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Trends in surface-water quality at selected National Stream Quality Accounting Network (NASQAN) stations, in Michigan

To demonstrate the value of long-term, water-quality monitoring, the Michigan Department of Environmental Quality (MDEQ), in cooperation with the U.S. Geological Survey (USGS), initiated a study to evaluate potential trends in water-quality constituents for selected National Stream Quality Accounting Network (NASQAN) stations in Michigan. The goal of this study is to assist the MDEQ in evaluating the effectiveness of water-pollution control efforts and the identification of water-quality concerns. The study included a total of nine NASQAN stations in Michigan. Approximately 28 constituents were analyzed for trend tests. Station selection was based on data availability, land-use characteristics, and station priority for the MDEQ Water Chemistry Monitoring Project. Trend analyses were completed using the uncensored Seasonal Kendall Test in the computer program Estimate Trend (ESTREND), a software program for the detection of trends in water-quality data. The parameters chosen for the trend test had (1) at least a 5-year period of record (2) about 5 percent of the observations censored at a single reporting limit, and (3) 40 percent of the values within the beginning one-fifth and ending one-fifth of the selected period. In this study, a negative trend indicates a decrease in concentration of a particular constituent, which generally means an improvement in water quality; whereas a positive trend means an increase in concentration and possible degradation of water quality. The results of the study show an overall improvement in water quality at the Clinton River at Mount Clemens, Manistee River at Manistee, and Pigeon River near Caseville. The detected trend for these stations show decreases in concentrations of various constituents such as nitrogen compounds, conductance, sulfate, fecal coliform bacteria, and fecal streptococci bacteria. The negative trend may indicate an overall improvement in agricultural practices, municipal and industrial wastewater-treatment processes, and effective regulations. Phosphorus data for most of the study stations could not be analyzed because of the data limitations for trend tests. The only station with a significant negative trend in total phosphorus concentration is the Clinton River at Mount Clemens. However, scatter-plot analyses of phosphorus data indicate decreasing concentrations with time for most of the study stations. Positive trends in concentration of nitrogen compounds were detected at the Kalamazoo River near Saugatuck and Muskegon River near Bridgeton. Positive trends in both fecal coliform and total fecal coliform were detected at the Tahquamenon River near Paradise. Various different point and nonpoint sources could produce such positive trends, but most commonly the increase in concentrations of nitrogen compounds and fecal coliform bacteria are associated with agricultural practices and sewage-plant discharges. The constituent with the most numerous and geographically widespread significant trend is pH. The pH levels increased at six out of nine stations on all the major rivers in Michigan, with no negative trend at any station. The cause of pH increase is difficult to determine, as it could be related to a combination of anthropogenic activities and natural processes occurring simultaneously in the environment. Trends in concentration of major ions, such as calcium, sodium, magnesium, sulfate, fluoride, chloride, and potassium, were detected at eight out of nine stations. A negative trend was detected only in sulfate and fluoride concentrations; a positive trend was detected only in calcium concentration. The major ions with the most widespread significant trends are sodium and chloride; three positive and two negative trends were detected for sodium, and three negative and two positive trends were detected for chloride. The negative trends in chloride concentrations outnumbered the positive trends. This result indicates a slight improvement in surface-water quality because chloride as a point source in natural water comes from deicing salt, sewage effluents, industrial wastes, and oil fields. For other major ions, such as magnesium and potassium, both positive and negative trends were detected. These changes in trends indicate changes in surface-water quality caused by a variety of point and non-point sources throughout Michigan, as well as natural changes in the environment.

Michigan↗

Simulation of the Regional Ground-Water-Flow System and Ground-Water/Surface-Water Interaction in the Rock River Basin, Wisconsin

A regional, two-dimensional, areal ground-water-flow model was developed to simulate the ground-water-flow system and ground-water/surface-water interaction in the Rock River Basin. The model was developed by the U.S. Geological Survey (USGS), in cooperation with the Rock River Coalition. The objectives of the regional model were to improve understanding of the ground-water-flow system and to develop a tool suitable for evaluating the effects of potential regional water-management programs. The computer code GFLOW was used because of the ease with which the model can simulate ground-water/surface-water interactions, provide a framework for simulating regional ground-water-flow systems, and be refined in a stepwise fashion to incorporate new data and simulate ground-water-flow patterns at multiple scales. The ground-water-flow model described in this report simulates the major hydrogeologic features of the modeled area, including bedrock and surficial aquifers, ground-water/surface-water interactions, and ground-water withdrawals from high-capacity wells. The steady-state model treats the ground-water-flow system as a single layer with hydraulic conductivity and base elevation zones that reflect the distribution of lithologic groups above the Precambrian bedrock and a regionally significant confining unit, the Maquoketa Formation. In the eastern part of the Basin where the shale-rich Maquoketa Formation is present, deep ground-water flow in the sandstone aquifer below the Maquoketa Formation was not simulated directly, but flow into this aquifer was incorporated into the GFLOW model from previous work in southeastern Wisconsin. Recharge was constrained primarily by stream base-flow estimates and was applied uniformly within zones guided by regional infiltration estimates for soils. The model includes average ground-water withdrawals from 1997 to 2006 for municipal wells and from 1997 to 2005 for high-capacity irrigation, industrial, and commercial wells. In addition, the model routes tributary base flow through the river network to the Rock River. The parameter-estimation code PEST was linked to the GFLOW model to select the combination of parameter values best able to match more than 8,000 water-level measurements and base-flow estimates at 9 streamgages. Results from the calibrated GFLOW model show simulated (1) ground-water-flow directions, (2) ground-water/surface-water interactions, as depicted in a map of gaining and losing river and lake sections, (3) ground-water contributing areas for selected tributary rivers, and (4) areas of relatively local ground water captured by rivers. Ground-water flow patterns are controlled primarily by river geometries, with most river sections gaining water from the ground-water-flow system; losing sections are most common on the downgradient shore of lakes and reservoirs or near major pumping centers. Ground-water contributing areas to tributary rivers generally coincide with surface watersheds; however the locations of ground-water divides are controlled by the water table, whereas surface-water divides are controlled by surface topography. Finally, areas of relatively local ground water captured by rivers generally extend upgradient from rivers but are modified by the regional flow pattern, such that these areas tend to shift toward regional ground-water divides for relatively small rivers. It is important to recognize the limitations of this regional-scale model. Heterogeneities in subsurface properties and in recharge rates are considered only at a very broad scale (miles to tens of miles). No account is taken of vertical variations in properties or pumping rates, and no provision is made to account for stacked ground-water-flow systems that have different flow patterns at different depths. Small-scale flow systems (hundreds to thousands of feet) associated with minor water bodies are not considered; as a result, the model is not currently designed for simulating site-specifi

Scientific Investigations Report↗

Hydrogeologic Framework, Groundwater Movement, and Water Budget in Tributary Subbasins and Vicinity, Lower Skagit River Basin, Skagit and Snohomish Counties, Washington

A study to characterize the groundwater-flow system in four tributary subbasins and vicinity of the lower Skagit River basin was conducted by the U.S. Geological Survey to assist Skagit County and the Washington State Department of Ecology in evaluating the effects of potential groundwater withdrawals and consumptive use on tributary streamflows. This report presents information used to characterize the groundwater and surface-water flow system in the subbasins, and includes descriptions of the geology and hydrogeologic framework of the subbasins; groundwater recharge and discharge; groundwater levels and flow directions; seasonal groundwater-level fluctuations; interactions between aquifers and the surface-water system; and a water budget for the subbasins. The study area covers about 247 mi2 along the Skagit River and its tributary subbasins (East Fork Nookachamps Creek, Nookachamps Creek, Carpenter Creek, and Fisher Creek) in southwestern Skagit County and northwestern Snohomish County, Washington. The geology of the area records a complex history of accretion along the continental margin, mountain building, deposition of terrestrial and marine sediments, igneous intrusion, and the repeated advance and retreat of continental glaciers. A simplified surficial geologic map was developed from previous mapping in the area, and geologic units were grouped into nine hydrogeologic units consisting of aquifers and confining units. A surficial hydrogeologic unit map was constructed and, with lithologic information from 296 drillers'logs, was used to produce unit extent and thickness maps and four hydrogeologic sections. Groundwater in unconsolidated aquifers generally flows towards the northwest and west in the direction of the Skagit River and Puget Sound. This generalized flow pattern is likely complicated by the presence of low-permeability confining units that separate discontinuous bodies of aquifer material and act as local groundwater-flow barriers. Groundwater-flow directions in the sedimentary aquifer likely reflect local topographic relief (radial flow from bedrock highs) and more regional westward flow from the mountains to the Puget Sound. The largest groundwater-level fluctuations observed during the monitoring period (October 2006 through September 2008) occurred in wells completed in the sedimentary aquifer, and ranged from about 3 to 27 feet. Water levels in wells completed in unconsolidated hydrogeologic units exhibited seasonal variations ranging from less than 1 to about 10 feet. Synoptic streamflow measurements made in August 2007 and June 2008 indicate a total groundwater discharge to creeks in the tributary subbasin area of about 13.15 and 129.6 cubic feet per second (9,520 and 93,830 acre-feet per year), respectively. Streamflow measurements illustrate a general pattern in which the upper reaches of creeks in the study area tended to gain flow from the groundwater system, and lower creek reaches tended to lose water. Large inflows from tributaries to major creeks in the study area suggest the presence of groundwater discharge from upland areas underlain by bedrock. The groundwater system within the subbasins received an average (September 1, 2006 to August 31, 2008) of about 92,400 acre-feet or about 18 inches of recharge from precipitation a year. Most of this recharge (65 percent) discharges to creeks, and only about 3 percent is withdrawn from wells. The remaining groundwater recharge (32 percent) leaves the subbasin groundwater system as discharge to the Skagit River and Puget Sound.

Scientific Investigations Report↗

External quality assurance project report for the National Atmospheric Deposition Program’s National Trends Network and Mercury Deposition Network, 2015–16

The U.S. Geological Survey Precipitation Chemistry Quality Assurance project operated five distinct programs to provide external quality assurance monitoring for the National Atmospheric Deposition Program’s (NADP) National Trends Network and Mercury Deposition Network during 2015–16. The National Trends Network programs include (1) a field audit program to evaluate sample contamination and stability, (2) an interlaboratory comparison program to evaluate analytical laboratory performance, and (3) a colocated sampler program to evaluate bias and variability attributed to automated precipitation samplers. The Mercury Deposition Network programs include the (4) system blank program and (5) an interlaboratory comparison program. The results indicate that NADP data continue to be of sufficient quality for the analysis of spatial distributions and time trends for chemical constituents in wet deposition. The field audit program results indicate increased sample contamination for calcium, magnesium, and potassium relative to 2010 levels, and slight fluctuation in sodium contamination. Nitrate contamination levels dropped slightly during 2014–16, and chloride contamination leveled off between 2007 and 2016. Sulfate contamination is similar to the 2000 level. Hydrogen ion contamination has steadily decreased since 2012. Losses of ammonium and nitrate resulting from potential sample instability were negligible. The NADP Central Analytical Laboratory produced interlaboratory comparison results with low bias and variability compared to other domestic and international laboratories that support atmospheric deposition monitoring. Significant absolute bias above the magnitudes of the detection limits was observed for nitrate and sulfate concentrations, but no analyte determinations exceeded the detection limits for blanks. Colocated sampler program results from dissimilar colocated collectors indicate that the retrofit of the National Trends Network with N-CON Systems Company, Inc. precipitation collectors could cause substantial shifts in NADP annual deposition (concentration multiplied by depth) values. Median weekly relative percent differences for analyte concentrations ranged from -4 to +76 percent for cations, from 5 to 6 percent for ammonium, from +14 to +25 percent for anions, and from -21 to +8 percent for hydrogen ion contamination. By comparison, weekly absolute concentration differences for paired identical N-CON Systems Company, Inc., collectors ranged from 4–22 percent for cations; 2–9 percent for anions; 4–5 percent for ammonium; and 13–14 percent for hydrogen ion contamination. The N-CON Systems Company, Inc. collector caught more precipitation than the Aerochem Metrics Model 301 collector (ACM) at the WA99/99WA sites, but it typically caught slightly less precipitation than the ACM at ND11/11ND, sites which receive more wind and snow than WA99/99WA. Paired, identical OTT Pluvio-2 and ETI Noah IV precipitation gages were operated at the same sites. Median absolute percent differences for daily measured precipitation depths ranged from 0 to 7 percent. Annual absolute differences ranged from 0.08 percent (ETI Noah IV precipitation gages) to 11 percent (OTT Pluvio-2 precipitation gages). The Mercury Deposition Network programs include the system blank program and an interlaboratory comparison program. System blank results indicate that maximum total mercury contamination concentrations in samples were less than the third percentile of all Mercury Deposition Network sample concentrations (1.098 nanograms per liter; ng/L). The Mercury Analytical Laboratory produced chemical concentration results with low bias and variability compared with other domestic and international laboratories that support atmospheric-deposition monitoring. The laboratory’s performance results indicate a +1-ng/L shift in bias between 2015 (-0.4 ng/L) and 2016 (+0.5 ng/L).

Scientific Investigations Report↗

Evaluation of the ground-water flow model for northern Utah Valley, Utah, updated to conditions through 2002

This report evaluates the performance of a numerical model of the ground-water system in northern Utah Valley, Utah, that originally simulated ground-water conditions during 1947-1980 and was updated to include conditions estimated for 1981-2002. Estimates of annual recharge to the ground-water system and discharge from wells in the area were added to the original ground-water flow model of the area. The files used in the original transient-state model of the ground-water flow system in northern Utah Valley were imported into MODFLOW-96, an updated version of MODFLOW. The main model input files modified as part of this effort were the well and recharge files. Discharge from pumping wells in northern Utah Valley was estimated on an annual basis for 1981-2002. Although the amount of average annual withdrawals from wells has not changed much since the previous study, there have been changes in the distribution of well discharge in the area. Discharge estimates for flowing wells during 1981-2002 were assumed to be the same as those used in the last stress period of the original model because of a lack of new data. Variations in annual recharge were assumed to be proportional to changes in total surface-water inflow to northern Utah Valley. Recharge specified in the model during the additional stress periods varied from 255,000 acre-feet in 1986 to 137,000 acre-feet in 1992. The ability of the updated transient-state model to match hydrologic conditions determined for 1981-2002 was evaluated by comparing water-level changes measured in wells to those computed by the model. Water-level measurements made in February, March, or April were available for 39 wells in the modeled area during all or part of 1981-2003. In most cases, the magnitude and direction of annual water-level change from 1981 to 2002 simulated by the updated model reasonably matched the measured change. The greater-than-normal precipitation that occurred during 1982-84 resulted in period-of-record high water levels measured in many of the observation wells in March 1984. The model-computed water levels at the end of 1982-84 also are among the highest for the period. Both measured and computed water levels decreased during the period representing ground-water conditions from 1999 to 2002. Precipitation was less than normal during 1999-2002. The ability of the model to adequately simulate climatic extremes such as the wetter-than-normal conditions of 1982-84 and the drier-than-normal conditions of 1999-2002 indicates that the annual variation of recharge to the ground-water system based on streamflow entering the valley, which in turn is primarily dependent upon precipitation, is appropriate but can be improved. The updated transient-state model of the ground-water system in northern Utah Valley can be improved by making revisions on the basis of currently available data and information.

Utah↗

Hydrology of the middle San Pedro area, southeastern Arizona

In the middle San Pedro Watershed in southeastern Arizona, groundwater is the primary source of water supply for municipal, domestic, industrial, and agricultural use. The watershed comprises two smaller subareas, the Benson subarea and the Narrows-Redington subarea. Early 21st century projections for heavy population growth in the watershed have not yet become a reality, but increased groundwater withdrawals could have undesired consequences - such as decreased base flow to the San Pedro River, and groundwater-level declines - that would lead to the need to deepen existing wells. This report describes the hydrology, hydrochemistry, water quality, and development of a groundwater budget for the middle San Pedro Watershed, focusing primarily on the elements of groundwater movement that could be most useful for the development of a groundwater model Precipitation data from Tombstone, Arizona, and base flow at the stream-gaging station on the San Pedro River at Charleston both show relatively dry periods during the 1960s through the mid-1980s and in the mid-1990s to 2009, and wetter periods from the mid-1980s through the mid-1990s. Water levels in four out of five wells near the mountain fronts show cyclical patterns of recharge, with rates of recharge greatest in the early 1980s through the mid-1990s. Three wells near the San Pedro River recorded their lowest levels during the 1950s to the mid-1960s. The water-level record from one well, completed in the confined part of the coarse-grained lower basin fill, showed a decline of approximately 21 meters. Annual flow of the San Pedro River, measured at the Charleston and Redington gages, has decreased since the 1940s. The median annual streamflow and base flow at the gaging station on the river near Tombstone has decreased by 50 percent between the periods 1968–1986 and 1997–2009. Estimates of streamflow infiltration along the San Pedro River during 1914–2009 have decreased 44 percent, with the largest decreases in the months June–October in the Benson subarea. In the Narrows-Redington subarea, streamflow infiltration has decreased about 65 percent during 1914–2009. The average annual outflow (27.6 hm 3 /year [cubic hectometers per year]) from the Benson subarea aquifer for water years 2001 through 2009 exceeded the inflows (20.0 hm 3 / yr) by 7.60 hm 3 /yr. In the Narrows-Redington subarea for the same period, the average annual outflow (15.7 hm 3 /yr) from the aquifer system exceeded the inflows (13.8 hm 3 /yr) by nearly 2 hm 3 /yr. The largest withdrawals of groundwater in both subareas are for irrigation; these withdrawals peaked in 1973 and have been steadily decreasing since then. Recharge from streamflow infiltration exceeded recharge from the mountain-front and from ephemeral channels in the Benson subarea. In the Narrows-Redington subarea, however, recharge from mountain-front and ephemeral channel recharge exceeded recharge from streamflow infiltration. Evapotranspiration by phreatophytes accounts for the largest outflow of groundwater for both subareas—78 percent of the outflow in the Narrows-Redington subarea and 62 percent of the outflow in the Benson subarea. Precipitation, surface-water, and groundwater chemistry and isotope data indicated the relative age and residence time of groundwater, the amount of interaction between geologic sources and groundwater, and how recharge elevation and season were related to the presence of modern water. The bedrock aquifer receives modern recharge (

Arizona↗

Volatile organic compound matrix spike recoveries for ground- and surface-water samples, 1997-2001

The U.S. Geological Survey's National Water-Quality Assessment (NAWQA) Program used field matrix spikes (FMSs), field matrix spike replicates (FMSRs), laboratory matrix spikes (LMSs), and laboratory reagent spikes (LRSs), in part, to assess the quality of volatile organic compound (VOC) data from water samples collected and analyzed in more than 50 of the Nation's largest river basins and aquifers (Study Units). The data-quality objectives of the NAWQA Program include estimating the extent to which variability, degradation, and matrix effects, if any, may affect the interpretation of chemical analyses of ground- and surface-water samples. In order to help meet these objectives, a known mass of VOCs was added (spiked) to water samples collected in 25 Study Units. Data within this report include recoveries from 276 ground- and surface-water samples spiked with a 25-microliter syringe with a spike solution containing 85 VOCs to achieve a concentration of 0.5 microgram per liter. Combined recoveries for 85 VOCs from spiked ground- and surface-water samples and reagent water were used to broadly characterize the overall recovery of VOCs. Median recoveries for 149 FMSs, 107 FMSRs, 20 LMSs, and 152 LRSs were 79.9, 83.3, 113.1, and 103.5 percent, respectively. Spike recoveries for 85 VOCs also were calculated individually. With the exception of a few VOCs, the median percent recoveries determined from each spike type for individual VOCs followed the same pattern as for all VOC recoveries combined, that is, listed from least to greatest recovery-FMSs, FMSRs, LRSs, and LMSs. The median recoveries for individual VOCs ranged from 63.7 percent to 101.5 percent in FMSs; 63.1 percent to 101.4 percent in FMSRs; 101.7 percent to 135.0 percent in LMSs; and 91.0 percent to 118.7 percent in LRSs. Additionally, individual VOC recoveries were compared among paired spike types, and these recoveries were used to evaluate potential bias in the method. Variability associated with field spiking, field handling, transport, and analysis was assessed by comparing recoveries between 107 pairs of FMR and FMSR samples. For most VOCs, FMSR recoveries were greater than the paired FMS recoveries. This may result from routinely processing the FMS sample first, allowing a more fluid and efficient technique when processing the FMSR. Degradation was examined by comparing VOC recoveries between 20 pairs of FMS and LMS samples. For all VOCs, the LMS recoveries were greater than FMS recoveries. However, data presented in a previously published VOC stability study were interpreted, and recoveries indicated that VOC degradation should not affect the recovery for most VOCs monitored by the NAWQA Program. Matrix effects were examined by comparing VOC recoveries from 20 pairs of LMS and LRS samples. With the exception of two VOCs, individual recoveries were not significantly different between LMSs and LRSs, indicating that most VOC recoveries are not affected by matrix effects. Additionally, matrix effects should be negligible due to the analytical technique (purge and trap capillary column gas chromatography/mass spectrometry) used for VOC analysis at the U.S. Geological Survey National Water Quality Laboratory (NWQL). The reason for the lower VOC recoveries from FMSs and FMSRs than from LMSs and LRSs may be associated with differences in spiking technique and experience, and to varying environmental conditions at the time of spiking. However, for all spike types, 87 percent of the individual VOC recoveries were within the range of 60 to 140 percent, a range that is considered acceptable by the U.S. Environmental Protection Agency's established analytical method. Additionally, the median recovery for each spike type was within the range of 60 to 140 percent. The excellent VOC recoveries from LMSs and LRSs demonstrate that low VOC concentrations can routinely and accurately be measured by the analytical methods used by the NWQL.

Scientific Investigations Report↗

An evaluation and review of water-use estimates and flow data for the Lower Klamath and Tule Lake National Wildlife Refuges, Oregon and California

The Lower Klamath and Tule Lake National Wildlife Refuges, located in the upper Klamath Basin of Oregon and California, encompass approximately 46,700 and 39,100 acres, respectively. Demand for water in the semiarid upper Klamath Basin has increased in recent years, resulting in the need to better quantify water availability and use in the refuges. This report presents an evaluation of water-use estimates for both refuges derived on the basis of two approaches. One approach used evaporation and evapotranspiration estimates and the other used measured inflow and outflow data. The quality of the inflow and outflow data also was assessed. Annual water use in the refuges, using evapotranspiration estimates, was computed with the use of different rates for each of four land-use categories. Annual water-use rates for grain fields, seasonal wetlands, permanently flooded wetlands with emergent vegetation, and open-water bodies were 2.5, 2.9, 2.63, and 4.07 feet per year, respectively. Total water use was estimated as the sum of the products of each rate and the number of acres in its associated land-use category. Mean annual (2003-2005) water use for the Lower Klamath and Tule Lake refuges was approximately 124,000 and 95,900 acre-feet, respectively. To estimate water deliveries needed for each refuge, first, annual precipitation for 2003-2005 was subtracted from the annual water use for those years. Then, an adjusted total was obtained by adding 20 percent to the difference to account for salinity flushing. Resulting estimated mean annual adjusted needed water deliveries in 2003-2005 for the Lower Klamath and Tule Lake refuges were 107,000 and 82,800 acre-feet, respectively. Mean annual net inflow to the refuges for 2003-2005 was computed by subtracting estimated and measured surface-water outflows from inflows. Mean annual net inflow during the 3-year period for the Lower Klamath refuge, calculated for a subsection of the refuge, was approximately 73,700 acre-feet. The adjusted needed water delivery for this section of the refuge, calculated from evapotranspiration estimates, was approximately 77,600 acre-feet. For the Tule Lake refuge, mean annual net inflow during the 3-year period was approximately 76,100 acre-feet, which is comparable to the estimated annual needed water delivery for the refuge of 82,800 acre-feet. For 1962-2005, mean annual net inflow to the Lower Klamath refuge was approximately 49,800 acre-feet, about 23,900 acre-feet less than for 2003-2005. Although mean April-September net inflows for 1962-2005 and 2003-2005 have remained fairly constant, annual net inflow has increased for October-March, which accounts for the difference. Consistently higher autumn and winter flow deliveries since the mid-1980s reflect a significant change in refuge management. More sections of the refuge are currently managed as seasonal wetlands than were in the 1960s and 1970s. Flow records for the Ady Canal at State Line Road, Klamath Straits Drain at State Line Road, and D Pumping Plant were evaluated for their data quality. On the basis of USGS flow-record criteria, all three flow records were rated as 'poor.' By definition, 95 percent of the daily flows in a record having this rating could be in error by more than 15 percent.

Scientific Investigations Report↗

Arc-related porphyry molybdenum deposit model

This report provides a descriptive model for arc-related porphyry molybdenum deposits. Presented within are geological, geochemical, and mineralogical characteristics that differentiate this deposit type from porphyry copper and alkali-feldspar rhyolite-granite porphyry molybdenum deposits. The U.S. Geological Survey's effort to update existing mineral deposit models spurred this research, which is intended to supplement previously published models for this deposit type that help guide mineral-resource and mineral-environmental assessments. Arc-related porphyry molybdenum deposits are a substantial resource for molybdenum metal and may have anomalous concentrations of tungsten. The deposits contain low-grade ore (0.03-0.22 percent molybdenum) as molybdenite, but are large-tonnage, making them amenable to bulk mining open-pit techniques. The mineralizing system usually has fluorine contents of less than 0.1 percent. The cogenetic intrusion is a differentiated calc-alkaline granitoid, typically granodiorite to quartz monzonite in composition, with low rubidium and niobium, and moderate to high strontium concentrations. Metals and hydrothermal fluids are sourced from these intrusions, with an additional meteoric fluid component contributing to peripheral alteration but not adding more metal. The lithology of the surrounding country rocks is not important to the formation of these deposits, but a surrounding carbonate unit may be altered to skarn that contains economic mineralization. The creation of contact-metamorphosed hornfels adjacent to the intrusion is common. Formation of arc-related porphyry molybdenum deposits typically occurs within a continental arc environment related to arc-continent or continent-continent collision and subduction. Few deposits are found in an island arc setting. Most classified arc-related porphyry molybdenum deposits are located in the western cordillera of North America, notably in British Columbia and Alaska. Hydrothermal alteration provides a key component to the identification of a deposit. Alteration usually is zoned from a core of potassic plus/minus silicic alteration outwards through phyllic to propylitic alteration. Argillic alteration may be irregular in shape and will overprint earlier hydrothermal alteration. Exploration should be limited to magmatic arc belts that have been unroofed and eroded to levels of a few kilometers depth. Important geological vectors toward areas of higher grade mineralization include intensity of hydrothermal alteration, veining, and faulting. Anomalous levels of molybdenum, tungsten, copper, lead, or zinc in soils, tills, stream sediments, and drainage waters may indicate the presence of an arc-related porphyry molybdenum deposit. Geophysical exploration techniques have been met with minimal success because of the overall low concentration of associated sulfide and oxide minerals. Geoenvironmental concerns are generally low because of low volumes of sulfide minerals. Most deposits are marginally acid-generating to non-acid-generating with drainage waters being near-neutral pH because of the acid generating potential of pyrite being partially buffered by late-stage calcite-bearing veins. The low ore content results in a waste:ore ratio of nearly 1:1 and large tailings piles from the open-pit method of mining.

Scientific Investigations Report↗

Characterization of streamflow and nutrient occurrence in the upper White River Basin, Colorado, 1980–2020

In 2016, Colorado Parks and Wildlife identified filamentous algae collected from the main stem White River as Cladophora glomerata , a pervasive nuisance aquatic alga. Excessive levels of filamentous algae can compromise aesthetic quality, limit recreational activities, and have negative effects on aquatic life including strong fluctuations in dissolved oxygen levels and a reduction in overall biodiversity. To increase understanding of the biology of the upper White River Basin in Colorado, identify potential factors promoting or limiting nuisance algal abundance, and outline information to aid in the understanding and protection of water resources, the U.S. Geological Survey (USGS), in cooperation with the White River and Douglas Creek Conservation Districts and the White River Algae Technical Advisory Group, initiated a study to collect and analyze physical, chemical, and biological information for the upper White River Basin. The report describes long-term changes and spatial variations in streamflow and nutrient concentrations and loads in the upper White River Basin and identifies possible nutrient sources in the basin. Long-term streamflow and nutrient data indicate that conditions in the upper White River Basin have become more favorable to benthic algae over varying timescales. Upward trends in total phosphorus concentrations and loads were found at three sites across the basin from 2000 to 2020. Total phosphorus loads increased around 50 percent, ranging from 18 to 48 pounds per year. Annual estimated concentrations of total phosphorus from 2005 to 2020 were above algal-specific nutrient criteria at the North Fork White River at Buford, Colo., indicating that phosphorus concentrations at this site likely promote algal growth. Discrete concentrations of total phosphorus exceeded algal-specific nutrient criteria on the South Fork and main stem White River during the summer season, though less frequently than samples collected from the North Fork White River. Nitrogen to phosphorus molar ratios collected from July to September indicate movement from colimitation (10–22) to nitrogen limited (less than 13) conditions at the North Fork White River at Buford, Colo. and the South Fork White River at Buford, Colo. starting in 2012. The magnitude of trends in phosphorus loads were generally greater than trends in concentrations across all sites, indicating that the largest changes in concentrations occurred during greater streamflow periods. At White River above Coal Creek, near Meeker, Colo., significant downward trends in streamflow were found in August and September for mean streamflow (15 and 14 percent per decade, respectively) and 7-day minimum streamflows (23 and 22 percent per decade, respectively). Significant downward trends in annual 7-day minimum streamflows of 24 percent per decade, or 66 percent over the 40-year period of analysis, were also observed. Though not significant based on 90-percent confidence intervals, downward trends in 1-day maximum and mean streamflows in May and June and corresponding increases in April may indicate a shift toward earlier snowmelt runoff, as observed across western North America and the Colorado River Basin. Alteration of the annual hydrograph can influence factors that influence algae including nutrient input and dilution potential, water temperature, dissolved oxygen, light availability, and physical disturbance. Results from a synoptic-style sampling identified the lower North Fork White River subbasin as a large source of phosphorus to the downstream system. Large increases in phosphorus loads were observed below Marvine Creek. Synoptic samples and samples collected during spring and summer of 2019 and 2020 also show large increases in total nitrogen, orthophosphate, and total phosphorus occurring at the furthest three downstream sites on the White River. To further evaluate sources of nitrogen in the upper White River Basin, the dual isotopic composition of nitrate was compared across four sites. The isotopic compositions of nitrate were all within the expected range of typical soil-derived nitrate, though the same values can also be derived from a mixture of agricultural fertilizer and manure or septic sources.

Colorado↗

Water Quality and Hydrology of Silver Lake, Barron County, Wisconsin, With Special Emphasis on Responses of a Terminal Lake to Changes in Phosphorus Loading and Water Level

Silver Lake is typically an oligotrophic-to-mesotrophic, soft-water, terminal lake in northwestern Wisconsin. A terminal lake is a closed-basin lake with surface-water inflows but no surface-water outflows to other water bodies. After several years with above-normal precipitation, very high water levels caused flooding of several buildings near the lake and erosion of soil around much of the shoreline, which has been associated with a degradation in water quality (increased phosphorus and chlorophyll a concentrations and decreased water clarity). To gain a better understanding of what caused the very high water levels and degradation in water quality and collect information to better understand the lake and protect it from future degradation, the U.S. Geological Survey did a detailed study from 2004 to 2008. This report describes results of the study; specifically, lake-water quality, historical changes in water level, water and phosphorus budgets for the two years monitored in the study, results of model simulations that demonstrate how changes in phosphorus inputs affect lake-water quality, and the relative importance of changes in hydrology and changes in the watershed to the water quality of the lake. From 1987 to about 1996, water quality in Silver Lake was relatively stable. Since 1996, however, summer average total phosphorus concentrations increased from about 0.008 milligrams per liter (mg/L) to 0.018 mg/L in 2003, before decreasing to 0.011 mg/L in 2008. From 1996 to 2003, Secchi depths decreased from about 14 to 7.4 feet, before increasing to about 19 feet in 2008. Therefore, Silver Lake is typically classified as oligotrophic to mesotrophic; however, during 2002-4, the lake was classified as mesotrophic to eutrophic. Because productivity in Silver Lake is limited by phosphorus, phosphorus budgets for the lake were constructed for monitoring years 2005 and 2006. The average annual input of phosphorus was 216 pounds: 78 percent from tributary and nearshore runoff and 22 percent from atmospheric deposition. Because Silver Lake is hydraulically mounded above the local groundwater system, little or no input of phosphorus to the lake is from groundwater and septic systems. Silver Lake had previously been incorrectly described as a groundwater flowthrough lake. Phosphorus budgets were constructed for a series of dry years (low water levels) and a series of wet years (high water levels). About 6 times more phosphorus was input to the lake during wet years with high water levels than during the dry years. Phosphorus from erosion represented 13-20 percent of the phosphorus input during years with very high water levels. Results from the Canfield and Bachman eutrophication model and Carlson trophic state index equations demonstrated that water quality in Silver Lake directly responds to changes in external phosphorus input, with the percent change in chlorophyll a being about 80 percent of the percent change in total phosphorus input and the change in Secchi depth and total phosphorus concentrations being about 40 and 50 percent of the percent change in input, respectively. Therefore, changes in phosphorus input should impact water quality. Specific scenarios were simulated with the models to describe the effects of natural (climate-driven) and anthropogenic (human-induced) changes. Results of these scenarios demonstrated that several years of above-normal precipitation cause sustained high water levels and a degradation in water quality, part of which is due to erosion of the shoreline. Results also demonstrated that 1) changes in tributary and nearshore runoff have a dramatic effect on lake-water quality, 2) diverting water into the lake to increase the water level is expected to degrade the water quality, and 3) removal of water to decrease the water level of the lake is expected to have little effect on water quality. Fluctuations in water levels since 1967, when records began for the lake, are representative

Scientific Investigations Report↗

Effects of Land-Use Changes and Ground-Water Withdrawals on Stream Base Flow, Pocono Creek Watershed, Monroe County, Pennsylvania

The Pocono Creek watershed drains 46.5 square miles in eastern Monroe County, Pa. Between 2000 and 2020, the population of Monroe County is expected to increase by 70 percent, which will result in substantial changes in land-use patterns. An evaluation of the effect of reduced recharge from land-use changes and additional ground-water withdrawals on stream base flow was done by the U.S. Geological Survey (USGS) in cooperation with the U.S. Environmental Protection Agency (USEPA) and the Delaware River Basin Commission as part of the USEPA?s Framework for Sustainable Watershed Management Initiative. Two models were used. A Soil and Water Assessment Tool (SWAT) model developed by the USEPA provided areal recharge values for 2000 land use and projected full buildout land use. The USGS MODFLOW-2000 ground-water-flow model was used to estimate the effect of reduced recharge from changes in land use and additional ground-water withdrawals on stream base flow. This report describes the ground-water-flow-model simulations. The Pocono Creek watershed is underlain by sedimentary rock of Devonian age, which is overlain by a veneer of glacial deposits. All water-supply wells are cased into and derive water from the bedrock. In the ground-water-flow model, the surficial geologic units were grouped into six categories: (1) moraine deposits, (2) stratified drift, (3) lake deposits, (4) outwash, (5) swamp deposits, and (6) undifferentiated deposits. The unconsolidated surficial deposits are not used as a source of water. The ground-water and surface-water systems are well connected in the Pocono Creek watershed. Base flow measured on October 13, 2004, at 27 sites for model calibration showed that streams gained water between all sites measured except in the lower reach of Pocono Creek. The ground-water-flow model included the entire Pocono Creek watershed. Horizontally, the modeled area was divided into a 53 by 155 cell grid with 6,060 active cells. Vertically, the modeled area was discretized into four layers. Layers 1 and 2 represented the unconsolidated surficial deposits where they are present and bedrock where the surficial deposits are absent. Layer 3 represented shallow bedrock and was 200 ft (feet) thick. Layer 4 represented deep bedrock and was 300 ft thick. A total of 873 cells representing streams were assigned to layer 1. Recharge rates for model calibration were provided by the USEPA SWAT model for 2000 land-use conditions. Recharge rates for 2000 for the 29 subwatersheds in the SWAT model ranged from 6.11 to 22.66 inches per year. Because the ground-water-flow model was calibrated to base-flow data collected on October 13, 2004, the 2000 recharge rates were multiplied by 1.18 so the volume of recharge was equal to the volume of streamflow measured at the mouth of Pocono Creek. During model calibration, adjustments were made to aquifer hydraulic conductivity and streambed conductance. Simulated base flows and hydraulic heads were compared to measured base flows and hydraulic heads using the root mean squared error (RMSE) between measured and simulated values. The RMSE of the calibrated model for base flow was 4.7 cubic feet per second for 27 locations, and the RMSE for hydraulic heads for 15 locations was 35 ft. The USEPA SWAT model was used to provide areal recharge values for 2000 and full buildout land-use conditions. The change in recharge ranged from an increase of 37.8 percent to a decrease of 60.8 percent. The ground-water-flow model was used to simulate base flow for 2000 and full buildout land-use conditions using steady-state simulations. The decrease in simulated base flow ranged from 3.8 to 63 percent at the streamflow-measurement sites. Simulated base flow at streamflow-gaging station Pocono Creek above Wigwam Run near Stroudsburg, Pa. (01441495), decreased 25 percent. This is in general agreement with the SWAT model, which estimated a 30.6-percent loss in base flow at the streamflow-gaging station.

Scientific Investigations Report↗

Quantifying viruses and bacteria in wastewater—Results, interpretation methods, and quality control

Membrane bioreactors (MBR), used for wastewater treatment in Ohio and elsewhere in the United States, have pore sizes small enough to theoretically reduce concentrations of protozoa and bacteria, but not viruses. Sampling for viruses in wastewater is seldom done and not required. Instead, the bacterial indicators Escherichia coli (E. coli) and fecal coliforms are the required microbial measures of effluents for wastewater-discharge permits. Information is needed on the effectiveness of MBRs in removing human enteric viruses from wastewaters, particularly as compared to conventional wastewater treatment before and after disinfection. A total of 73 regular and 28 quality-control (QC) samples were collected at three MBR and two conventional wastewater plants in Ohio during 23 regular and 3 QC sampling trips in 2008-10. Samples were collected at various stages in the treatment processes and analyzed for bacterial indicators E. coli, fecal coliforms, and enterococci by membrane filtration; somatic and F-specific coliphage by the single agar layer (SAL) method; adenovirus, enterovirus, norovirus GI and GII, rotavirus, and hepatitis A virus by molecular methods; and viruses by cell culture. While addressing the main objective of the study-comparing removal of viruses and bacterial indicators in MBR and conventional plants-it was realized that work was needed to identify data analysis and quantification methods for interpreting enteric virus and QC data. Therefore, methods for quantifying viruses, qualifying results, and applying QC data to interpretations are described in this report. During each regular sampling trip, samples were collected (1) before conventional or MBR treatment (post-preliminary), (2) after secondary or MBR treatment (post-secondary or post-MBR), (3) after tertiary treatment (one conventional plant only), and (4) after disinfection (post-disinfection). Glass-wool fiber filtration was used to concentrate enteric viruses from large volumes, and small volume grab samples were collected for direct-plating analyses for bacterial indicators and coliphage. After filtration, the viruses were eluted from the filter and further concentrated. The final concentrated sample volume (FCSV) was used for enteric virus analysis by use of two methods-cell culture and a molecular method, polymerase chain reaction (PCR). Quantitative PCR (qPCR) for DNA viruses and quantitative reverse-transcriptase PCR (qRT-PCR) for RNA viruses were used in this study. To support data interpretations, the assay limit of detection (ALOD) was set for each virus assay and used to determine sample reporting limits (SRLs). For qPCR and qRT-PCR the ALOD was an estimated value because it was not established according to established method detection limit procedures. The SRLs were different for each sample because effective sample volumes (the volume of the original sample that was actually used in each analysis) were different for each sample. Effective sample volumes were much less than the original sample volumes because of reductions from processing steps and (or) from when dilutions were made to minimize the effects from PCR-inhibiting substances. Codes were used to further qualify the virus data and indicate the level of uncertainty associated with each measurement. Quality-control samples were used to support data interpretations. Field and laboratory blanks for bacteria, coliphage, and enteric viruses were all below detection, indicating that it was unlikely that samples were contaminated from equipment or processing procedures. The absolute value log differences (AVLDs) between concurrent replicate pairs were calculated to identify the variability associated with each measurement. For bacterial indicators and coliphage, the AVLD results indicated that concentrations <10 colony-forming units or plaque-forming units per 100 mL can differ between replicates by as much as 1 log, whereas higher concentrations can differ by as much as 0.3 log. The AVLD results for viruses indicated that differences between replicates can be as great as 1.2 log genomic copies per liter, regardless of the concentration of virus. Relatively large differences in molecular results for viruses between replicate pairs were likely due to lack of precision for samples with small effective volumes. Concentrations of E. coli, fecal coliforms, enterococci, and somatic and F-specific coliphage in post-secondary and post-tertiary samples in conventional plants were higher than those in post-MBR samples. In post-MBR and post-secondary samples, concentrations of somatic coliphage were higher than F-specific coliphage. In post-disinfection samples from two MBR plants (the third MBR plant had operational issues) and the ultraviolet conventional plant, concentrations for all bacterial indicators and coliphage were near or below detection; from the chlorine conventional plant, concentrations in post-disinfection samples were in the single or double digits. All of the plants met the National Pollutant Discharge Elimination System required effluent limits established for fecal coliforms. Norovirus GII and hepatitis A virus were not detected in any samples, and rotavirus was detected in one sample but could not be quantified. Adenovirus was found in 100 percent, enterovirus in over one-half, and norovirus GI in about one-half of post-preliminary wastewater samples. Adenovirus and enterovirus were detected throughout the treatment processes, and norovirus GI was detected less often than the other two enteric viruses. Culturable viruses were detected in post-preliminary samples and in only two post-treatment samples from the plant with operational issues.

Scientific Investigations Report↗

Trends in Streamflow and Nutrient and Suspended-Sediment Concentrations and Loads in the Upper Mississippi, Ohio, Red, and Great Lakes River Basins, 1975-2004

Many actions have been taken to reduce nutrient and suspended-sediment concentrations and the amount of nutrients and sediment transported in streams as a result of the Clean Water Act and subsequent regulations. This report assesses how nutrient and suspended-sediment concentrations and loads in selected streams have changed during recent years to determine if these actions have been successful. Flow-adjusted and overall trends in concentrations and trends in loads from 1993 to 2004 were computed for total nitrogen, dissolved ammonia, total organic nitrogen plus ammonia, dissolved nitrite plus nitrate, total phosphorus, dissolved phosphorus, total suspended material (total suspended solids or suspended sediment), and total suspended sediment for 49 sites in the Upper Mississippi, Ohio, Red, and Great Lakes Basins. Changes in total nitrogen, total phosphorus, and total suspended-material loads were examined from 1975 to 2003 at six sites to provide a longer term context for the data examined from 1993 to 2004. Flow-adjusted trends in total nitrogen concentrations at 19 of 24 sites showed tendency toward increasing concentrations, and overall trends in total nitrogen concentrations at 16 of the 24 sites showed a general tendency toward increasing concentrations. The trends in these flow-adjusted total nitrogen concentrations are related to the changes in fertilizer nitrogen applications. Flow-adjusted trends in dissolved ammonia concentrations from 1993 to 2004 showed a widespread tendency toward decreasing concentrations. The widespread, downward trends in dissolved ammonia concentrations indicate that some of the ammonia reduction goals of the Clean Water Act are being met. Flow-adjusted and overall trends in total organic plus ammonia nitrogen concentrations from 1993 to 2004 did not show a distinct spatial pattern. Flow-adjusted and overall trends in dissolved nitrite plus nitrate concentrations from 1993 to 2004 also did not show a distinct spatial pattern. Flow-adjusted trends in total phosphorus concentrations were upward at 24 of 40 sites. Overall trends in total phosphorus concentrations were mixed and showed no spatial pattern. Flow-adjusted and overall trends in dissolved phosphorus concentrations were consistently downward at all of the sites in the eastern part of the basins studied. The reduction in phosphorus fertilizer use and manure production east of the Mississippi River could explain most of the observed trends in dissolved phosphorus. Flow-adjusted trends in total suspended-material concentrations showed distinct spatial patterns of increasing tendencies throughout the western part of the basins studied and in Illinois and decreasing concentrations throughout most of Wisconsin, Iowa, and in the eastern part of the basins studied. Flow-adjusted trends in total phosphorus were strongly related to the flow-adjusted trends in suspended materials. The trends in the flow-adjusted suspended-sediment concentrations from 1993 to 2004 resembled those for suspended materials. The long-term, nonmonotonic trends in total nitrogen, total phosphorus, and suspended-material loads for 1975 to 2003 were described by local regression, LOESS, smoothing for six sites. The statistical significance of those trends cannot be determined; however, the long-term changes found for annual streamflow and load data indicate that the monotonic trends from 1993 to 2004 should not be extrapolated backward in time.

Scientific Investigations Report↗

Assessment of surface-water quantity and quality, Eagle River watershed, Colorado, 1947-2007

From the early mining days to the current tourism-based economy, the Eagle River watershed (ERW) in central Colorado has undergone a sequence of land-use changes that has affected the hydrology, habitat, and water quality of the area. In 2000, the USGS, in cooperation with the Colorado River Water Conservation District, Eagle County, Eagle River Water and Sanitation District, Upper Eagle Regional Water Authority, Colorado Department of Transportation, City of Aurora, Town of Eagle, Town of Gypsum, Town of Minturn, Town of Vail, Vail Resorts, City of Colorado Springs, Colorado Springs Utilities, and Denver Water, initiated a retrospective analysis of surface-water quantity and quality in the ERW. Surface-water quantity data and surface-water quality data were obtained from local, State, and Federal agencies to assist in the analysis of surface-water conditions in the ERW 1947-2007. Surface-water-quality data from 293 sites and 12 different source agencies were compiled into 192 unique sites located on streams and rivers in the ERW. Approximately 39 percent of the unique sites had fewer than 5 samples; while 23 percent of the sites had more than 100 samples. Physical properties were the most abundant type of samples collected, with major ions, nutrients, and trace elements also commonly collected. For selected water-quality properties and constituents in the watershed, this report: (1) characterizes available water quantity and water-quality data, (2) identifies spatial and seasonal variability in water quantity and water quality, (3) provides comparisons to Federal and State water-quality standards or recommendations, (4) characterizes temporal changes in water quality, and (5) where possible, identifies potential causes of these changes. This report provides reconnaissance-level statistical summaries and comparisons of water-quality conditions and characteristics using available data within the ERW. The report also includes streamflow statistics such as: mean annual runoff totals, peak-flood-frequency recurrence intervals, and minimum 7-day mean streamflows for selected sites within the watershed. The spatial patterns for concentrations of trace metals (aluminum, cadmium, copper, iron, manganese, and zinc) indicate an increase in dissolved concentrations of these metals near historical mining areas in the Eagle River and several tributaries near Belden. In general, concentrations decrease downstream from mining areas. Concentrations typically are near or below reporting limits in Gore Creek and other tributaries within the watershed. Concentrations for trace elements (arsenic, selenium, and uranium) in the watershed usually are below the reporting limit, and no prevailing spatial patterns were observed in the data. Step-trend analysis and temporal-trend analysis provide evidence that remediation of historical mining areas in the upper Eagle River have led to observed decreases in metals concentrations in many surface-waters. Comparison of pre- and post-remediation concentrations for many metals indicates significant decreases in metals concentrations for cadmium, manganese, and zinc at sites downstream from the Eagle Mine Superfund Site. Some sites show order of magnitude reductions in median concentrations between these two periods. Evaluation of monotonic trends for dissolved metals concentrations show downward trends at numerous sites in, and downstream from, historic mining areas. The spatial pattern of nutrients shows lower concentrations on many tributaries and on the Eagle River upstream from Red Cliff with increases in nutrients downstream of major urban areas. Seasonal variations show that for many nutrient species, concentrations tend to be lowest May-June and highest January-March. The gradual changes in concentrations between seasons may be related to dilution effects from increases and decreases in streamflow. Upward trends in nutrients between the towns of Gypsum and Avon were detected for nitrate, orthophosphate, and total phosphorus. An upward trend in nitrite was detected in Gore Creek. No trends were detected in un-ionized ammonia within the ERW. Exceedances of State water-quality standards (nitrite, nitrate, and un-ionized ammonia) and levels higher than U.S. Environmental Protection Agency recommendations (total phosphorus) occur in several areas within the ERW. The majority of the exceedances are from comparisons to the U.S. Environmental Protection Agency total phosphorus recommendations. A positive correlation was observed between suspended sediment and total phosphorus. An upward trend in total dissolved solids in Gore Creek may be the result of increases in chloride salts. Highly significant trends were detected in sodium, potassium, and chloride with a significant upward trend in magnesium and a weakly significant upward trend in calcium. A quantitative analysis of the relative abundance of calcium, magnesium, sodium, and potassium to the available anions suggests that chloride salts likely are the source for the detected upward trends because chloride is the only commonly occurring anion with a trend in Gore Greek. A potential source for the observed chloride salts may be the chemical anti-icing and deicing products used during winter road maintenance in municipal areas and on Interstate-70. A downward trend in dissolved solids in the Eagle River between Gypsum and Avon may be contributing to the detected trend on the Eagle River at Gypsum. Significant downward trends were detected in specific ions such as calcium, magnesium, sulfate, and silica. Measures of total dissolved solids as well as comparisons to specific ions show that in water-quality samples within the ERW concentrations generally are lower in the headwaters, with increases downstream from Wolcott. Differences in concentrations likely result from increased abundance of salt-bearing geologic units downstream from Avon. Few sites had measured concentrations that exceeded the State standards for chloride.

Scientific Investigations Report↗

Hydrogeology, water quality, and water-supply potential of the Lower Floridan Aquifer, coastal Georgia, 1999-2002

The hydrogeology and water quality of the upper permeable and Fernandina permeable zones of the Lower Floridan aquifer were studied at seven sites in the 24-county study area encompassed by the Georgia Coastal Sound Science Initiative. Although substantially less than the Upper Floridan aquifer in coastal Georgia, transmissivities for the Lower Floridan aquifer are in the same range as other water-supply aquifers in Georgia and South Carolina and could meet the needs of public drinking-water supply. Water of the upper permeable zone of the Lower Floridan aquifer exceeds the Federal secondary drinking-water standards for sulfate and total dissolved solids at most coastal Georgia sites and the Federal secondary drinking-water standard for chloride at the Shellman Bluff site. The top of the Lower Floridan aquifer correlates within 50 feet of the previously reported top, except at the St Simons Island site where the top is more than 80 feet higher. Based on the hydrogeologic characteristics, the seven sites are divided into the northern sites at Shellman Bluff, Richmond Hill, Pembroke, and Pineora; and southern sites at St Marys, Brunswick, and St Simons Island. At the northern sites, the Lower Floridan aquifer does not include the Fernandina permeable zone, is thinner than the overlying Upper Floridan aquifer, and consists of only strata of the middle Eocene Avon Park Formation. Transmissivities in the Lower Floridan aquifer are 8,300 feet squared per day at Richmond Hill and 6,000 feet squared per day at Shellman Bluff, generally one tenth the transmissivity of the Upper Floridan aquifer at these sites. At the southern sites, the upper permeable zone of the Lower Floridan aquifer is thicker than the Upper Floridan aquifer and consists of porous limestone and dolomite interbedded with nonporous strata of the middle Eocene Avon Park and early Eocene Oldsmar Formations. Transmissivities for the upper permeable zone of the Lower Floridan aquifer are 500 feet squared per day at the St Simons Island site and 13,000 feet squared per day at the St Marys site. The Lower Floridan aquifer at the Brunswick and St Marys sites includes the Fernandina permeable zone, which consists of saltwater-bearing dolomite. Hydrographs of Coastal Sound Science Initiative wells and other nearby wells open to the Upper Floridan aquifer, and the upper permeable and Fernandina permeable zones of the Lower Floridan aquifer have similar trends. Water levels in wells open to the Upper and Lower Floridan aquifers are below land surface at the northern sites and the St Simons Island site, and above land surface at the Brunswick and St Marys sites, as of January 1, 2004. Freshwater is present in the Lower Floridan aquifer at Pineora, Pembroke, and St Marys, and from 1,259 to 1,648 feet below land surface at Brunswick. Slightly saline water is present in the Lower Floridan aquifer at Richmond Hill, Shellman Bluff, St Simons Island, and from 1,679 to 1,970 feet below land surface in well 34H495 at Brunswick. The upper permeable zone of the Lower Floridan aquifer contains bicarbonate water at the Pembroke site, sulfate-bicarbonate water at the Brunswick site, and sulfate water at the St Simons Island, Shellman Bluff, St Marys, and Richmond Hill sites. The bicarbonate, sulfate-bicarbonate, and sulfate waters are saturated relative to calcite and dolomite, and undersaturated with gypsum and anhydrite. The Fernandina permeable zone in well 34H495 includes moderately saline water, very saline water, and brine. The Fernandina permeable zone of the Lower Floridan aquifer beneath downtown Brunswick contains chloride water that is slightly undersaturated to saturated with gypsum and anhydrite. Concentrations of total dissolved solids, sulfate, and chloride exceeded the Federal secondary drinking-water standards. The chloride-contaminated plumes beneath downtown Brunswick would require at least a 12- to 20-percent contribution of very saline water from the Fernandi

Georgia↗

Hydrologic and water-quality characteristics for Bear Creek near Silver Hill, Arkansas, and selected Buffalo River sites, 1999-2004

The purpose of this report is to describe and compare the hydrologic and water-quality characteristics of Bear Creek near Silver Hill, Arkansas, to two sites on the Buffalo River upstream from the confluence of Bear Creek, to a site on Calf Creek, a smaller tributary to the Buffalo River, to selected undeveloped sites across the Nation, and to a developed site in Arkansas. A better understanding of the hydrology and water quality of Bear Creek is of interest to many, including the National Park Service, which administers the Buffalo National River, to evaluate its effects on the hydrology and water quality of the Buffalo River. The streamflow at Bear Creek near Silver Hill varied seasonally and annually from January 1999 to March 2004. The mean annual streamflow at Bear Creek for calendar years 1999 to 2003 was 86.0 cubic feet per second. The highest annual mean streamflow occurred in 2002 (158 cubic feet per second) and the lowest annual mean streamflow occurred in 1999 (56.4 cubic feet per second). The mean annual streamflow for calendar years 1999 to 2003 at the Buffalo River near Boxley and Buffalo River near St. Joe was 102 and 881 cubic feet per second, respectively. Concentrations of nitrogen measured for Bear Creek generally were greater than concentrations measured at the two Buffalo River sites and were similar to concentrations measured at Calf Creek. Concentrations of phosphorus measured at Bear Creek generally were greater than concentrations measured at the two Buffalo River sites and were similar to concentrations measured at Calf Creek. Fecal indicator bacteria concentrations generally were greater at Bear Creek than concentrations measured at the Buffalo River and similar to concentrations at Calf Creek. Bear Creek had significantly greater suspended-sediment concentrations than the Buffalo River near Boxley and the Buffalo River near St. Joe and similar concentrations to Calf Creek. Nutrients, dissolved organic carbon, and suspended-sediment loads at Bear Creek and two Buffalo River sites varied because of differences in land use and contributing drainage area for each site. In general, the Buffalo River near St. Joe had the greatest annual loads of nutrients, dissolved organic carbon, and suspended sediment. The Buffalo River near Boxley had the least annual nutrient and suspended-sediment loads amongthe three sites. Buffalo River near Boxley had lesser annual loads than the other two sites probably because of the higher percentage of forested land in the basin and smaller contributing drainage area. Mean annual nutrient, dissolved organic carbon, and suspended- sediment yields computed for Bear Creek were greater than yields computed for both of the Buffalo River sites. Bear Creek had greater median annual nutrient yields than selected undeveloped basins across the Nation and less median annual nutrient yields than the Illinois River south of Siloam Springs, Arkansas, which is representative of a developed basin. Bear Creek had greater median annual flow-weighted nutrient concentrations than the Buffalo River near St. Joe, the Buffalo River near Boxley, and selected undeveloped sites across the Nation. Bear Creek had less median flow-weighted nutrient concentrations than the Illinois River.

Scientific Investigations Report↗

Geochemical characterization of water, sediment, and biota affected by mercury contamination and acidic drainage from historical gold mining, Greenhorn Creek, Nevada County, California, 1999-2001

In 1999, the U.S. Geological Survey (USGS) initiated studies of mercury and methylmercury occurrence, transformation, and transport in the Bear River and Yuba River watersheds of the northwestern Sierra Nevada. Because these watersheds were affected by large-scale, historical gold extraction using mercury amalgamation beginning in the 1850s, they were selected for a pilot study of mercury transport by the USGS and other cooperating agencies. This report presents data on methylmercury (MeHg) and total mercury (THg) concentrations in water, bed sediment, invertebrates, and frogs collected at 40 stations during 1999-2001 in the Greenhorn Creek drainage, a major tributary to Bear River. Results document several mercury contamination “hot spots” that represent potential targets for ongoing and future remediation efforts at abandoned mine sites in the study area. Water-quality samples were collected one or more times at each of 29 stations. The concentrations of total mercury in 45 unfiltered water samples ranged from 0.80 to 153,000 nanograms per liter (ng/L); the median was 9.6 ng/L. Total mercury concentrations in filtered water (41 samples) ranged from less than 0.3 to 8,000 ng/L; the median was 2.7 ng/L. Concentrations of methylmercury in the unfiltered water (40 samples) ranged from less than 0.04 to 9.1 ng/L; the median was 0.07 ng/L. Methylmercury in filtered water (13 samples) ranged from less than 0.04 to 0.27 ng/L; the median was 0.04 ng/L. Acidic drainage with pH values as low as 3.4 was encountered in some of the mined areas. Elevated concentrations of aluminum, cadmium, copper, iron, manganese, nickel, and zinc were found at several stations, especially in the more acidic water samples. Total mercury concentrations in sediment were determined by laboratory and field methods. Total mercury concentrations (determined by laboratory methods) in ten samples from eight stations ranged from about 0.0044 to 12 µg/g (microgram per gram, equivalent to parts per million). Methylmercury concentrations in these samples ranged from less than 0.00011 to 0.0095 µg/g. A field panning method was used to determine the concentration of liquid elemental mercury in 22 samples from 14 stations. Measured quantities of elemental mercury recovered by panning ranged from a trace amount estimated at 100 milligrams per kilogram (equivalent to parts per million) to 45,000 milligrams per kilogram (equivalent to 4.5 per cent, by weight). In total, 194 invertebrate samples were collected at 31 stations; 78 of the samples were analyzed for concentrations of THg and MeHg and used to calculate MeHg to THg ratios. A total of 69 frog samples were collected at 19 stations, and all were analyzed only for THg. Ranges of MeHg concentrations (µg/g, wet weight) in invertebrate samples and number of samples (n) were 0.0012-0.048 for banana slugs (Arionidae, n = 27), 0.027-0.39 for dobsonflies (Corydalidae, n = 14), 0.029-0.50 for predaceous diving beetles (Dytiscidae, n = 31), 0.026-0.52 for predaceous stoneflies (Perlidae, n = 18), 0.011-1.6 for dragonflies (Odonata, n = 46), and 0.061-0.55 for water striders (Gerridae, n = 56). The ratio of MeHg to THg in invertebrates was greater than 50 percent for 74 of 78 samples. The data from this reconnaissance sampling effort have been used by land-management agencies in selecting abandoned mine sites for remediation. The Forest Service has remediated the Sailor Flat site, and the Bureau of Land Management has initiated plans to remediate the Boston Mine drainage tunnel.

California↗