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USGS1994

Hydrogeology and selected water-quality aspects of the Hueco Bolson Aquifer at the Hueco Bolson Recharge Project area, El Paso, Texas

Samples of ground water and tertiary-treated water were evaluated to determine the distribution of injected water and trihalomethane compounds in the Hueco bolson aquifer near El Paso, Texas. Chloride and nitrate concentrations and oxygen-18/oxygen-16 (δ 18 O) values were used with end-member mixing analysis to estimate the fractional contributions of injected water, irrigation-affected water, saline ground water, and freshwater to ground-water chemistry. Several laterally continuous sand and gravel layers are the principal water-yielding lithologies in the aquifer. The potentiometric surface sloped toward the south and southwest during January 1990. Average linear ground-water velocities were as large as 1.4 feet per day near the zone of largest hydraulic conductivity and were substantially smaller farther south and east. Ground-water samples from as far as 2,900 feet from an injection well contained injectedwater tracers and trihalomethane compounds. Ground-water samples with injected-water tracers and no trihalomethane compounds may indicate infiltration from septic systems or oxidation ponds. Apparent breakthrough velocities of injected water in the aquifer ranged from 0.13 to 1.3 feet per day. Irrigation-affected water and saline water also were identified in water from several wells. Ground-water transport of bromoform and dibromochloromethane is attenuated relative to injected water, chloroform, and dichlorobromomethane. Microbial transformation of bromoform and dibromochloromethane probably was responsible for their disappearance from ground water. Chloroform and dichlorobromomethane concentrations were affected principally by advective and dispersive transport of injected water.

Texas↗

USGS1998

Water quality assessment of the Sacramento River Basin, California: Environmental setting and study design

This report describes the environmental setting and investigative activities of the Sacramento River Basin study unit of the National Water-Quality Assessment Program. The Sacramento River Basin is one of 60 study units located throughout the United States that has been scheduled for study as part of the National Water-Quality Assessment Program. The Sacramento River Basin is the most important source of freshwater in California. Water quality studies in the Sacramento River Basin study unit focus on the Sacramento Valley because it is here that the principal uses of water and potential impacts on water quality occur. Investigative activities include a network of surface water sites, where water chemistry and aquatic biological sampling are done, and a variety of ground water studies. In addition, investigations of the cycling and distribution of volatile organic compounds in the urban environment and the distribution of total and methyl mercury in the Sacramento River and tributaries will be completed.

California↗

USGS1995

Estimates of ground-water recharge rates for two small basins in central Nevada

Estimates of ground-water recharge rates developed from hydrologic modeling studies are presented for 3-Springs and East Stewart basins. two small basins (analog sites) located in central Nevada. The analog-site studies were conducted to aid in the estimation of recharge to the paleohydrologic regime associated with ground water in the vicinity of Yucca Mountain under wetter climatic conditions. The two analog sites are located to the north and at higher elevations than Yucca Mountain, and the prevailing (current) climatic conditions at these sites is thought to be representative of the possible range of paleoclimatic conditions in the general area of Yucca Mountain during the Quaternary. Two independent modeling approaches were conducted at each of the analog sites using observed hydrologic data on precipitation, temperature, solar radiation stream discharge, and chloride-ion water chemistry for a 6-year study period (October 1986 through September 1992). Both models quantify the hydrologic water-balance equation and yield estimates of ground-water recharge, given appropriate input data. The first model uses a traditional approach to quantify watershed hydrology through a precipitation-runoff modeling system that accounts for the spatial variability of hydrologic inputs, processes, and responses (outputs) using a dailycomputational time step. The second model is based on the conservative nature of the dissolved chloride ion in selected hydrologic environments, and its use as a natural tracer allows the computation of acoupled, water and chloride-ion, mass-balance system of equations to estimate available water (sum ofsurface runoff and groundwater recharge). Results of the modeling approaches support the conclusion that reasonable estimates of average-annual recharge to ground water range from about 1 to 3 centimeters per year for 3-Springs basin (the drier site), and from about 30 to 32 centimeters per year for East Stewart basin (the wetter site). The most reliable results are those derived from a reduced form of the chloride-ion model because they reflect integrated, basinwide processes in terms of only three measured variables: precipitation amount, precipitation chemistry, and streamflow chemistry.

Nevada↗

USGS1998

Chemical weathering in a tropical watershed, Luquillo Mountains, Puerto Rico: I. Long-term versus short-term weathering fluxes

The pristine Rio Icacos watershed in the Luquillo Mountains in eastern Puerto Rico has the fastest documented weathering rate of silicate rocks on the Earth's surface. A regolith propagation rate of 58 m Ma-1 calculated from iso-volumetric saprolite formation from quartz diorite, is comparable to the estimated denudation rate (25-50 Ma-1) but is an order of magnitude faster than the global average weathering rate (6 Ma-1). Weathering occurs in two distinct environments; plagioclase and hornblende react at the saprock interface and biotite and quartz weather in the overlying thick saprolitic regolith. These environments produce distinctly different water chemistries, with K, Mg, and Si increasing linearly with depth in saprolite porewaters and with stream waters dominated by Ca, Na, and Si. Such differences are atypical of less intense weathering in temperate watersheds. Porewater chemistry in the shallow regolith is controlled by closed-system recycling of inorganic nutrients such as K. Long-term elemental fluxes through the regolith (e.g., Si = 1.7 ?? 10-8 moles m-2 s-1) are calculated from mass losses based on changes in porosity and chemistry between the regolith and bedrock and from the age of the regolith surface (200 Ma). Mass losses attributed to solute fluxes are determined using a step-wise infiltration model which calculates mineral inputs to the shallow and deep saprolite porewaters and to stream water. Pressure heads decrease with depth in the shallow regolith (-2.03 m H2O m-1), indicating that both increasing capillary tension and graviometric potential control porewater infiltration. Interpolation of experimental hydraulic conductivities produces an infiltration rate of 1 m yr-1 at average field moisture saturation which is comparable with LiBr tracer tests and with base discharge from the watershed. Short term weathering fluxes calculated from solute chemistries and infiltration rates (e.g., Si = 1.4 ?? 10-8 moles m-2 s-1) are compared to watershed flux rates (e.g., Si = 2.7 ?? 10-8 moles m-2 s-1). Consistency between three independently determined sets of weathering fluxes imply that possible changes in precipitation, temperature, and vegetation over the last several hundred thousand years have not significantly impacted weathering rates in the Luquillo Mountains of Puerto Rico. This has important ramifications for tropical environments and global climate change. Copyright ?? 1998 Elsevier Science Ltd.

Geochimica et Cosmochimica Acta↗

USGS2008

Effects of forest harvesting on ecosystem health in the headwaters of the New York City Water Supply, Catskill Mountains, New York

The effects of forest clearcutting and selective harvesting on forest soils, soil and stream water chemistry, forest regrowth, and aquatic communities were studied in four small headwater catchments. This research was conducted to identify the sensitivity of forested ecosystems to forest disturbance in the northeastern United States. The study area was in the headwaters of the Neversink Reservoir watershed, part of the New York City water supply system, in the Catskill Mountains of southeastern New York. Two sub-catchments of the Shelter Creek watershed were selectively harvested, one in its northern half and one more heavily in its southern half in 1995?96, the Dry Creek watershed was clearcut in the winter of 1996?97, and the Clear Creek watershed was left undisturbed and monitored as a control site. Monitoring was conducted from 4 years before the harvests until 4 years after the harvests. Clearcutting caused a large release of nitrate (NO3-) from watershed soils and a concurrent release of inorganic monomeric aluminum (Alim), which is toxic to some aquatic biota. The increased soil NO3- concentrations measured after the harvest could be completely accounted for by the decrease in nitrogen (N) uptake by watershed trees, rather than an increase in N mineralization and nitrification. The large increase in stream water NO3- and Alim concentrations caused 100-percent mortality of caged brook trout (Salvelinus fontinalis) during the first year after the clearcut and adversely affected macroinvertebrate communities for 2 years after the harvest. Nutrient uptake and biomass accumulation increased in uncut mature trees after the two selective harvests. There was no increase in stream-water NO3- or Alim concentrations, and so there were no adverse affects on macroinvertebrate or trout communities. The amount of tree biomass that can be removed without causing a sharp increase in stream-water NO3- and Alim stream-water concentrations is unknown, but probably depends on the history of forest-disturbance and acid deposition and the level of soil acidification. Results of this study indicate that macroinvertebrate and brook trout communities were sensitive to clearcutting and that deer browsing may affect water quality by suppressing forest regeneration and nutrient uptake. Further studies of selective harvests could identify the harvesting threshold below which changes in water quality and soil chemistry are minimized, and nutrient retention is maximized, thus reducing the damage that logging can inflict on stream and aquatic communities.

New York↗

USGS2008

Infiltration from an impoundment for coal‐bed natural gas, Powder River Basin, Wyoming: Evolution of water and sediment chemistry

Development of coal‐bed natural gas (CBNG) in the Powder River Basin, Wyoming, has increased substantially in recent years. Among environmental concerns associated with this development is the fate of groundwater removed with the gas. A preferred water‐management option is storage in surface impoundments. As of January 2007, permits for more than 4000 impoundments had been issued within Wyoming. A study was conducted on changes in water and sediment chemistry as water from an impoundment infiltrated the subsurface. Sediment cores were collected prior to operation of the impoundment and after its closure and reclamation. Suction lysimeters were used to collect water samples from beneath the impoundment. Large amounts of chloride (12,300 kg) and nitrate (13,500 kg as N), most of which accumulated naturally in the sediments over thousands of years, were released into groundwater by infiltrating water. Nitrate was more readily flushed from the sediments than chloride. If sediments at other impoundment locations contain similar amounts of chloride and nitrate, impoundments already permitted could release over 48 × 10 6 kg of chloride and 52 × 10 6 kg of nitrate into groundwater in the basin. A solute plume with total dissolved solid (TDS) concentrations at times exceeding 100,000 mg/L was created in the subsurface. TDS concentrations in the plume were substantially greater than those in the CBNG water (about 2300 mg/L) and in the ambient shallow groundwater (about 8000 mg/L). Sulfate, sodium, and magnesium are the dominant ions in the plume. The elevated concentrations are attributed to cation‐exchange‐enhanced gypsum dissolution. As gypsum dissolves, calcium goes into solution and is exchanged for sodium and magnesium on clays. Removal of calcium from solution allows further gypsum dissolution.

Water Resources Research↗

USGS2009

Flow and geochemistry of groundwater beneath a back-barrier lagoon: The subterranean estuary at Chincoteague Bay, Maryland, USA

To better understand large-scale interactions between fresh and saline groundwater beneath an Atlantic coastal estuary, an offshore drilling and sampling study was performed in a large barrier-bounded lagoon, Chincoteague Bay, Maryland, USA. Groundwater that was significantly fresher than overlying bay water was found in shallow plumes up to 8 m thick extending more than 1700 m offshore. Groundwater saltier than bay surface water was found locally beneath the lagoon and the barrier island, indicating recharge by saline water concentrated by evaporation prior to infiltration. Steep salinity and nutrient gradients occur within a few meters of the sediment surface in most locations studied, with buried peats and estuarine muds acting as confining units. Groundwater ages were generally more than 50 years in both fresh and brackish waters as deep as 23 m below the bay bottom. Water chemistry and isotopic data indicate that freshened plumes beneath the estuary are mixtures of water originally recharged on land and varying amounts of estuarine surface water that circulated through the bay floor, possibly at some distance from the sampling location. Ammonium is the dominant fixed nitrogen species in saline groundwater beneath the estuary at the locations sampled. Isotopic and dissolved-gas data from one location indicate that denitrification within the subsurface flow system removed terrestrial nitrate from fresh groundwater prior to discharge along the western side of the estuary. Similar situations, with one or more shallow semi-confined flow systems where groundwater geochemistry is strongly influenced by circulation of surface estuary water through organic-rich sediments, may be common on the Atlantic margin and elsewhere.

Marine Chemistry↗

USGS2006

Mixing of shallow and deep groundwater as indicated by the chemistry and age of karstic springs

Large karstic springs in east-central Florida, USA were studied using multi-tracer and geochemical modeling techniques to better understand groundwater flow paths and mixing of shallow and deep groundwater. Spring water types included Ca-HCO3 (six), Na-Cl (four), and mixed (one). The evolution of water chemistry for Ca-HCO3 spring waters was modeled by reactions of rainwater with soil organic matter, calcite, and dolomite under oxic conditions. The Na-Cl and mixed-type springs were modeled by reactions of either rainwater or Upper Floridan aquifer water with soil organic matter, calcite, and dolomite under oxic conditions and mixed with varying proportions of saline Lower Floridan aquifer water, which represented 4-53% of the total spring discharge. Multiple-tracer data-chlorofluorocarbon CFC-113, tritium (3H), helium-3 (3Hetrit), sulfur hexafluoride (SF6) - for four Ca-HCO3 spring waters were consistent with binary mixing curves representing water recharged during 1980 or 1990 mixing with an older (recharged before 1940) tracer-free component. Young-water mixing fractions ranged from 0.3 to 0.7. Tracer concentration data for two Na-Cl spring waters appear to be consistent with binary mixtures of 1990 water with older water recharged in 1965 or 1975. Nitrate-N concentrations are inversely related to apparent ages of spring waters, which indicated that elevated nitrate-N concentrations were likely contributed from recent recharge. ?? Springer-Verlag 2006.

Hydrogeology Journal↗

USGS2008

Long-term change in limnology and invertebrates in Alaskan boreal wetlands

Climate change is more pronounced at high northern latitudes, and may be affecting the physical, chemical, and biological attributes of the abundant wetlands in boreal forests. On the Yukon Flats, located in the boreal forest of northeast Alaska, wetlands originally sampled during 1985-1989 were re-sampled for water chemistry and macroinvertebrates in summer 2001-2003. Wetlands sampled lost on average 19% surface water area between these periods. Total nitrogen and most metal cations (Na, Mg, and Ca, but not K) increased between these periods, whereas total phosphorus and chlorophyll a (Chl a) declined. These changes were greater in wetlands that had experienced more drying (decreased surface area). Compared with 1985-1989, densities of cladocerans, copepods, and ostracods in both June and August were much higher in 2002-2003, whereas densities of amphipods, gastropods, and chironomid larvae were generally lower. In comparisons among wetlands in 2002-2003 only, amphipod biomass was lower in wetlands with lower Chl a, which might help explain the decline of amphipods since the late 1980s when Chl a was higher. The decline in Chl a corresponded to greatly increased zooplankton density in June, suggesting a shift in carbon flow from scrapers and deposit-feeders to water-column grazers. Declines in benthic and epibenthic deposit-feeding invertebrates suggest important food web effects of climate change in otherwise pristine wetlands of the boreal forest. ?? 2008 Springer Science+Business Media B.V.

Hydrobiologia↗

USGS2026

Post-wildfire water quality and aquatic ecosystem response in the U.S. Pacific Northwest: science and monitoring gaps

An increase in the occurrence of large, high severity wildfires in the western Pacific Northwest (PNW), USA, has created an urgent need for science to better inform forest management and policy decisions to maintain source water quality in the region. The western PNW faces similar challenges to other regions with shifting wildfire regimes and large population centers reliant on surface water from forested catchments. However, the uniquely wet and highly seasonal climate of the western PNW suggests that findings from other, more frequently burned regions may not be directly applicable. To identify science, monitoring, and management gaps and opportunities in the western PNW, this review was collaboratively undertaken by academics, non-government and industry representatives, and local, state, and federal government entities who have been working together since the 2020 Labor Day fires in Oregon. Focusing on Oregon and Washington, we found that monitoring networks for continuous water quantity and quality cover much of the state with greater representation in western U.S. ecoregions, but few studies have analyzed and published these data to capture and communicate the post-wildfire response. Approximately half of the streamgages in Oregon and Washington record major water quality parameters, and hundreds of sites in the area have discrete sampling for a wide range of water quality constituents. Still, numerous gaps exist in understanding the short- and long-term impacts of wildfire on hydrology, water chemistry, including pH and dissolved oxygen, mobilization of metals, aquatic ecosystems, and downstream drinking water treatment. Collective action to further collect, analyze, interpret, and publish the key data could help improve our understanding of post-wildfire water quality impacts in this and other increasingly wildfire-affected regions.

Oregon, Washington↗

USGS2001

Sources of salinity near a coal mine spoil pile, north-central Colorado

A small (1 km 2 ) salt-affected stream drainage on the High Plains north of Denver, Colorado was sampled to determine the near-surface dispersion of soluble salts and metals from low-sulfur coal mining waste (spoil). Surface waters collected along the 0.8-km stream reach, and aqueous leachates of spoil and naturally saline local soil, were analyzed for chemical constituents and sulfur isotopes. In this semiarid setting with abundant carbonate-bearing surficial sediments, the limited, mildly acidic drainage from the spoil pile is quickly neutralized, restricting the mobility of many elements. However, some spoil-derived constituents were clearly traceable within the upper 0.4 km of the stream reach. Spoil leachates and surface water near the spoil pile have distinctive compositions of major anions and cations, and elevated levels of dissolved nitrate compared with downstream waters. Spoil-derived sulfate was traceable because it has generally positive values of δ 34 S that contrasted with generally negative values of δ 34 S in soil leachates and evaporite salts from the surrounding area. Spatial–chemical sampling of surface water showed an abrupt increase in dissolved U, Se, B, Li, and Mn in the lower 0.4 km of the stream reach where shallow ground water from surrounding irrigated fields contributed to surface flow. The downstream evolution of surface water chemistry and sulfur isotopic composition is consistent with mixing between spoil-affected upstream water and irrigation-return water. The methods described should be applicable at other sites in similar settings where the environmental effect of low-sulfur coal mining waste must be assessed and where access to samples of shallow ground water is limited.

Colorado↗

USGS2008

Simulations of ground-water flow and particle pathline analysis in the zone of contribution of a public-supply well in Modesto, eastern San Joaquin Valley, California

Shallow ground water in the eastern San Joaquin Valley is affected by high nitrate and uranium concentrations and frequent detections of pesticides and volatile organic compounds (VOC), as a result of ground-water development and intensive agricultural and urban land use. A single public-supply well was selected for intensive study to evaluate the dominant processes affecting the vulnerability of public-supply wells in the Modesto area. A network of 23 monitoring wells was installed, and water and sediment samples were collected within the approximate zone of contribution of the public-supply well, to support a detailed analysis of physical and chemical conditions and processes affecting the water chemistry in the well. A three-dimensional, steady-state local ground-water-flow and transport model was developed to evaluate the age of ground water reaching the well and to evaluate the vulnerability of the well to nonpoint source input of nitrate and uranium. Particle tracking was used to compute pathlines and advective travel times in the ground-water flow model. The simulated ages of particles reaching the public-supply well ranged from 9 to 30,000 years, with a median of 54 years. The age of the ground water contributed to the public-supply well increased with depth below the water table. Measured nitrate concentrations, derived primarily from agricultural fertilizer, were highest (17 milligrams per liter) in shallow ground water and decreased with depth to background concentrations of less than 2 milligrams per liter in the deepest wells. Because the movement of water is predominantly downward as a result of ground-water development, and because geochemical conditions are generally oxic, high nitrate concentrations in shallow ground water are expected to continue moving downward without significant attenuation. Simulated long-term nitrate concentrations indicate that concentrations have peaked and will decrease in the public-supply well during the next 100 years because of the low nitrate concentrations in recharge beneath the urban area and the increasing proportion of urban-derived ground water reaching the well. The apparent lag time between peak input concentrations and peak concentrations in the well is about 20 to 30 years. Measured uranium concentrations were also highest (45 micrograms per liter) in shallow ground water, and decreased with depth to background concentrations of about 0.5 microgram per liter. Naturally-occurring uranium adsorbed to aquifer sediments is mobilized by oxygen-rich, high-alkalinity water. Alkalinity increased in shallow ground water in response to agricultural development. As ground-water pumping increased in the 1940s and 1950s, this alkaline water moved downward through the ground-water flow system, mobilizing the uranium adsorbed to aquifer sediments. Ground water with high alkalinity and high uranium concentrations is expected to continue to move deeper in the system, resulting in increased uranium concentrations with depth in ground water. Because alkalinity (and correspondingly uranium) concentrations were high in shallow ground water beneath both the urban and the agricultural land, long-term uranium concentrations in the public-supply well are expected to increase as the proportion of uranium-affected water contributed to the well increases. Assuming that the alkalinity near the water table remains the same, the simulation of long-term alkalinity in the public-supply well indicates that uranium concentrations in the public-supply well will likely approach the maximum contaminant level; however, the time to reach this level is more than 100 years because of the significant proportion of old, unaffected water at depth that is contributed to the public-supply well.

California↗

USGS1995

Ground-water conditions and effects of mine dewatering in Desert Valley, Humboldt and Pershing Counties, northwestern Nevada, 1962-91

Desert Valley is a 1,200-square-mile, north- trending, structural basin, about 30 miles northwest of Winnemucca, Nevada. Unconsolidated basin-fill deposits exceeding 7,000 feet in thickness constitute the primary ground-water reservoir. Dewatering operations at an open-pit mine began in the Spring of 1985 in the northeast part of Desert Valley. Ground-water withdrawal for mine dewatering in 1991 was greater than three times the estimated average annual recharge from precipitation. The mine discharge water has been allowed to flow to areas west of the mine where it has created an artificial wetlands. This report documents the 1991 hydrologic conditions in Desert Valley and the change in conditions since predevelopment (pre-1962). It also summarizes the results of analyzing the simulated effects of open-pit mine dewatering on a basin-wide scale over time. Water-level declines associated with the dewatering have propagated north and south of the mine, but have been attenuated to the west due to the infiltration beneath the artificial wetlands. Maximum water-level declines beneath the open pits at the mine, as of Spring 1991, are about 300 feet. Changes in the hydrologic conditions since predevelopment are observed predominantly near the dewatering operations and the associated discharge lakes. General ground-water chemistry is essentially unchanged since pre- development. On the basis of a ground-water flow model used to simulate mine dewatering, a new equilibrium may slowly be approached only after 100 years of recovery from the time mine dewatering ceases.

Water-Resources Investigations Report↗

USGS2003

Identification of linear and threshold responses in streams along a gradient of urbanization in Anchorage, Alaska

We examined biotic and physiochemical responses in urbanized Anchorage, Alaska, to the percent of impervious area within stream basins, as determined by high-resolution IKONOS satellite imagery and aerial photography. Eighteen of the 86 variables examined, including riparian and instream habitat, macroinvertebrate communities, and water/sediment chemistry, were significantly correlated with percent impervious area. Variables related to channel condition, instream substrate, water chemistry, and residential and transportation right-of-way land uses were identified by principal components analysis as significant factors separating site groups. Detrended canonical correspondence analysis indicated that the macroinvertebrate communities responded to an urbanization gradient closely paralleling the percent of impervious area within the subbasin. A sliding regression analysis of variables significantly correlated with percent impervious area revealed 8 variables exhibiting threshold responses that correspond to a mean of 4.4-5.8% impervious area, much lower than mean values reported in other, similar investigations. As contributing factors to a subbasin's impervious area, storm drains and roads appeared to be important elements influencing the degradation of water quality with respect to the biota.

Alaska↗

USGS1988

Microbial methane in the shallow Paleozoic sediments and glacial deposits of Illinois, U.S.A.

Methane formed by the microbial decomposition of buried organic matter is virtually ubiquitous in the groundwaters of Illinois. Chemical and carbon isotopic compositions are reported for gas samples collected from over 200 private and municipal water wells and from 39 small gas wells completed in glacial deposits (drift-gas wells). Carbon and hydrogen isotopic data for methane, carbon dioxide and water show that these gases were formed by the carbon dioxide reduction pathway, the same mechanism which has been previously shown to be responsible for microbial methane formation in the marine environment. The isotopic composition of methane in these samples can be closely correlated with the chemical composition of the gas and with water chemistry. The data are interpreted as indicating that isotopically very light methane is found in waters where the residence time of groundwater in the methanogenesis zone was very short relative to the methane production rate. ?? 1988.

Chemical Geology↗

USGS2009

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park: IV Acid-sulfate waters

Many waters sampled in Yellowstone National Park, both high-temperature (30-94 ??C) and low-temperature (0-30 ??C), are acid-sulfate type with pH values of 1-5. Sulfuric acid is the dominant component, especially as pH values decrease below 3, and it forms from the oxidation of elemental S whose origin is H2S in hot gases derived from boiling of hydrothermal waters at depth. Four determinations of pH were obtained: (1) field pH at field temperature, (2) laboratory pH at laboratory temperature, (3) pH based on acidity titration, and (4) pH based on charge imbalance (at both laboratory and field temperatures). Laboratory pH, charge imbalance pH (at laboratory temperature), and acidity pH were in close agreement for pH < 2.7. Field pH measurements were predominantly used because the charge imbalance was <??10%. When the charge imbalance was generally >??10%, a selection process was used to compare acidity, laboratory, and charge balance pH to arrive at the best estimate. Differences between laboratory and field pH can be explained based on Fe oxidation, H2S or S2O3 oxidation, CO2 degassing, and the temperature-dependence of pK2 for H2SO4. Charge imbalances are shown to be dependent on a speciation model for pH values <3. The highest SO4 concentrations, in the thousands of mg/L, result from evaporative concentration at elevated temperatures as shown by the consistently high ??18O values (-10??? to -3???) and a ??D vs. ??18O slope of 3, reflecting kinetic fractionation. Low SO4 concentrations (<100 mg/L) for thermal waters (>350 mg/L Cl) decrease as the Cl- concentration increases from boiling which appears inconsistent with the hypothesis of H2S oxidation as a source of hydrothermal SO4. This trend is consistent with the alternate hypothesis of anhydrite solubility equilibrium. Acid-sulfate water analyses are occasionally high in As, Hg, and NH3 concentrations but in contrast to acid mine waters they are low to below detection in Cu, Zn, Cd, and Pb concentrations. Even concentrations of SO4, Fe, and Al are much lower in thermal waters than acid mine waters of the same pH. This difference in water chemistry may explain why certain species of fly larvae live comfortably in Yellowstone's acid waters but have not been observed in acid rock drainage of the same pH.

Applied Geochemistry↗

USGS2014

Hydrogeochemistry of prairie pothole region wetlands: Role of long-term critical zone processes

This study addresses the geologic and hydrogeochemical processes operating at a range of scales within the prairie pothole region (PPR). The PPR is a 750,000 km 2 portion of north central North America that hosts millions of small wetlands known to be critical habitat for waterfowl and other wildlife. At a local scale, we characterized the geochemical evolution of the 92-ha Cottonwood Lake study area (CWLSA), located in North Dakota, USA. Critical zone processes are the long-term determinant of wetland water and groundwater geochemistry via the interaction of oxygenated groundwater with pyrite in the underlying glacial till. Pyrite oxidation produced a brown, iron oxide-bearing surface layer locally over 13 m thick and an estimated minimum of 1.3 × 10 10 g sulfate (SO 4 2 − ) at CWLSA. We show that the majority of this SO 4 2− now resides in solid-phase gypsum (CaSO 4 •2H 2 O) and gypsum-saturated groundwater. Results from the CWLSA were scaled up to a 9700 km 2 area surrounding CWLSA using ~ 1800 drill logs and literature data on wetland water chemistry for 178 wetlands within this larger area. The oxidized brown zone depth and wetland water compositional trends are very similar to the CWLSA. Additionally, surface water data from 176 southern Canadian pothole wetlands that conform to the same wetland water geochemical trends as those recorded in the CWLSA further corroborate that SO 4 2 − accumulation driven by pyrite oxidation is a nearly ubiquitous process in the prairie pothole region and distinguishes PPR wetlands from other wetlands worldwide that have a similar overall hydrology.

Manitoba, North Dakota, Saskatchewan↗

USGS2007

Rare-earth elements in the Permian Phosphoria formation: Paleo proxies of ocean geochemistry

The geochemistry of deposition of the Meade Peak Member of the Phosphoria Formation (MPM) in southeast Idaho, USA, a world-class sedimentary phosphate deposit of Permian age that extends over 300,000 km 2 , is ascertained from its rare earth element (REE) composition. Ratios of REE:Al 2 O 3 suggest two sources—seawater and terrigenous debris. The seawater-derived marine fraction identifies bottom water in the Phosphoria Sea as O 2 -depleted, denitrifying (suboxic) most of the time, and seldom sulfate-reducing (anoxic). This interpretation is supported by earlier research that showed progressively greater ratios in the marine sediment fraction of Cr:Ni>V:Ni⪢Mo:Ni, relative to their ratios in seawater; for which marine Cr, V, and Mo can have a dominantly O 2 –depleted bottom-water source and Ni a photic-zone, largely algal, source. The water chemistry was maintained by a balance between bacterial oxidation of organic matter settling through the water column, determined largely by primary productivity in the photic zone, and the flux of oxidants into the bottom water via advection of seawater from the open ocean. Samples strongly enriched in carbonate fluorapatite, the dominant REE host mineral, have variable Er/Sm, Tm/Sm, and Yb/Sm ratios. Their distribution may represent greater advection of seawater between the Phosphoria Sea and open ocean during deposition of two ore zones than a center waste and greater upwelling of nutrient-enriched water into the photic zone. However, the mean rate of deposition of marine Ni, a trace nutrient of algae, and PO 4 3− , a limiting nutrient, indicate that primary productivity was probably high throughout the depositional history. An alternative interpretation of the variable enrichments of Er, Tm, and Yb, relative to Sm, is that they may reflect temporally variable carbonate alkalinity of open-ocean seawater in Permian time. A more strongly negative Ce anomaly for all phosphatic units than the Ce anomaly of modern pelletal phosphate is further indicative of an elevated O 2 concentration in the Permo-Carboniferous open ocean, as proposed by others, in contrast to the depletion of O 2 in the bottom water of the Phosphoria Sea itself. The oceanographic conditions under which the deposit accumulated were likely similar to conditions under which many sedimentary phosphate deposits have accumulated and to conditions under which many black shales that are commonly phosphate poor have accumulated. A shortcoming of several earlier studies of these deposits has resulted from a failure to examine the marine fraction of elements separate from the terrigenous fraction.

Idaho↗