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Increasing chloride in rivers of the conterminous U.S. and linkages to potential corrosivity and lead action level exceedances in drinking water

Corrosion in water-distribution systems is a costly problem and controlling corrosion is a primary focus of efforts to reduce lead (Pb) and copper (Cu) in tap water. High chloride concentrations can increase the tendency of water to cause corrosion in distribution systems. The effects of chloride are also expressed in several indices commonly used to describe the potential corrosivity of water, the chloride-sulfate mass ratio (CSMR) and the Larson Ratio (LR). Elevated CSMR has been linked to the galvanic corrosion of Pb whereas LR is indicative of the corrosivity of water to iron and steel. Despite the known importance of chloride, CSMR, and LR to the potential corrosivity of water, monitoring of seasonal and interannual changes in these parameters is not common among water purveyors. We analyzed long-term trends (1992–2012) and the current status (2010–2015) of chloride, CSMR, and LR in order to investigate the short and long-term temporal variability in potential corrosivity of US streams and rivers. Among all sites in the trend analyses, chloride, CSMR, and LR increased slightly, with median changes of 0.9 mg L − 1 , 0.08, and 0.01, respectively. However, urban-dominated sites had much larger increases, 46.9 mg L − 1 , 2.50, and 0.53, respectively. Median CSMR and LR in urban streams (4.01 and 1.34, respectively) greatly exceeded thresholds found to cause corrosion in water distribution systems (0.5 and 0.3, respectively). Urbanization was strongly correlated with elevated chloride, CSMR, and LR, especially in the most snow-affected areas in the study, which are most likely to use road salt. The probability of Pb action-level exceedances (ALEs) in drinking water facilities increased along with raw surface water CSMR, indicating a statistical connection between surface water chemistry and corrosion in drinking water facilities. Optimal corrosion controlwill require monitoring of critical constituents reflecting the potential corrosivity in surface waters.

Science of the Total Environment

Microbial sulfate reduction and metal attenuation in pH 4 acid mine water

Sediments recovered from the flooded mine workings of the Penn Mine, a Cu-Zn mine abandoned since the early 1960s, were cultured for anaerobic bacteria over a range of pH (4.0 to 7.5). The molecular biology of sediments and cultures was studied to determine whether sulfate-reducing bacteria (SRB) were active in moderately acidic conditions present in the underground mine workings. Here we document multiple, independent analyses and show evidence that sulfate reduction and associated metal attenuation are occurring in the pH-4 mine environment. Water-chemistry analyses of the mine water reveal: (1) preferential complexation and precipitation by H2S of Cu and Cd, relative to Zn; (2) stable isotope ratios of 34S/32S and 18O/16O in dissolved SO4 that are 2-3 ??? heavier in the mine water, relative to those in surface waters; (3) reduction/oxidation conditions and dissolved gas concentrations consistent with conditions to support anaerobic processes such as sulfate reduction. Scanning electron microscope (SEM) analyses of sediment show 1.5-micrometer, spherical ZnS precipitates. Phospholipid fatty acid (PLFA) and denaturing gradient gel electrophoresis (DGGE) analyses of Penn Mine sediment show a high biomass level with a moderately diverse community structure composed primarily of iron- and sulfate-reducing bacteria. Cultures of sediment from the mine produced dissolved sulfide at pH values near 7 and near 4, forming precipitates of either iron sulfide or elemental sulfur. DGGE coupled with sequence and phylogenetic analysis of 16S rDNA gene segments showed populations of Desulfosporosinus and Desulfitobacterium in Penn Mine sediment and laboratory cultures. ?? 2007 Church et al; licensee BioMed Central Ltd.

Geochemical Transactions

Hydrogeologic factors in the selection of shallow land burial sites for the disposal of low-level radioactive waste

In the United States, low-level radioactive waste is disposed of by shallow land burial. Commercial low-level radioactive waste has been buried at six sites, and low-level radioactive waste generated by the Federal Government has been buried at nine major and several minor sites. Several existing low-level radioactive waste sites have not provided expected protection of the environment. These shortcomings are related, at least in part, to an inadequate understanding of site hydrogeology at the time the sites were selected. To better understand the natural systems and the effect of hydrogeologic factors on long-term site performance, the U.S. Geological Survey has conducted investigations at five of the six commercial low-level radioactive waste sites and at three Federal sites. These studies, combined with those of other Federal and State agencies, have identified and confirmed important hydrogeologic factors in the effective disposal of low-level radioactive waste by shallow land burial. These factors include precipitation, surface drainage, topography, site stability, geology, thickness of the host soil-rock horizon, soil and sediment permeability, soil and water chemistry, and depth to the water table.

Circular

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

Ground-water quality in the approximately 3,000 square-mile Kern County Subbasin study unit (KERN) was investigated from January to March, 2006, as part of the Priority Basin Assessment Project of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA Priority Basin Assessment project was developed in response to the Groundwater Quality Monitoring Act of 2001, and is being conducted by the California State Water Resources Control Board (SWRCB) in collaboration with the U.S. Geological Survey (USGS) and the Lawrence Livermore National Laboratory (LLNL). The Kern County Subbasin study was designed to provide a spatially unbiased assessment of raw (untreated) ground-water quality within KERN, as well as a statistically consistent basis for comparing water quality throughout California. Samples were collected from 50 wells within the San Joaquin Valley portion of Kern County. Forty-seven of the wells were selected using a randomized grid-based method to provide a statistical representation of the ground-water resources within the study unit. Three additional wells were sampled to aid in the evaluation of changes in water chemistry along regional ground-water flow paths. The ground-water samples were analyzed for a large number of man-made organic constituents (volatile organic compounds [VOCs], pesticides, and pesticide degradates), constituents of special interest (perchlorate, N-nitrosodimethylamine [NDMA], and 1,2,3-trichloropropane [1,2,3-TCP]), naturally occurring inorganic constituents (nutrients, major and minor ions, and trace elements), radioactive constituents, and microbial indicators. Naturally occurring isotopes (tritium, carbon-14, and stable isotopes of hydrogen, oxygen, nitrogen, and carbon) and dissolved noble gases also were measured to help identify the source and age of the sampled ground water. Quality-control samples (blanks, replicates, and laboratory matrix spikes) were collected and analyzed at approximately 10 percent of the wells, and the results for these samples were used to evaluate the quality of the data from the ground-water samples. Assessment of the quality-control information resulted in censoring of less than 0.4 percent of the data collected for ground-water samples. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, raw ground water typically is treated, disinfected, or blended with other waters to maintain acceptable water quality. Regulatory thresholds apply, not to the raw ground water, but to treated water that is served to the consumer. However, to provide some context for the results, concentrations of constituents measured in the raw ground water were compared with health-based thresholds established by the U.S. Environmental Protection Agency (USEPA) and the California Department of Public Health (CDPH), and as well as with thresholds established for aesthetic concerns (secondary maximum contaminant levels, SMCL-CA) by CDPH. VOCs and pesticides each were detected in approximately 60 percent of the grid wells, and detections of all compounds but one were below health-based thresholds. The fumigant, 1,2-dibromo-3-chloropropane (DBCP), was detected above the USEPA maximum contaminant level (MCL-US) in one sample. Detections of most inorganic constituents were also below health-based thresholds. Constituents detected above health-based thresholds include: nitrate, (MCL-US, 2 samples), arsenic (MCL-US, 2 samples), and vanadium (California notification level, NL-CA, 1 sample). All detections of radioactive constituents were below health-based thresholds, although nine samples had activities of radon-222 above the lower proposed MCL-US. Most of the samples from KERN wells had concentrations of major elements, total dissolved solids, and trace elements below the non-enforceable thresholds set for aesthetic concerns.

California

Ground-Water Quality Data in the Coachella Valley Study Unit, 2007: Results from the California GAMA Program

Ground-water quality in the approximately 820 square-mile Coachella Valley Study Unit (COA) was investigated during February and March 2007 as part of the Priority Basin Project of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA Priority Basin Project was developed in response to the Groundwater Quality Monitoring Act of 2001, and is being conducted by the U.S. Geological Survey (USGS) in cooperation with the California State Water Resources Control Board (SWRCB). The study was designed to provide a spatially unbiased assessment of raw ground water used for public-water supplies within the Coachella Valley, and to facilitate statistically consistent comparisons of ground-water quality throughout California. Samples were collected from 35 wells in Riverside County. Nineteen of the wells were selected using a spatially distributed, randomized grid-based method to provide statistical representation of the study unit (grid wells). Sixteen additional wells were sampled to evaluate changes in water chemistry along selected ground-water flow paths, examine land use effects on ground-water quality, and to collect water-quality data in areas where little exists. These wells were referred to as 'understanding wells'. The ground-water samples were analyzed for a large number of organic constituents (volatile organic compounds [VOC], pesticides and pesticide degradates, pharmaceutical compounds, and potential wastewater-indicator compounds), constituents of special interest (perchlorate and 1,2,3-trichloropropane [1,2,3-TCP]), naturally occurring inorganic constituents (nutrients, major and minor ions, and trace elements), radioactive constituents, and microbial indicators. Naturally occurring isotopes (uranium, tritium, carbon-14, and stable isotopes of hydrogen, oxygen, and boron), and dissolved noble gases (the last in collaboration with Lawrence Livermore National Laboratory) also were measured to help identify the source and age of the sampled ground water. A quality-control sample (blank, replicate, or matrix spike) was collected at approximately one quarter of the wells, and the results for these samples were used to evaluate the quality of the data for the ground-water samples. Assessment of the quality-control information resulted in V-coding less than 0.1 percent of the data collected. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, water typically is treated, disinfected, and (or) blended with other waters to maintain acceptable water quality. Regulatory thresholds apply to treated water that is supplied to the consumer, not to raw ground water. However, to provide some context for the results, concentrations of constituents measured in the raw ground water were compared with health-based thresholds established by the U.S. Environmental Protection Agency (USEPA) and the California Department of Public Health (CDPH) and thresholds established for aesthetic purposes (secondary maximum contaminant levels, SMCL-CA) by CDPH. Most constituents detected in ground-water samples were at concentrations below drinking-water thresholds. Volatile organic compounds, pesticides, and pesticide degradates were detected in less than one-third of the grid well samples collected. All VOC and pesticide concentrations measured were below health-based thresholds. Potential waste-water indicators were detected in less than half of the wells sampled, and no detections were above health-based thresholds. Perchlorate was detected in seven grid wells; concentrations from two wells were above the CDPH maximum contaminant level (MCL-CA). Most detections of trace elements in samples collected from COA Study Unit wells were below water-quality thresholds. Exceptions include five samples of arsenic that were above the USEPA maximum contaminant level (MCL-US), two detections of boron above the CDPH notification level (NL-CA), and two detections of mol

Data Series

Hydrogeologic data from a test well in east-central Duval County, Florida

A 2,112-foot test well was drilled in east-central Duval County, Florida, to obtain geologic, hydrologic, and water chemistry data. Drill cuttings and water samples were collected, and water-level measurements and lithologic and geophysical logs were made. Deposits to a depth of 575 feet consist of sand, clayey sand, phosphatic sandy clay, coquina, sandy limestone, and dolostone. Below 575 feet, the deposits consist of fragmented and granular limestone, dolomitic limestone, and massive to finely crystalline dolostone, which comprise the Floridan aquifer system in the area. Water levels were measured near or at the bottom of the drill hole through the drill stem and in the annular space between the drilled hole and drill stem at the well head as drilling progressed from 770 to 2,112 feet in depth. Water levels measured through the drill stem ranged from 1.17 feet above land surface at a depth of 2,107 feet to 15.0 feet above land surface at a depth of 1,574 feet. Water levels measured in the annular space ranged from 7.5 feet above land surface at a depth of 770 feet to 14.9 feet at various depths from 1,574 to 1,721 feet. Chloride concentrations of water sampled through the drill stem from a depth of 711 to 1 ,616 feet ranged from 22 to 150 milligrams per liter at 1,648 feet. Chloride concentrations then ranged from 345 to about 800 milligrams per liter to a depth of 2,071 feet and then increased to a maximum of 5,450 milligrams per liter at 2,107 feet. (USGS)

Open-File Report

Integrated investigations of environmental effects of historical mining in the Basin and Boulder Mining Districts, Boulder River watershed, Jefferson County, Montana

The Boulder River watershed is one of many watersheds in the western United States where historical mining has left a legacy of acid mine drainage and elevated concentrations of potentially toxic trace elements. Abandoned mine lands commonly are located on or affect Federal land. Cleaning up these Federal lands will require substantial investment of resources. As part of a cooperative effort with Federal land-management agencies, the U.S. Geological Survey implemented an Abandoned Mine Lands Initiative in 1997. The goal of the initiative was to use the watershed approach to develop a strategy for gathering and communicating the scientific information needed to formulate effective and cost-efficient remediation of affected lands in a watershed. The watershed approach is based on the premise that contaminated sites that have the most profound effect on water and ecosystem quality within an entire watershed should be identified, characterized, and ranked for remediation. The watershed approach provides an effective means to evaluate the overall status of affected resources and helps to focus remediation at sites where the most benefit will be gained in the watershed. Such a large-scale approach can result in the collection of extensive information on the geology and geochemistry of rocks and sediment, the hydrology and water chemistry of streams and ground water, and the diversity and health of aquatic and terrestrial organisms. During the assessment of the Boulder River watershed, we inventoried historical mines, defined geological conditions, assessed fish habitat, collected and chemically analyzed hundreds of water and sediment samples, conducted toxicity tests, analyzed fish tissue and indicators of physiological malfunction, examined invertebrates and biofilm, and defined hydrological regimes. Land- and resource-management agencies are faced with evaluating risks associated with thousands of potentially harmful mine sites, and this level of effort is not always feasible for every affected watershed. The detailed work described in this report can help Federal land-management agencies decide which characterization efforts would be most useful in characterization of other affected watersheds.

Montana

Reconnaissance of ground-water quality in the North Platte Natural Resources District, western Nebraska, June-July 1991

One-hundred twenty wells completed in unconfined Quaternary alluvial, Ogallala, Arikaree, Brule fractured, sand and confined Chadron and undifferentiated Cretaceous water-bearing units were sampled in June and July 1991 to characterize the quality of ground water in the study area. More than 75 percent of the water samples had nitrate and nitrite as nitrogen concentrations equal to or less than 6.0 milligrams per liter. Samples from six wells completed in Quaternary alluvial and Brule fractured water-bearing units exceeded the U.S. Environmental Protection Agency Maximum Contaminant Level of 10 milligrams per liter nitrate and nitrite as nitrogen. Water from several wells completed in Quaternary alluvial and the Brule water-bearing units had detectable concentrations of alachlor, atrazine, deethylatrazine, or prometon. Major element concentrations in water from 44 wells indicated that the water-bearing units had distinct chemistry. Water from unconfined water- bearing units generally was a calcium bicarbonate type and water from the confined water-bearing units generally was a sodium bicarbonate type. Measurements of pH and concentrations of dissolved solids, sulfate, chloride, fluoride, arsenic, beryllium, manganese, adjusted gross alpha activities, radon, and uranium in ground water exceeded final or proposed U.S. Environmental Protection Agency Maximum Contaminant Levels or Secondary Maximum Contaminant Levels.

Water-Resources Investigations Report

Flow and geochemistry along shallow ground-water flowpaths in an agricultural area in southeastern Wisconsin

Water-quality and geohydrologic data were collected from 19 monitor wells and a stream in an agricultural area in southeastern Wisconsin. These sites were located along a 2,700-ft transect from a local ground-water high to the stream. The transect is approximately parallel to the horizontal direction of ground-water flow at the water table. Most of the wells were installed in unconsolidated deposits at five locations along the transect and include an upgradient well nest, a midgradient well nest, a downgradient well nest, wells in the lowland area near the stream, and wells installed in the stream bottom. The data collected from this study site were used to describe the water quality and geohydrology of the area and to explain and model the variations in water chemistry along selected ground-water flowpaths. Water samples from most wells and the stream were analyzed for major ions, nutrients, pesticides, dissolved organic carbon, aluminum, tritium, CFCs, 15N, 18O, and dissolved gases. Measurements of temperature, pH, specific conductance, and dissolved oxygen were made in the field. Concentrations of all dissolved constituents were below Wisconsin ground-water quality enforcement standards. The concentrations of both nitrate and ammonium in precipitation concentrated by evapotranspiration are roughly equal to the concentrations of either in the shallow ground waters. The nitrogen and oxygen isotope data, however, indicate that soil ammonium, ammonium fertilizer, and animal waste are possible nitrate sources. Concentrated precipitation can also supply dissolved sulfate to the shallow ground waters and may be a principal source of pesticides to the ground water. However, some input of dissolved chloride to the ground water from mineral or anthropogenic sources is necessary. X-ray diffraction analyses of samples from 2 cores show the most abundant mineral to be dolomite, with subordinate quartz, microclme, and plagioclase, and minor amounts of mica, hornblende, and chlorite. Hydraulic conductivities determined from slug tests at selected wells range from 0.006 to 55 feet per day, with most values between 0.4 and 12 feet per day. A cross-sectional ground-water flow model, representing the water-table flow system, was developed for the site and was used to identify possible ground-water flowpaths for geocli^mical modeling. The model was calibrated against measured water levels and was most sensitive to variation in recharge and hydraulic conductivity. The calibrated model shows that downward flow from shallow to deeper wells within a nest may occur at the upgradient and midgradient well nests, but that flow from each well nest travels beneath downgradient nests to the stream. Pathline and travel-time analysis performed on the calibrated flow-model output yielded travel times to well screens that range from 5.8 to 59 years with a recharge of 4 inches per yr. Recharge dates based on tritium and CFC concentrations range from pre-1955 to 1986 and are consistent with flowpaths1 and travel times in the calibrated flow model. Changes in water quality along ground-water flowpaths were evaluated using the geochemical model PHREEQC. Geochemical mole balance models of shallow ground-water formation show that the principal reaction, by an order of magnitude, is dissolution of dolomite with CO2 . Concentration factors in the mole-balance models range from 1 to 11, with most values between 5 and 10, which provides independent support for the concentration factor of 8 based on recharge estimates used in the flow model. Ground water recharging at mid- and downgradient wells is oxic and contains dissolved nitrate, whereas the ground water discharging to the stream is anoxic and contains dissolved ammonium. Redox environments were defined at each well on the basis of relative concentrations of various dissolved redox-active species. Chemically permissible flowpaths inferred from the observed sequence of redox environments at well sites are consistent with flowpaths in the ground-water flow model. The transition from nitrate in recharging ground water to ammonium in ground water discharging to the stream suggests the possibility of nitrate reduction along the flowpath. None of the techniques employed in this study, however, were able to prove the occurrence of this reaction.

Michigan, Wisconsin

Uptake and transport of heavy metals by heated seawater: A summary of the experimental results

In general, the chemistry of seawater experimentally reacted with basalt is in accord with the observed chemistry of the 350°C vent waters from 21°N on the East Pacific Rise. Experiments at 350°C, 500 bar, and a water/rock ratio of ≤10 reproduce most of the major components in the vent waters, in particular the low Mg and SO 4 and high Si0 2 , Ca, and K. In comparison with the vent waters however the experimental fluids are deficient in H + and heavy metals. Experiments with natural and evolved seawater (Mg and SO 4 depleted) at ≥400 C and 500 bars or 375°C and ~375 bars under rock-dominated conditions more closely reproduce the vent-water chemistry.

Book chapter

Water volumes, heat flow, and solute discharge from Old Faithful Geyser eruptions, Yellowstone National Park, USA

The iconic Old Faithful Geyser in Yellowstone National Park, USA, has attracted a significant amount of research because of the relative regularity and impressive size of its eruptions. Numerous studies have included observations, measurements, and analyses that informed models of geyser eruptions. However, fundamental quantities, including the associated mass and heat discharged, remain poorly constrained. In April 2025 we measured the volume of water from 45 Old Faithful Geyser eruptions using a portable flume in an outflow channel and specific conductance measurements in the Firehole River. We used high-speed video to perform velocimetry, measured changes in water chemistry to calculate the volume of water evaporated along the outflow channels, and used thermodynamic calculations to estimate the volume of water erupted as steam and to quantify the geyser's heat output. The calculated average volume of water discharged by Old Faithful Geyser in each eruption is 27.9 ± 9.4 m 3 , with no relation between eruption volume and the length of the preceding eruption interval. Video analysis of the eruption's liquid-dominated phase yields similar volumes of 21–30 m 3 . The calculated heat flow from the geyser is 2.2–2.4 MW and the average annual discharge of chloride, fluoride, and arsenic are 63 tons, 3.9 tons, and 241 kg, respectively. Average annual silica deposition rate on the geyser cone and along the outflow channels is 7 tons. This study provides a methodology for future studies at geysers worldwide and a baseline for monitoring future activity changes at Old Faithful.

Wyoming

Ground-water quality data in the San Fernando-San Gabriel study unit, 2005— Results from the California GAMA program

Ground-water quality in the approximately 460 square mile San Fernando-San Gabriel study unit (SFSG) was investigated between May and July 2005 as part of the Priority Basin Assessment Project of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA Priority Basin Assessment Project was developed in response to the Groundwater Quality Monitoring Act of 2001 and is being conducted by the U.S. Geological Survey (USGS) in cooperation with the California State Water Resources Control Board (SWRCB). The San Fernando-San Gabriel study was designed to provide a spatially unbiased assessment of raw ground-water quality within SFSG, as well as a statistically consistent basis for comparing water quality throughout California. Samples were collected from 52 wells in Los Angeles County. Thirty-five of the wells were selected using a spatially distributed, randomized grid-based method to provide statistical representation of the study area (grid wells), and seventeen wells were selected to aid in the evaluation of specific water-quality issues or changes in water chemistry along a historic ground-water flow path (understanding wells). The ground-water samples were analyzed for a large number of synthetic organic constituents [volatile organic compounds (VOCs), pesticides and pesticide degradates], constituents of special interest [perchlorate, N-nitrosodimethylamine (NDMA), 1,2,3-trichloropropane (1,2,3-TCP), and 1,4-dioxane], naturally occurring inorganic constituents (nutrients, major and minor ions, and trace elements), radioactive constituents, and microbial indicators. Naturally occurring isotopes (tritium, and carbon-14, and stable isotopes of hydrogen, oxygen, and carbon), and dissolved noble gases also were measured to help identify the source and age of the sampled ground water. Quality-control samples (blanks, replicates, samples for matrix spikes) were collected at approximately one-fifth (11 of 52) of the wells, and the results for these samples were used to evaluate the quality of the data for the ground-water samples. Assessment of the quality-control results showed that the data had very little bias or variability and resulted in censoring of less than 0.7 percent (32 of 4,484 measurements) of the data collected for ground-water samples. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, water typically is treated, disinfected, or blended with other waters to maintain acceptable water quality. Regulatory thresholds apply to treated water that is served to the consumer, not to raw ground water. However, to provide some context for the results, concentrations of constituents measured in the raw ground water were compared with health-based thresholds established by the U.S. Environmental Protection Agency (USEPA) and California Department of Public Health (CDPH) and thresholds established for aesthetic concerns (secondary maximum contaminant levels, SMCL-CA) by CDPH. VOCs were detected in more than 90 percent (33 of 35) of grid wells. For all wells sampled for SFSG, nearly all VOC detections were below health-based thresholds, and most were less than one-tenth of the threshold values. Samples from seven wells had at least one detection of PCE, TCE, tetrachloromethane, NDMA, or 1,2,3-TCP at or above a health-based threshold. Pesticides were detected in about 90 percent (31 of 35) grid wells and all detections in samples from SFSG wells were below health-based thresholds. Major ions, trace elements, and nutrients in samples from 17 SFSG wells were all below health-based thresholds, with the exception of one detection of nitrate that was above the USEPA maximum contaminant level (MCL-US). With the exception of 14 samples having radon-222 above the proposed MCL-US, radioactive constituents were below health-based thresholds for 16 of the SFSG wells sampled. Total dissolved solids in 6 of the 24 SFSG wells that were sampled ha

California

Bedrock aquifers in the Denver basin, Colorado; a quantitative water-resources appraisal

The Denver metropolitan area is experiencing a rapid population growth that is requiring increasing supplies of potable water to be pumped from bedrock aquifers in order to meet demand. In an effort to determine the ability of the aquifers to continue to meet this demand, the Colorado Department of Natural Resources, the Denver Board of Water Commissioners, and Adams, Arapahoe, Douglas, Elbert and El Paso Counties joined with the U.S. Geological Survey in undertaking a hydrologic evaluation of the ground-water resources of the basin. This involved mapping of aquifer extent, thickness, structure, hydraulic characteristics, and water-level and water-quality conditions. This enabled ground-water modeling techniques to be used to simulate aquifer response to various pumpage estimates and ground-water development plans. The Laramie-Fox Hills aquifer (the deepest aquifer) underlies the 6,700-square-mile study area and is overlain by the more permeable Arapahoe aquifer, the Denver aquifer, and the Dawson aquifer, which crops out in the southern part of the study area. It is estimated that 260x10 6 acre-feet of recoverable ground water are in storage in these four bedrock aquifers. However, less than 0.1 percent of this volume of water is stored under confined conditions. The larger volume of water stored under unconfined conditions will be available for use only when the water levels in the confined aquifers decline below the top of the individual aquifer, allowing water-table conditions to develop. Annual precipitation on the Denver basin supplies an average of 6,900 cubic feet per second of water to the area; about 55 cubic feet per second of this recharges the bedrock aquifers, principally through the Dawson Arkose. The direction of ground-water movement is generally from ground-water divides in the southern part of the area northward toward the margins of the aquifers. Pumpage has ranged from about 5 cubic feet per second in 1884 to about 41 cubic feet per second in 1978. Pumpage exceeds recharge in the metropolitan area and has caused water-level declines (1958-78) to exceed 200 feet in a 135-square-mile area of the Arapahoe aquifer southeast of Denver. A quasi-three-dimensional finite-difference model of the aquifer system was constructed and calibrated under steady-state and transient-state conditions. Steady-state calibration indicated that lateral hydraulic conductivity within the aquifers is about 100,000 times larger than the vertical hydraulic conductivity between the aquifers. Transient-state calibration indicated that between 1958 and 1978, 374,000 acre-feet of water was pumped from the aquifers, producing a 90,000-acre-foot net decrease in the volume of water in storage in the aquifers. During this time, pumpage also changed the rates of interaquifer flow, induced additional recharge, and caused capture of natural discharge. Three 1979-2050 pumpage estimates were made for use in simulating the effects of various ground-water development plans. Simulations using each of these pumpage estimates indicate that by the year 2050 large water-level declines could occur, particularly in the deeper aquifers. Maximum water-level declines of 410, 1,700, and 1,830 feet were produced using the small, medium, and large pumping rates. Four plans for supplementing the Denver water supply include pumping a satellite well field, pumping a municipal well field, pumping to irrigate parks, and injecting water during periods of low demand for later use during periods of peak demand. Model simulation of these plans indicates that the satellite well field will yield twice as much water as the municipal well field, but will produce larger and more widespread water-level declines in the four aquifers. The municipal well field would not significantly affect water levels in the Dawson aquifer. Pumping the Arapahoe aquifer to supply irrigation water to selected parks was shown to produce only small water-level declines in the aquifer. Results of simulating injection-pumpage well fields at two locations indicate that simulated injection rates could range from 1.7 to 10 cubic feet per second, depending on the choice of site. The volume of water that could be stored in the bedrock aquifer is, thus, sensitive to the hydrologic characteristics of the chosen site. More study is needed to evaluate water-chemistry compatibility of native and injected water.

Colorado

Summary of the Snake River plain Regional Aquifer-System Analysis in Idaho and eastern Oregon

Regional aquifers underlying the 15,600-square-mile Snake River Plain in southern Idaho and eastern Oregon was studied as part of the U.S. Geological Survey's Regional Aquifer-System Analysis program. The largest and most productive aquifers in the Snake River Plain are composed of Quaternary basalt of the Snake River Group, which underlies most of the 10,8000-square-mile eastern plain. Aquifer tests and simulation indicate that transmissivity of the upper 200 feet of the basalt aquifer in the eastern plain commonly ranges from about 100,000 to 1,000,000 feet squared per day. However, transmissivity of the total aquifer thickness may be as much as 10 million feet squared per day. Specific yield of the upper 200 feet of the aquifer ranges from about 0.01 to 0.20. Average horizontal hydraulic conductivity of the upper 200 feet of the basalt aquifer ranges from less than 100 to 9,000 feet per day. Values may be one to several orders of magnitude higher in parts in individual flows, such as flow tops. Vertical hydraulic conductivity is probably several orders of magnitude lower than horizontal hydraulic conductivity and is generally related to the number of joints. Pillow lava in ancestral Snake River channels has the highest hydraulic conductivity of all rock types. Hydraulic conductivity of the basalt decreases with depth because of secondary filling of voids with calcite and silica. An estimated 80 to 120 million acre-feet of water is believed to be stored in the upper 200 feet of the basalt aquifer in the eastern plain. The most productive aquifers in the 4,800-square-mile western plain are alluvial sand and gravel in the Boise River valley. Although aquifer tests indicate that transmissivity of alluvium in the Boise River valley ranges from 5,000 to 160,000 feet squared per day, simulation suggests that average transmissivity of the upper 500 feet is generally less than 20,000 feet squared per day. Vertically averaged horizontal hydraulic conductivity of the upper 500 feet of alluvium ranges from about 4 to 40 feet per day; higher values can be expected in individual sand and gravel zones. Vertical hydraulic conductivity is considerably lower because of the presence of clay layers. Hydraulic heads measured in piezometers, interpreted from diagrams showing ground-water flow and equipotential lines and estimated by computer simulation, demonstrate that water movement is three dimensional through the rock framework. Natural recharge takes place along the margins of the plain where head decreases with depth; discharge takes place near some reaches of the Snake River and the Boise River where head increases with depth. Geothermal water in rhyolitic rocks in the western plain and western part of the eastern plain has higher hydraulic head than the overlying cold water. Geothermal water, therefore, moves upward and merges into the cold-water system. Basin water-budget analyses indicate that the volume of cold water. Carbon-14 age determinations, which indicate that residence time of geothermal water is 17,700 to 20,300 years, plus or minus 4,000 years, imply slow movement of water through the geothermal system. Along much of its length, the Snake River gains large quantities of ground water. On the eastern plain, the river gained about 1.9 million acre-feet of water between Blackfoot and Neeley, Idaho, in 1980. Between Milner and King Hill, Idaho, the river gained 4.7 million acre-feet, mostly as spring flow from the north side. Upstream from Blackfoot and in the vicinity of Lake Walcott, the rover loses flow to ground water during parts or all of the year. On the western plain, river gains from ground water are small relative to those on the eastern plain; most are from seepage. Streams in tributary drainage basins supply calcium/bicarbonate type and calcium/magnesium/bicarbonate type water to the plain. Water type is a reflection of the chemical composition of rocks in the drainage basin, Concentrations of dissolved solids are smallest, about 50 milligrams per liter, in streams such as the Boise River that drain areas of granitic rocks; concentrations are greatest, about 400 milligrams per liter, in streams such as the Owyhee and Raft Rivers that drain area of sedimentary rocks. Water chemistry reflects the interaction of surface water and ground water. The chemical composition of ground water in the plain is essentially the same as that in streamflow and groundwater discharge from tributary drainage basins. Tributary drainage basins supplied 85 percent of the ground-water recharge in the eastern plain during 1980 and a nearly equivalent percentage of the solute load in ground water; human activities and dissolution of minerals supplied the other solutes. Dissolved-solids concentrations in ground water were generally less than 400 milligrams per liter. Water from the lower geothermal system is chemically different from water from the upper cold-water system. Geothermal water typically has greater concentrations of sodium, bicarbonate, sulfate, chloride, fluoride, silica, arsenic, boron, and lithium and smaller concentrations of calcium, magnesium, and hydrogen. Difference are attributed to ion exchange as geothermal moves through the rock framework. Irrigation, mostly on the Snake River Plain, accounted for about 96 percent of consumptive water use in Idaho during 1980. The use of surface water for irrigation for more than 100 years has caused major changes in the hydrologic system on the plain. Construction of dams, reservoirs, and diversifications effected planned changes in the surface-water system but resulted in largely unplanned changes in the ground-water system. During those years of irrigation, annual recharge in the main part of the eastern plain increased to about 6.7 million acre-feet in 1980, or by about 70 percent. Most of the increase was from percolation of surface water diverted for irrigation. From preirrigation to 1952, groundwater storage increased about 24 million acre-feet, and storage decreased from 1952 to 1964 and from 1976 to 1980 because of below-normal precipitation and increased withdrawals of ground water for irrigation. Annual ground-water discharge increased to about 7.1 million acre-feet in 1980, or about 80 percent since the start of irrigation. About 10 percent of the 1980 total discharge was ground-water pumpage. About 3.1 million acres, or almost one-third of the plain, was irrigated during 1980: 2.0 million acres with surface water, 1.0 million acres with ground water, and 0.1 million acres with combined surface and ground water. About 8.9 million acre-feet of Snake River water was diverted for irrigation during 1980 and 2.3 million acre-feet of ground water was pumped from 5,300 wells. Most irrigation wells on the eastern plain are open to basalt. About two-thirds of them yield more than 1,500 gallons per minute with a reported maximum of 7,240 gallons per minute; drawdown is less than 20 feet in two-thirds of the wells. Most irrigation wells on the western plain are open to sedimentary rocks. About one-third of them yield more than 1,00 gallons per minute with a reported maximum of 3,850 gallons per minute; drawndown is less than 20 feet in about one-fifth of the wells. The major instream use of water on the Snake River Plain is hydroelectric power generation. Fifty-two million acre-feet of water generated 2.6 million megawatthours of electricity during 1980. Digital computer ground-water flows models of the eastern and western plain reasonably simulated regional changes in water levels and ground-water discharges from 1880 (preirrigation) to 1980. Model results support the concept of three-dimensional flow and the hypotheses of no underflow between the eastern and western plain. Simulation of the regional aquifer system in the eastern plain indicates that is 1980 hydrologic conditions, including pumpage, were to remain the same for another 30 years, moderate declines in ground-water levels and decreases in spring discharges would continue. Increased ground-water pumpage to irrigate an additional 1 million acres could cause ground-water levels to decline a few tens of feet in the central part of the plain and could cause corresponding decreases in ground-water discharge. A combination of actions such as increased ground-water pumpage and decreased use of surface water for irrigation (resulting in reduced recharge) would accentuate the changes.

Idaho;Oregon

Coordination and standardization of federal sedimentation activities

In August 1964, the Bureau of the Budget issued Circular A-67 to set forth guidelines for the coordination of water-data acquisition activities throughout the Federal government. The U.S. Department of the Interior was assigned the task of implementing Circular A-67, which in turn redelegated this responsibility to the U.S. Geological Survey (USGS). Delegation of the lead responsibility for water-data coordination to the USGS occurred because of its historical role as the primary agency for water-data acquisition in the United States. To provide overall leadership for implementing the provisions of Circular A-67, the USGS established the Office of Water Data Coordination in the Water Resources Division (WRD). In addition, regional and district offices of the WRD were delegated responsibility for coordinating water data within their geographic areas of responsibility. On December 10, 1991, the Office of Management and Budget issued OMB Number Memorandum M-92-01, which expands the USGS's coordination role to encompass all water information. This includes data critical to water resources in the following categories: - surface- and ground-water quality and quantity, - sediment, - constituent transport, - erosion, - water chemistry, and - precipitation information critical to water resources management. Memorandum M-92-01 covers primarily freshwater bodies and includes activities, such as "development and distribution of consensus standards, field-data collection and laboratory analytical methods, data processing and interpretation, data-base management, quality control and quality assurance, and water- resources appraisals, assessments, and investigations." Research activities are not included.

Conference Paper

Wetlands, groundwater and seasonality influence the spatial distribution of stream chemistry in a low-relief catchment

Evaluating stream water chemistry patterns provides insight into catchment ecosystem and hydrologic processes. Spatially distributed patterns and controls of stream solutes are well-established for high-relief catchments where solute flow paths align with surface topography. However, the controls on solute patterns are poorly constrained for low-relief catchments where hydrogeologic heterogeneities and river corridor features, like wetlands, may influence water and solute transport. Here, we provide a data set of solute patterns from 58 synoptic surveys across 28 sites and over 32 months in a low-relief wetland-rich catchment to determine the major surface and subsurface controls along with wetland influence across the catchment. In this low-relief catchment, the expected wetland storage, processing, and transport of solutes is only apparent in solute patterns of the smallest subcatchments. Meanwhile, downstream seasonal and wetland influence on observed chemistry can be masked by large groundwater contributions to the main stream channel. These findings highlight the importance of incorporating variable groundwater contributions into catchment-scale studies for low-relief catchments, and that understanding the overall influence of wetlands on stream chemistry requires sampling across various spatial and temporal scales. Therefore, in low-relief wetland-rich catchments, given the mosaic of above and below ground controls on stream solutes, modeling efforts may need to include both surface and subsurface hydrological data and processes.

Michigan

Hydrogeochemistry of Bermuda: A case history of ground-water diagenesis of biocalcarenites

Bermuda is composed of relatively young skeletal limestones currently undergoing diagenesis by the ground water passing through them. The saturated zone consists of separate fresh-water bodies laterally surrounded and underlain by extensive brackish aureoles, in which the meteoric water is mixed with sea water. The meteoric water enters the aquifer after passing through the soil or through marshes (outcrops of the ground-water bodies), in each case causing an influx of CO 2 to the saturated zone. Examination of the ground-water chemistry enables mapping of (a) the extent of mixing of meteoric ground water and sea water; (b) P CO2 ; (c) the extent of saturation with calcite and aragonite; (d) concentration of Sr; and (e) the amount of calcium and magnesium derived from the limestones. It is concluded that three processes control the chemistry of Bermudian ground water: (a) generation of elevated CO 2 partial pressures in soils and marshes; (b) dissolution of metastable carbonate minerals (principally aragonite); and (c) mixing with sea water. Bermuda ground water apparently approaches a steady state of aragonite dissolution (at slight subsaturation) and concurrent precipitation of calcite cement. Large Sr/Ca ratios in the ground water indicate that the dissolution of aragonite is incongruent. Dissolution is most pronounced near the marshes where CO 2 content is highest. Mixing with sea water is not significant in controlling calcite saturation. Only small amounts of magnesium enter the ground water by incongruent dissolution of magnesium calcite, an apparently slow process on the time scale of passage of the ground water through the saturated zone. All of the waters are well undersaturated with respect to dolomite. It is estimated that the present rate of recrystallization of aragonite to calcite is about 0.32 cm 3 of aragonite to calcite per m 3 of the saturated zone per year. At the present rate of chemical weathering, 360 m 3 of the saturated zone is lost each year through solution and transported to the sea by ground water.

Geological Society of America Bulletin

Borehole geophysical monitoring of amendment emplacement and geochemical changes during vegetable oil biostimulation, Anoka County Riverfront Park, Fridley, Minnesota

The U.S. Geological Survey ( USGS ) conducted a series of geophysical investigations to monitor a field-scale biostimulation pilot project at the Anoka County Riverfront Park ( ACP ), downgradient from the Naval Industrial Reserve Ordnance Plant, in Fridley, Minnesota. The pilot project was undertaken by the U.S. Naval Facilities Engineering Command, Southern Division, for the purpose of evaluating biostimulation using emulsified vegetable oil to treat ground water contaminated with chlorinated hydrocarbons. Vegetable oil was introduced to the subsurface to serve as substrate for naturally occurring microbes, which ultimately break down chlorinated hydrocarbons into chloride, carbon dioxide, and water through oxidation-reduction reactions. In support of this effort, the USGS collected cross-borehole radar data and conventional borehole geophysical data in five site visits over 1.5 years to evaluate the effectiveness of geophysical methods for monitoring emplacement of the vegetable oil emulsion and for tracking changes in water chemistry. Radar zero-offset profile ( ZOP ) data, radar traveltime tomograms, electromagnetic ( EM ) induction logs, natural gamma logs, neutron porosity logs, and magnetic susceptibility logs were collected and analyzed. In order to facilitate data interpretation and to test the effectiveness of radar for monitoring oil-emulsion placement and movement, three injection mixtures with different radar signatures were used: (1) vegetable oil emulsion, (2) vegetable oil emulsion with a colloidal iron tracer, and (3) vegetable oil emulsion with a magnetite tracer. Based on petrophysical modeling, mixture (1) was expected to increase radar velocity and decrease radar attenuation relative to background—a water-saturated porous medium; mixtures (2) and (3) were expected to increase radar velocity and increase radar attenuation because of their greater electrical conductivity compared to background ground water. Radar ZOP data and tomograms show increased EM velocity in the vicinity of injection wells. Comparison of pre- and post-injection datasets shows that velocity anomalies are observed only in planes connected to injection wells, indicating that the emulsified vegetable oil does not migrate far after injection. In contrast to the localization of velocity anomalies, radar attenuation anomalies are observed in all zero-offset profiles, particularly those downgradient from the injection wells. Despite the expected signatures of different tracers, increases in attenuation are observed downgradient from all three injection wells; thus, we infer that the attenuation changes do not result from the iron tracers alone. Over the period of data collection, the slowness (reciprocal velocity) anomalies are relatively stable, whereas the attenuation anomalies generally increase in magnitude and extent. One explanation for the attenuation changes is that products of vegetable oil-enhanced biodegradation (for example, chloride) increase the specific conductance of ground water and thus bulk electrical conductivity and radar attenuation. This interpretation is supported by the results of EM-induction and magnetic susceptibility logs, which indicate increases in electrical conductivity in the absence of magnetic anomalies that might result from the iron and magnetite. Based on the geophysical data, conceptual models of the distributions of emulsified vegetable oil and ground water with altered chemistry were developed. The field data indicate that, in several cases, the plume of ground water with altered chemistry would not be detected by direct chemical sampling given the construction of monitoring wells; hence the geophysical data provide valuable site-specific insights for the interpretation of water samples and monitoring of biostimulation projects. Application of geophysical methods to data from the ACP demonstrated the utility of radar for monitoring biostimulation injections.

Minnesota