcium to magnesium, silica, bicarbonate, and sodium, were negatively correlated with flow because concentrations of these constituents were diluted by runoff. Seasonal differences in water chemistry, which are most likely related to increased biologic effects on the uptake and release of chemicals in the stream and near-stream areas, also were observed. Water temperature, orthophosphate, δ 15 N of nitrate, bicarbonate, sodium, and the ratio of sodium to chloride were higher during the warm season, and dissolved oxygen, total nitrogen, nitrate, magnesium, sulfate, and manganese were higher during the cool season. Surrogate-regression models developed by using continuous water-quality data showed that the annual sediment load for the 2013 water year was about 2,600 tons, with more than 90 percent of this sediment contributed during two storms. The total phosphorus load in 2013 was about 13,000 pounds with more than 90 percent contributed during the same two storms as sediment. The load of total nitrogen, 140,000 pounds, accumulated steadily throughout the 2013 water year as nitrate in groundwater continuously discharged into the stream. The same two large storms that contributed 90 percent of the suspended-sediment and total phosphorus load only contributed about 20 percent of the annual total nitrogen load. Extensive water-quality monitoring of stream base flow throughout the Upper Chester River watershed identified how differences in land use and hydrogeology affected water chemistry. In parts of the watershed with well-drained soil and thick sandy aquifer sediments, concentrations of nitrate and other chemicals associated with fertilizer and lime application increased in streams as agricultural land use increased. More than 90 percent of the nitrogen in streams from these areas was in the form of nitrate, and concentrations ranged from about 5 milligrams per liter (mg/L) to 8 mg/L as nitrogen in the two largest tributaries. Stream nitrate concentrations were about 1 mg/L as nitrogen where soils were more poorly drained, the surficial aquifer sediments were thinner, and forests and wetlands were more widespread than agriculture. Nitrate isotope data were consistent with inorganic fertilizers ± atmospheric deposition and N 2 fixation as sources of nitrogen, and with nitrification as the dominant nitrate-forming process. Nitrate reduction was indicated by elevated δ 15 N and δ 18 O values in some samples from streams draining watersheds with poorly drained soils. An analysis of land-use data and SPARROW modeling input data attributed almost 90 percent of the nitrogen sources in the Upper Chester River watershed to inorganic fertilizer and fixation of atmospheric nitrogen by legumes, which is in agreement with the isotopic characteristics of nitrate in this watershed. Local sources of manure are limited in this area. Total phosphorus concentrations during base flow ranged from below detection to about 0.2 mg/L. Stream phosphorus concentrations during base flow were generally lower than those measured during storms because most phosphorus transport likely occurs as phosphorus attached to sediment particles during runoff. Because manure is not widely used in this area, the major source of phosphorus is likely fertilizer. The implementation of conservation practices in the Upper Chester River watershed increased substantially during the study period, with a total implementation of 1,194 U.S. Department of Agriculture-compliant practices. The most frequently used practices were oriented towards nutrient and sediment control, including cover crops, nutrient management planning, conservation crop rotation, conservation tillage, and irrigation management. The current Chesapeake Bay model for this area predicts that implementation of best management practices should result in a 13-percent decrease in overall delivery of nitrogen to the Upper Chester River. Because most nitrogen travels through the groundwater system for years to decades before being discharged to streams, the time period of monitoring was not sufficient to see the effects of these practices on water quality. The magnitude of the effect that may eventually be detected will depend on the degree to which nitrate leaching into the groundwater system is reduced over time. Loadings of phosphorus and sediment are primarily transported during large runoff events and are difficult to control and analyze for trends because of their timing and episodic nature. Conewago Creek Conewago Creek has two primary monitoring locations—one near the middle of the 47-mi 2 watershed and the other near the outlet just upstream of the Susquehanna River. The base-flow index was 47.3 percent for 2012–2013, indicating that on average, approximately 53 percent of the streamflow in Conewago Creek exited the watershed as surface flow, which suggests that the stormwater runoff was somewhat greater than groundwater discharge (base flow). A series of cluster and principal components analyses demonstrated that the majority of the variability in the Conewago Creek water quality could be attributed to hydrologic and seasonal variability. Statistically significant positive correlations with flow were observed at both monitoring sites for ammonium, total phosphorus, orthophosphate, iron, and manganese; additionally, at the upstream monitoring station, total nitrogen demonstrated a statistically significant positive correlation with flow. Statistically significant inverse correlations with flow were observed at both sites for water temperature, specific conductance (at the downstream site only), sulfate, chloride, calcium, and magnesium. Statistically significant seasonal patterns were observed for several water-quality constituents. Water temperature, phosphorus (upstream site only), and orthophosphate were higher during the warm season, and nitrate and total nitrogen (upstream site only) were higher during the cool season. Surrogate regression models were developed to compute sediment and nutrient load in Conewago Creek by using the continuous water-quality monitors and water-quality samples. Conewago Creek sediment load was approximately 9,900 tons in 2012 and approximately 18,900 tons in 2013, with nearly 80 percent of the sediment load in 2013 contributed by the three largest storm events. Annual total nitrogen loads could not be estimated due to poor model performance. The addition of continued monitoring or a continuously recording nitrate sensor could improve estimates of total nitrogen loads. During 2012 and 2013, phosphorus loads in Conewago Creek were approximately 50,000 pounds in each year. Combining data from one high-flow synoptic sampling with the data from routine sampling revealed how the geology and hydrology interact to result in variable water chemistry throughout the Conewago Creek watershed. The areas above the upstream gage in the headwaters are generally underlain by forested non-carbonate bedrock and are characterized by relatively low nitrate, specific conductance, calcium, and magnesium, as well as relatively low concentrations of phosphorus, ammonium, iron, and manganese. The more developed, agricultural areas below the upstream site were generally characterized by higher ionic strength waters with higher nutrient and metal concentrations. An analysis of land-use data and SPAtially Referenced Regressions On Watershed (SPARROW) modeling data indicates that manure sources of nitrogen dominate the input of nitrogen to the watershed. Implementation of conservation practices increased in the Conewago Creek watershed during the study period, and while a broad range of practice types were implemented, the most common practices included residue and tillage management, cover crops, nutrient management, terracing, and stream fencing (for animal exclusion or bank restoration). While the implementation of these conservation practices is encouraging, the cumulative effects of these practices probably will not be detected in Conewago Creek water quality for several years. The magnitude of the effects of these conservation practices on water quality in Conewago Creek will depend largely on the extent to which nutrient loading (septic, manure, and commercial fertilizer) and sediment-producing activities are reduced over time. Difficult Run The Difficult Run watershed is a 57.82-mi 2 watershed that drains to the Potomac River. The long-term Difficult Run base-flow index (from 1936 to 2010) was 57.9, indicating that approximately 58 percent of streamflow exited the watershed as base flow and 42 percent as stormflow; however, with continued development and urbanization of the watershed, the base-flow index has decreased to 50 percent during the last 20 years. This base-flow index was less than those of the other watersheds evaluated in this study, likely because the Difficult Run watershed largely is underlain by crystalline piedmont metamorphic rocks and has a greater proportion of impervious urban land cover. A series of cluster and principal components analyses indicated that most of the variability in Difficult Run water quality could be attributed to hydrologic variability and seasonality. Statistically significant positive correlations with flow were observed for turbidity, dissolved oxygen, suspended sediments, ammonium, orthophosphate, iron, and total phosphorus. Statistically significant inverse correlations with flow were observed for water temperature, pH, specific conductance, bicarbonate, calcium, magnesium, nitrate, δ 15 N of nitrate, and silica. Statistically significant seasonal patterns were observed for numerous water-quality constituents: water temperature, ammonium, orthophosphate, and δ 15 N of nitrate were higher during the warm season, and dissolved oxygen, nitrate, and manganese were higher during the cool season. Surrogate regression models were developed to compute sediment and nutrient loading rates. The Difficult Run sediment load was approximately 8,000 tons per year, with greater than 95 percent of the sediment load in the 2013 water year contributed by the seven largest storm events. The total phosphorus load in Difficult Run was approximately 14,000 pounds of phosphorus per year, with the majority of the load contributed during stormflow periods. The total nitrogen load in Difficult Run is estimated to have been approximately 140,000 pounds per year, with total nitrogen accumulation less dominated by stormflow contributions than that of phosphorus and strongly affected by base-flow export of nitrogen from the basin. Extensive water-quality monitoring throughout the Difficult Run watershed revealed relatively uniform generation of flow per unit of watershed area, as well as spatial variation in water quality that is strongly related to land-use activities. Elevated nitrate concentrations were observed in a subset of monitoring sites that are inversely correlated with population density and positively correlated to the septic system density within each subwatershed. The majority of the elevated nitrate concentrations for these sites are hypothesized to be caused by nitrate leaching from septic systems, more so than homeowner fertilizer usage among these subwatersheds that have lower population densities than other parts of the watershed. Nitrate isotope data, temporal patterns in the water-quality data, mass-balance computations, and a separate land-use analysis all generally indicate that leachate from septic systems was the likely source of the elevated nitrate. Another group of water-quality sites have relatively low nitrogen concentrations, are located in areas that are served by city sewer lines, and have experienced stream restoration activities. A final group of sites drained the areas with the highest imperviousness and had strongly elevated specific conductance, chloride, and sodium, which were likely caused by a combination of road salting and other anthropogenic sources draining these urbanized areas in the watershed. A fourth group of sites represents a mixture of water sources and had water quality similar to that at the Difficult Run streamgage. Analysis of the nitrate isotope data generally indicates a broad range of composition indicative of mixed natural and anthropogenic nitrogen sources. Implementation of conservation practices increased in the Difficult Run watershed during the study period, and while a broad range of practice types was implemented, the most common practices included stream restoration. While the implementation of these conservation practices is encouraging, the cumulative effect of these practices probably will not be detected in Difficult Run water quality for several years.

Maryland, Pennsylvania, Virginia

Selected Physical, Chemical, and Biological Data Used to Study Urbanizing Streams in Nine Metropolitan Areas of the United States, 1999-2004

This report documents and summarizes physical, chemical, and biological data collected during 1999-2004 in a study titled Effects of Urbanization on Stream Ecosystems, undertaken as part of the U.S. Geological Survey's National Water-Quality Assessment Program. Data-collection methods and data processing are described in this report for streamflow; stream temperature; instream chemistry; instream aquatic habitat; and algal, macroinvertebrate, and fish communities. Data summaries prepared for analytical use are presented in downloadable data tables.

Data Series

Statistical models for the analysis and design of digital polymerase chain (dPCR) experiments

Statistical methods for the analysis and design of experiments using digital PCR (dPCR) have received only limited attention and have been misused in many instances. To address this issue and to provide a more general approach to the analysis of dPCR data, we describe a class of statistical models for the analysis and design of experiments that require quantification of nucleic acids. These models are mathematically equivalent to generalized linear models of binomial responses that include a complementary, log–log link function and an offset that is dependent on the dPCR partition volume. These models are both versatile and easy to fit using conventional statistical software. Covariates can be used to specify different sources of variation in nucleic acid concentration, and a model’s parameters can be used to quantify the effects of these covariates. For purposes of illustration, we analyzed dPCR data from different types of experiments, including serial dilution, evaluation of copy number variation, and quantification of gene expression. We also showed how these models can be used to help design dPCR experiments, as in selection of sample sizes needed to achieve desired levels of precision in estimates of nucleic acid concentration or to detect differences in concentration among treatments with prescribed levels of statistical power.

Analytical Chemistry

Comparison of ion-exchange resin counterions in the nutrient measurement of calcareous soils: Implications for correlative studies of plant-soil relationships

For more than 40 years, ion-exchange resins have been used to characterize nutrient bioavailability in terrestrial and aquatic ecosystems. To date, however, no standardized methodology has been developed, particularly with respect to the counterions that initially occupy resin exchange sites. To determine whether different resin counterions yield different measures of soil nutrients and rank soils differently with respect to their measured nutrient bioavailability, we compared nutrient measurements by three common counterion combinations (HCl, HOH, and NaHCO 3 ). Five sandy calcareous soils were chosen to represent a range of soil characteristics at Canyonlands National Park, Utah, and resin capsules charged with the different counterions equilibrated in saturated pastes of these soils for one week. Data were converted to proportions of total ions of corresponding charge for ANOVA. Results from the different methods were not comparable with respect to any nutrient. Of eleven nutrients measured, all but iron (Fe 2+ ), manganese (Mn 2+ ), and zinc (Zn 2+ ) differed significantly ( p ≤0.05) as a function of soil×counterion interactions; Fe 2+ and Zn 2+ varied as functions of counterion alone. Of the counterion combinations, HCl-resins yielded the most net ion exchange with all measured nutrients except Na + , and the three of which desorbed in the greatest quantities from HOH-resins. Conventional chemical extractions using ammonium acetate generally yielded high proportional values of Ca 2+ , K + , and Na + . Further, among-soil rankings of nutrient bioavailability varied widely among methods. This study highlights the fact that various ion-exchange resin techniques for measuring soil nutrients may have differential effects on the soil-resin environment and yield data that should not be compared nor considered interchangeable. The most appropriate methods for characterizing soil-nutrient bioavailability depends on soil characteristics and likely on the physiological uptake mechanisms of plants or functional groups of interest. The effects of different extraction techniques on nutrient measures should be understood before selecting an extraction method. For example, in the calcareous soils used for this experiment, nutrient extraction methods that alter soil carbonates through dissolution or precipitation could compromise the accurate measurement of plant-available nutrients. The implications of this study emphasize the universal importance of understanding the differential effects of alternate methods on soil chemistry.

Communications in Soil Science and Plant Analysis

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

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

Colorado

Preliminary geochemical assessment of water in selected streams, springs, and caves in the Upper Baker and Snake Creek drainages in Great Basin National Park, Nevada, 2009

Water in caves, discharging from springs, and flowing in streams in the upper Baker and Snake Creek drainages are important natural resources in Great Basin National Park, Nevada. Water and rock samples were collected from 15 sites during February 2009 as part of a series of investigations evaluating the potential for water resource depletion in the park resulting from the current and proposed groundwater withdrawals. This report summarizes general geochemical characteristics of water samples collected from the upper Baker and Snake Creek drainages for eventual use in evaluating possible hydrologic connections between the streams and selected caves and springs discharging in limestone terrain within each watershed. Generally, water discharging from selected springs in the upper Baker and Snake Creek watersheds is relatively young and, in some cases, has similar chemical characteristics to water collected from associated streams. In the upper Baker Creek drainage, geochemical data suggest possible hydrologic connections between Baker Creek and selected springs and caves along it. The analytical results for water samples collected from Wheelers Deep and Model Caves show characteristics similar to those from Baker Creek, suggesting a hydrologic connection between the creek and caves, a finding previously documented by other researchers. Generally, geochemical evidence does not support a connection between water flowing in Pole Canyon Creek to that in Model Cave, at least not to any appreciable extent. The water sample collected from Rosethorn Spring had relatively high concentrations of many of the constituents sampled as part of this study. This finding was expected as the water from the spring travelled through alluvium prior to being discharged at the surface and, as a result, was provided the opportunity to interact with soil minerals with which it came into contact. Isotopic evidence does not preclude a connection between Baker Creek and the water discharging from Rosethorn Spring. The residence time of water discharging into the caves and from selected springs sampled as part of this study ranged from 10 to 25 years. Within the upper Snake Creek drainage, the results of this study show geochemical similarities between Snake Creek and Outhouse Spring, Spring Creek Spring, and Squirrel Spring Cave. The strontium isotope ratio ( 87 Sr/ 86 Sr) for intrusive rock samples representative of the Snake Creek drainage were similar to carbonate rock samples. The water sample collected from Snake Creek at the pipeline discharge point had lower strontium concentrations than the sample downstream and a similar 87 Sr/ 86 Sr value as the carbonate and intrusive rocks. The chemistry of the water sample was considered representative of upstream conditions in Snake Creek and indicates minimal influence of rock dissolution. The results of this study suggest that water discharging from Outlet Spring is not hydrologically connected to Snake Creek but rather is recharged at high altitude(s) within the Snake Creek drainage. These findings for Outlet Spring largely stem from the relatively high specific conductance and chloride concentration, the lightest deuterium (δD) and oxygen-18 (δ 18 O) values, and the longest calculated residence time (60 to 90 years) relative to any other sample collected as part of this study. With the exception of water sampled from Outlet Spring, the residence time of water discharging into Squirrel Spring Cave and selected springs in the upper Snake Creek drainage was less than 30 years.

Nevada

USGS research on energy resources, 1986; program and abstracts

The extended abstracts in this volume are summaries of the papers presented orally and as posters in the second V. E. McKelvey Forum on Mineral and Energy Resources, entitled "USGS Research on Energy Resources-1986." The Forum has been established to improve communication between the USGS and the earth science community by presenting the results of current USGS research on nonrenewable resources in a timely fashion and by providing an opportunity for individuals from other organizations to meet informally with USGS scientists and managers. It is our hope that the McKelvey Forum will help to make USGS programs more responsive to the needs of the earth science community, particularly the mining and petroleum industries, and Win foster closer cooperation between organizations and individuals. The Forum was named after former Director Vincent E. McKelvey in recognition of his lifelong contributions to research, development, and administration in mineral and energy resources, as a scientist, as Chief Geologist, and as Director of the U.S. Geological Survey. The Forum will be an annual event, and its subject matter will alternate between mineral and energy resources. We expect that the format will change somewhat from year to year as various approaches are tried, but its primary purpose will remain the same: to encourage direct communication between USGS scientists and the representatives of other earth-science related organizations. Energy programs of the USGS include oil and gas, coal, geothermal, uranium-thorium, and oil shale; work in these programs spans the national domain, including surveys of the offshore Exclusive Economic Zone. The topics selected for presentation at this McKelvey Forum represent an overview of the scientific breadth of USGS research on energy resources. They include aspects of petroleum occurrence in Eastern United States rift basins, the origin of magnetic anomalies over oil fields, accreted terranes and energy-resource implications, coal quality, geothermal energy sources, integrated geology and chemistry in uranium-deposit studies, and interpretations of sea-floor geology seen in reconnaissance-scale sidescan-sonar mosaics of the Gulf of Mexico and west coast Exclusive Economic Zone. Data are presented that are being used in building models of geothermal energy settings, basin histories, and the occurrence of energy resources. In addition to the technical sessions presenting the results of USGS research, each congressionally mandated USGS Mineral Resource Program has a display outlining plans and progress. We are all excited about this continuing opportunity to disseminate and discuss our research with our colleagues in industry and academia, and we welcome your suggestions on improving this series of Forums.

Circular

Effects of historical coal mining and drainage from abandoned mines on streamflow and water quality in Bear Creek, Dauphin County, Pennsylvania — March 1999–December 2002

More than 100 years of anthracite coal mining has changed surface- and ground-water hydrology and contaminated streams draining the Southern Anthracite Coal Field in east-central Pennsylvania. Bear Creek drains the western prong of the Southern Anthracite Coal Field and is affected by metals in drainage from abandoned mines and streamwater losses. Total Maximum Daily Loads (TMDL) developed for dissolved iron of about 5 lb/d (pounds per day) commonly are exceeded in the reach downstream of mine discharges. Restoration of Bear Creek using aerobic ponds to passively remove iron in abandoned mine drainage is under consideration (2004) by the Dauphin County Conservation District. This report, prepared in cooperation with the Dauphin County Conservation District, evaluates chemical and hydrologic data collected in Bear Creek and its receiving waters prior to implementation of mine-drainage treatment. The data collected represent the type of baseline information needed for documentation of water-quality changes following passive treatment of mine drainage in Pennsylvania and in other similar hydrogeologic settings. Seven surface-water sites on Bear Creek and two mine discharges were monitored for nearly three years to characterize the chemistry and hydrology of the following: (1) Bear Creek upstream of the mine discharges (BC-UMD), (2) water draining from the Lykens-Williamstown Mine Pool at the Lykens Water-Level Tunnel (LWLT) and Lykens Drift (LD) discharges, (3) Bear Creek after mixing with the mine discharges (BC-DMD), and (4) Bear Creek prior to mixing with Wiconisco Creek (BCM). Two sites on Wiconisco Creek, upstream and downstream of Bear Creek (WC-UBC and WC-DBC, respectively), were selected to evaluate changes in streamflow and water quality upon mixing with Bear Creek. During periods of below-normal precipitation, streamwater loss was commonly 100 percent upstream of site BC-UMD (streamflow range = 0 to 9.7 ft3/s (cubic feet per second)) but no loss was detected downstream owing to sustained mine water drainage from the Lykens Water-Level Tunnel (range = 0.41 to 3.7 ft3/s), Lykens Drift (range = 0.40 to 6.1 ft3/s), and diffuse zones of seepage. Collectively, mine water inputs contributed about 84 percent of base flow and 53 percent of stormflow measured in the downstream reach. An option under consideration by the Dauphin County Conservation District for treatment of the discharge from the LWLT requires the source of the discharge to be captured and rerouted downstream, bypassing approximately 1,000 feet of stream channel. Because streamwater loss upstream of the tunnel was commonly 100 percent, rerouting the discharge from the LWLT may extend the reach of Bear Creek that is subject to dryness. Differences in the chemistry of water discharging from the LWLT compared to the LD suggest that the flow path through the Lykens-Williamstown Mine Pool to each mine discharge is unique. The LWLT is marginally alkaline (median net acid neutralizing capacity (ANC) = 9 mg/L (milligrams per liter) as CaCO3; median pH = 5.9), commonly becomes acidic (minimum net ANC = -74 mg/L as CaCO3) at low flow, and may benefit from alkaline amendments prior to passive treatment. Water discharging from the LD provides excess ANC (median net ANC = 123 mg/L as CaCO3; median pH = 6.5) to the downstream reach and is nearly anoxic at its source (median dissolved oxygen = 0.5 mg/L). Low dissolved oxygen water with relatively high ANC and metals concentrations discharging from the LD is characteristic of a deeper flow path and longer residence time within the mine pool than the more acidic, oxygenated water discharging from the LWLT. TMDLs for iron have been developed for dissolved species only. Consequently, distinguishing between dissolved and suspended iron in Bear Creek is important for evaluating water-quality improvement through TMDL attainment. Median total iron concentration increased from 550 mg/L (micrograms per liter) at site BC-UM

Pennsylvania

Surface variable‐based machine learning for scalable arsenic prediction in undersampled areas

In the United States, private wells are not federally regulated, and many households do not test for Arsenic (As). Chronic exposure is linked with multiple health outcomes, and risk can change sharply over short distances and with well depth. Coarse maps or sparse sampling often miss exceedances. Most existing models operate at ∼1 km resolution and use groundwater chemistry or detailed geologic logs, which limits their use in undersampled areas where improved guidance is most needed. We overcome these limitations by developing a machine learning model for Minnesota, USA, that predicts As exposure risk using only surficial variables from remote sensing and global data sets. Variables related to surface water hydrology and geomorphology are selected based on mechanistic links that control redox conditions and As mobilization. Local training was essential, and surficial geology variables that are more sensitive to local conditions were needed to maximize model accuracy. The resulting complete model was sufficiently sensitive to generate accurate and detailed risk maps and depth profiles of As concentrations above the 10 μg/L maximum contaminant level. Accuracy depended on local training data density. We identified a training data density of 0.07 wells/km 2 as a practical target for stable county-level performance. Maps of exceedance probabilities highlight priority areas for testing that are particularly important in rural communities that have received less sampling. These results support public health action by guiding where to install wells and where to test them, how much new sampling is needed, and where treatment outreach is most urgent.

Minnesota

Biological relevance of streamflow metrics: Regional and national perspectives

Protecting the health of streams and rivers requires identifying ecologically significant attributes of the natural flow regime. Streamflow regimes are routinely quantified using a plethora of hydrologic metrics (HMs), most of which have unknown relevance to biological communities. At regional and national scales, we evaluated which of 509 commonly used HMs were associated with biological indicators of fish and invertebrate community integrity. We quantified alteration of each HM by using statistical models to predict site-specific natural baseline values for each of 728 sites across the USA where streamflow monitoring data were available concurrent with assessments of invertebrate or fish community integrity. We then ranked HMs according to their individual association with biological integrity based on random forest models that included HMs and other relevant covariates, such as land cover and stream chemistry. HMs were generally the most important predictors of biological integrity relative to the covariates. At a national scale, the most influential HMs were measures of depleted high flows, homogenization of flows, and erratic flows. Unique combinations of biologically relevant HMs were apparent among regions. We discuss the implications of our findings to the challenge of selecting HMs for streamflow research and management.

Freshwater Science