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At least 1,351 records · Page 75Linked to original sources

USGS1996

Weathering rates as a function of flow through an alpine soil

The effect of flow on release rates of solutes from soil in a 39-m2 alpine catchment in the Colorado Rockies was measured during the summers of 1990-1994. Flow rates through the soil were varied by augmenting natural rainfall with deionized irrigation water. Daily water inputs averaged between 96 and 216 1 day-1 during the five field seasons, and mean discharge (inputs minus evapotranspiration) varied from 35 to 175 1 day-1. Volume-weighted mean concentrations of base cations and silica decreased only moderately in response to the increased water inputs. Input fluxes of solutes in precipitation were similar in each of the study seasons, but output fluxes of base cations and silica in surface outflow increased substantially in conjunction with the average water input rate for the season. Weathering rates calculated from the chemical fluxes increased substantially in response to increases in water input rates. The increases appear to be largely attributable to enhanced transport of solutes from the soil matrix under high flow conditions. At high flow, physical flushing of micropores presumably occurs to a greater extent than during low-flow periods because of greater soil wetness and higher hydrologic head. Increased flushing would also cause an increased rate of diffusion of solutes from microcracks in mineral surfaces and constricted pore spaces in response to an increased concentration gradient between those regions and adjacent areas in the soil matrix. Another consequence of the increased flushing that occurs during periods of high flow is that concentrations throughout the soil matrix tend to be lower, which might increase chemical weathering rates of some silicate minerals such as microcline, which are relatively close to saturation. Decreased Si concentrations under high-flow conditions appear to promote dissolution of amorphous aluminosilicates or desorption of Si from mineral surfaces, buffering Si concentrations in the soil solutions. Thus, both physical transport of solutes and subsequent chemical effects appear to be responsible for the positive relation observed between fluxes of weathering products and water input rates.

Chemical Geology↗

USGS2012

The physical hydrogeology of ore deposits

Hydrothermal ore deposits represent a convergence of fluid flow, thermal energy, and solute flux that is hydrogeologically unusual. From the hydrogeologic perspective, hydrothermal ore deposition represents a complex coupled-flow problem—sufficiently complex that physically rigorous description of the coupled thermal (T), hydraulic (H), mechanical (M), and chemical (C) processes (THMC modeling) continues to challenge our computational ability. Though research into these coupled behaviors has found only a limited subset to be quantitatively tractable, it has yielded valuable insights into the workings of hydrothermal systems in a wide range of geologic environments including sedimentary, metamorphic, and magmatic. Examples of these insights include the quantification of likely driving mechanisms, rates and paths of fluid flow, ore-mineral precipitation mechanisms, longevity of hydrothermal systems, mechanisms by which hydrothermal fluids acquire their temperature and composition, and the controlling influence of permeability and other rock properties on hydrothermal fluid behavior. In this communication we review some of the fundamental theory needed to characterize the physical hydrogeology of hydrothermal systems and discuss how this theory has been applied in studies of Mississippi Valley-type, tabular uranium, porphyry, epithermal, and mid-ocean ridge ore-forming systems. A key limitation in the computational state-of-the-art is the inability to describe fluid flow and transport fully in the many ore systems that show evidence of repeated shear or tensional failure with associated dynamic variations in permeability. However, we discuss global-scale compilations that suggest some numerical constraints on both mean and dynamically enhanced crustal permeability. Principles of physical hydrogeology can be powerful tools for investigating hydrothermal ore formation and are becoming increasingly accessible with ongoing advances in modeling software.

Economic Geology↗

USGS2002

Multispecies reactive tracer test in an aquifer with spatially variable chemical conditions, Cape Cod, Massachusetts: Dispersive transport of bromide and nickel

Dispersive transport of groundwater solutes was investigated as part of a multispecies reactive tracer test conducted under spatially variable chemical conditions in an unconfined, sewage‐contaminated sand and gravel aquifer on Cape Cod, Massachusetts. Transport of the nonreactive tracer bromide (Br) reflected physical and hydrologic processes. Transport of the reactive tracer nickel (Ni) complexed with an organic ligand (NiEDTA) varied in response to pH and other chemical conditions within the aquifer. A loss of about 14% of the Ni mass was calculated from the distribution of tracers through time. This loss is consistent with reversible adsorption of NiEDTA onto the iron and aluminum oxyhydroxide coatings on the aquifer sediments. The Ni consistently lagged behind Br with a calculated retardation coefficient of 1.2. Longitudinal dispersivities reached constant values of 2.2 and 1.1 m for Br and Ni, respectively, by at least 69 m of travel. The smaller dispersivity for Ni possibly was due to nonlinear or spatially variant adsorption of NiEDTA. In the upper, uncontaminated zone of the aquifer, longitudinal dispersion of Ni was greater than that of Br early in the test as a result of reversible adsorption of NiEDTA. In general, transverse dispersivities were much smaller (horizontal: 1.4–1.5 × 10 −2 m; vertical: 0.5–3.8 × 10 −3 m) than the longitudinal dispersivities. The Br results are similar to those from a test conducted eight years earlier, suggesting that transport parameters are spatially stationary within the aquifer at the scale of 300 m covered by the spatially overlapping tests. A significant difference between the two tests was the travel distance (69 and 26 m) needed to reach a constant longitudinal dispersivity.

Massachusetts↗

USGS2016

Assessment of canyon wall failure process from multibeam bathymetry and Remotely Operated Vehicle (ROV) observations, U.S. Atlantic continental margin

Over the last few years, canyons along the northern U.S. Atlantic continental margin have been the focus of intensive research examining canyon evolution, submarine geohazards, benthic ecology and deep-sea coral habitat. New high-resolution multibeam bathymetry and Remotely Operated Vehicle (ROV) dives in the major shelf-breaching and minor slope canyons, provided the opportunity to investigate the size of, and processes responsible for, canyon wall failures. The canyons cut through thick Late Cretaceous to Recent mixed siliciclastic and carbonate-rich lithologies which impart a primary control on the style of failures observed. Broad-scale canyon morphology across much of the margin can be correlated to the exposed lithology. Near vertical walls, sedimented benches, talus slopes, and canyon floor debris aprons were present in most canyons. The extent of these features depends on canyon wall cohesion and level of internal fracturing, and resistance to biological and chemical erosion. Evidence of brittle failure over different spatial and temporal scales, physical abrasion by downslope moving flows, and bioerosion, in the form of burrows and surficial scrape marks provide insight into the modification processes active in these canyons. The presence of sessile fauna, including long-lived, slow growing corals and sponges, on canyon walls, especially those affected by failure provide a critical, but as yet, poorly understood chronological record of geologic processes within these systems.

Book chapter↗

USGS2015

Enhanced microbial coalbed methane generation: A review of research, commercial activity, and remaining challenges

Coalbed methane (CBM) makes up a significant portion of the world’s natural gas resources. The discovery that approximately 20% of natural gas is microbial in origin has led to interest in microbially enhanced CBM (MECoM), which involves stimulating microorganisms to produce additional CBM from existing production wells. This paper reviews current laboratory and field research on understanding processes and reservoir conditions which are essential for microbial CBM generation, the progress of efforts to stimulate microbial methane generation in coal beds, and key remaining knowledge gaps. Research has been primarily focused on identifying microbial communities present in areas of CBM generation and attempting to determine their function, in-situ reservoir conditions that are most favorable for microbial CBM generation, and geochemical indicators of metabolic pathways of methanogenesis (i.e., acetoclastic or hydrogenotrophic methanogenesis). Meanwhile, researchers at universities, government agencies, and companies have focused on four primary MECoM strategies: 1) microbial stimulation (i.e., addition of nutrients to stimulate native microbes); 2) microbial augmentation (i.e., addition of microbes not native to or abundant in the reservoir of interest); 3) physically increasing microbial access to coal and distribution of amendments; and 4) chemically increasing the bioavailability of coal organics. Most companies interested in MECoM have pursued microbial stimulation: Luca Technologies, Inc., successfully completed a pilot scale field test of their stimulation strategy, while two others, Ciris Energy and Next Fuel, Inc., have undertaken smaller scale field tests. Several key knowledge gaps remain that need to be addressed before MECoM strategies can be implemented commercially. Little is known about the bacterial community responsible for coal biodegradation and how these microorganisms may be stimulated to enhance microbial methanogenesis. In addition, research is needed to understand what fraction of coal is available for biodegradation, and methods need to be developed to determine the extent of in-situ coal biodegradation by MECoM processes for monitoring changes to coal quality. Questions also remain about how well field-scale pilot tests will scale to commercial production, how often amendments will need to be added to maintain new methane generation, and how well MECoM strategies transfer between coal basins with different formation water geochemistries and coal ranks. Addressing these knowledge gaps will be key in determining the feasibility and commercial viability of MECoM technology.

International Journal of Coal Geology↗

USGS2002

Employment of Gibbs-Donnan-based concepts for interpretation of the properties of linear polyelectrolyte solutions

Earlier research has shown that the acid dissociation and metal ion complexation equilibria of linear, weak-acid polyelectrolytes and their cross-linked gel analogues are similarly sensitive to the counterion concentration levels of their solutions. Gibbs-Donnan-based concepts, applicable to the gel, are equally applicable to the linear polyelectrolyte for the accommodation of this sensitivity to ionic strength. This result is presumed to indicate that the linear polyelectrolyte in solution develops counterion-concentrating regions that closely resemble the gel phase of their analogues. Advantage has been taken of this description of linear polyelectrolytes to estimate the solvent uptake by these regions. ?? 1991 American Chemical Society.

Journal of Physical Chemistry↗

USGS2006

Mineral mapping and applications of imaging spectroscopy

Spectroscopy is a tool that has been used for decades to identify, understand, and quantify solid, liquid, or gaseous materials, especially in the laboratory. In disciplines ranging from astronomy to chemistry, spectroscopic measurements are used to detect absorption and emission features due to specific chemical bonds, and detailed analyses are used to determine the abundance and physical state of the detected absorbing/emitting species. Spectroscopic measurements have a long history in the study of the Earth and planets. Up to the 1990s remote spectroscopic measurements of Earth and planets were dominated by multispectral imaging experiments that collect high-quality images in a few, usually broad, spectral bands or with point spectrometers that obtained good spectral resolution but at only a few spatial positions. However, a new generation of sensors is now available that combines imaging with spectroscopy to create the new discipline of imaging spectroscopy. Imaging spectrometers acquire data with enough spectral range, resolution, and sampling at every pixel in a raster image so that individual absorption features can be identified and spatially mapped (Goetz et al., 1985).

Conference Paper↗

USGS2008

Effectiveness of an alluvial wetland on improving ground-water quality in a municipal well field, Cedar Rapids, Iowa, 1998-2006

Nutrients and pesticides are water-quality topics of concern in Iowa. Nitrate concentrations in the Cedar River and other streams in Iowa are among the highest in the Nation. A 12-mile reach of the Cedar River upstream from Cedar Rapids, Iowa, is identified on the Total Maximum Daily Load list for nitrate impairment by the U.S. Environmental Protection Agency. In addition, pesticide concentrations in water samples from alluvial aquifers in Iowa have been ranked as some of the largest in the Nation. The Cedar River, like many rivers with alluvium, affects the alluvial aquifer that is used as a municipal water supply for Cedar Rapids, Iowa. A continuing challenge for the Cedar Rapids Water Department is to provide drinking water that meets all drinking-water regulations; this is made more of a challenge because of the high (often over 10 milligrams per liter) nitrate concentrations in the Cedar River and the presence of other potential chemicals of concern, such as pesticides. An alluvial wetland proved useful in improving water quality. Samples from observation wells completed in the alluvial wetland near the municipal well field had nitrate concentrations that were four to six times lower when compared to river or upland sites; however, iron and manganese concentrations in samples from observation wells in the wetland areas were an order of magnitude higher when compared to the river or an upgradient well. Biological and chemical reduction processes were determined to mobilize inorganic constituents in accordance with physical chemistry principles. Generally, selected pesticides and two pesticide degradates of atrazine that were sampled for in alluvial wetland wells remained relatively unchanged, and indicated only a slight decrease in concentration compared to the Cedar River water samples. Pesticides were not detected above regulatory limits in any of the observation wells; however, one sample from the Cedar River had an atrazine detection at 4.5 micrograms per liter, which is above the maximum contaminant level of 3.0 micrograms per liter for drinking-water regulations for that compound. Results indicate that alluvial wetlands may provide substantial reductions of nitrate concentrations in ground water, and may be a useful strategy for the reduction of nitrate for municipal wells. Results for reducing pesticides were less dramatic than for nitrate, as pesticide concentrations were reduced slightly from the river to the wetland.

Iowa↗

USGS2003

The effect of chamber mixing velocity on bias in measurement of sediment oxygen demand rates in the Tualatin River basin, Oregon

Three sediment oxygen demand (SOD) measurement chambers were deployed in the Tualatin River near Tigard, Oregon, at river mile 10 in August 2000. SOD rates were calculated for three different circulation velocities during each chamber deployment. The SOD rate at each velocity was calculated from a graph of dissolved oxygen concentration versus elapsed time. An acoustic doppler current profiler (ADCP) was used to measure stream discharge and near-bottom water velocities in the Tualatin at river mile 10 and at two upstream locations. Measured river and chamber velocities were similar, indicating that results from the chambers were representative of instream effects. At low to moderate chamber circulation velocities (less than about 7.5 centimeters per second), the measured SOD rate appeared to be only slightly affected by the circulation velocity, indicating that the measured rates reflect the rate of oxygen utilization by chemical and biological reactions in the sediment rather than the rate of physical transport of oxygen to the sediment-water interface. Above about 7.5 centimeters per second, however, the measured oxygen depletion rate was affected by the circulation velocity, as sufficient energy was generated within the chamber to resuspend bottom sediment, as evidenced by increased turbidity. The resuspended sediment particles contributed to the measured oxygen loss rate by increasing the surface area of decomposing material in contact with the water column, resulting in a measured SOD rate that was anomalously high. Two different alignments of the chamber circulation diffusers were tested. With both diffuser alignments, SOD rates were similar at circulation velocities low enough to avoid sediment resuspension. The same resuspension effect probably exists in the Tualatin River during storm-runoff events following prolonged periods of low flow, when increased stream velocity may result in the resuspension of bottom sediments. The resuspension causes increased turbidity and increased oxygen demand, resulting in lower instream dissolved oxygen concentrations.

Water-Resources Investigations Report↗

USGS2014

Assessment of the geoavailability of trace elements from selected zinc minerals

This assessment focused on five zinc-bearing minerals. The minerals were subjected to a number of analyses including quantitative X-ray diffraction, optical microscopy, leaching tests, and bioaccessibility and toxicity studies. Like a previous comprehensive assessment of five copper-bearing minerals, the purpose of this assessment was to obtain structural and chemical information and to characterize the reactivity of each mineral to various simulated environmental and biological conditions. As in the copper minerals study, analyses were conducted consistent with widely accepted methods. Unless otherwise noted, analytical methods used for this study were identical to those described in the investigation of copper-bearing minerals. Two sphalerite specimens were included in the zinc-minerals set. One sphalerite was recovered from a mine in Balmat, New York; the second came from a mine in Creede, Colorado. The location and conditions of origin are significant because, as analyses confirmed, the two sphalerite specimens are quite different. For example, data acquired from a simulated gastric fluid (SGF) study indicate that the hydrothermally formed Creede sphalerite contains orders of magnitude higher arsenic, cadmium, manganese, and lead than the much older metamorphic Balmat sphalerite. The SGF and other experimental results contained in this report suggest that crystallizing conditions such as temperature, pressure, fluidization, or alteration processes significantly affect mineral properties—properties that, in turn, influence reactivity, solubility, and toxicity. The three remaining minerals analyzed for this report—smithsonite, hemimorphite, and hydrozincite—are all secondary minerals or alteration products of zinc-ore deposits. In addition, all share physical characteristics such as tenacity, density, streak, and cleavage. Similarities end there. The chemical composition, unit-cell parameters, acid-neutralizing potential, and other observable and quantifiable properties indicate very different minerals. Only one of each of these minerals was studied. Had this assessment included multiples of these minerals, geochemical and mineralogical distinctions would have emerged, similar to the results for the two sphalerite specimens.

Arizona;Chihuahua;Colorado;New York↗

USGS1989

Reactive iron transport in an acidic mountain stream in Summit County, Colorado: A hydrologic perspective

A pH perturbation experiment was conducted in an acidic, metal-enriched, mountain stream to identify relative rates of chemical and hydrologic processes as they influence iron transport. During the experiment the pH was lowered from 4.2 to 3.2 for three hours by injection of sulfuric acid. Amorphous iron oxides are abundant on the streambed, and dissolution and photoreduction reactions resulted in a rapid increase in the dissolved iron concentration. The increase occurred simultaneously with the decrease in pH. Ferrous iron was the major aqueous iron species. The changes in the iron concentration during the experiment indicate that variation exists in the solubility properties of the hydrous iron oxides on the streambed with dissolution of at least two compartments of hydrous iron oxides contributing to the iron pulse. Spatial variations of the hydrologic properties along the stream were quantified by simulating the transport of a coinjected tracer, lithium. A simulation of iron transport, as a conservative solute, indicated that hydrologie transport had a significant role in determining downstream changes in the iron pulse. The rapidity of the changes in iron concentration indicates that a model based on dynamic equilibrium may be adequate for simulating iron transport in acid streams. A major challenge for predictive solute transport models of geochemical processes may be due to substantial spatial and seasonal variations in chemical properties of the reactive hydrous oxides in such streams, and in the physical and hydrologic properties of the stream.

Geochimica et Cosmochimica Acta↗

USGS1990

Modelling streamwater chemistry as a mixture of soilwater end-members - An application to the Panola Mountain catchment, Georgia, U.S.A.

Streamwater chemistry at Panola Mountain research catchment, Georgia, U.S.A., is explained as a mixture of representative soilwater solutions that are considered to be temporally invariant to a first approximation. The selection of three end-members from all sampled soil waters is evaluated by comparing the observed and predicted streamwater concentration of six solutes (alkalinity, sulfate, sodium, magnesium, calcium and dissolved silica), which are assumed to mix conservatively, and by assessing the consistency of the implied hydrograph separation with the hydrological mechanisms that are believed to be operating in this catchment. The percentage of variation in the streamwater solute concentrations explained by the end-member mixing analysis (EMMA) ranges from 82 to >97%, and the hydrograph separation is, intuitively, physically reasonable. If the correct end-members have been identified, the streamwater chemical response to different levels of acidic deposition can be predicted by examining the change in each end-member under different loads; no hydrological model is required. If a traditional hydrochemical model, which is driven by rainfall quantity and quality, is desired, this analysis provides an indication of the model structure that would be necessary to reproduce both streamwater and soilwater chemistry.

Georgia↗

USGS2015

Geological processes and orchid biogeography with applications to southeast central America

This contribution owes its origins to a paper presentation by Dr. Calloway H. Dodson at the Second International Conference on Neotropical Orchidology held in San José, Costa Rica in May of2003 (Dodson 2003). Dr. Dodson outlined some ofthe reasons to suspect that regional geological fac-tors may play important roles in orchid speciation and biogeography and gave examples from the northwestern South America. He also suggested that evolutionary change in orchid might occur over fairly short time periods, perhaps even as short as decades, centuries or millennia (Dodson 2003, SHK lecture notes). These ideas stimulated the author, a professional earth scientist, to begin thinking about how these exciting ideas could begin to be tested in Costa Rica neighboring and Central American countries, an area that has drawn him to return frequently over the last decade. The present contribution is a proposal for integrating geological observations, such as the chronology of arc volcanic activity in Nicaragua,Costa Rica, and Panama, in hypothesis forming and testing of the geographic distribution of orchids (and possibly other biota). I initially focus on comparisons between orchid inventories on the windward slopes of mountainous regions (elevation > 1000 m)with high rainfall (> 1-2 m) in tropical regions, the so-called tropical cloud forests. These regions represent the tropical pre-montane rain forestto lower montane tropical rain forest life zones of Holdridge(1967) and the montane vegetation zone applied to Costa Rica and Panama by Dressler (1993). An important message of this paper is that such tropical mountainous regions are not necessarily static, but may change in elevation over geologic time due to active tectonic deformation and uplift and that the presence of active volcanism in a mountain range may also introduce additional chemical factors, such as volcanic gases, acid rain, and volcanic soils, and also physical factors, such as interruption of gene flow by explosive eruptions and coverage by their air fall products such as ash (tephra), lava flows, and lahars (volcanic mudflows). Thus over a given geological time interval, forests may be slowly increasing in elevation by tectonic uplift or by the accumulation of volcanic products such as steep-sided strato volcanoes (built from both lavas and tephra), or by down-slope accumulations of lava flows or lahars. Mountains may also lose elevation by erosion or by tectonic subsidence. As we shall see, tropical Central America shows an extraordinarily high level of tectonic and volcanic history that has changed its geography and, by implication, climate, life zones,and likely orchid distribution. My working hypo thesis put forward for testing is that orchid adaptations to these changes may have led to the development of new species and endemism in this region.

Lankesteriana↗

USGS1981

Water-quality data for selected stations in the East Everglades, Florida

The results of water-quality samples collected from April 1978 through April 1980 from three canal stations, four marsh stations, and two ground-water stations within the East Everglades, Dade County, Florida, are tabulated in 37 tables. The major categories of parameters analyzed are field measurements, physical characteristics, macronutrients (carbon, nitrogen, and phosphorus), major ions, trace elements, and algae. Chemical data for bulk-precipitation stations within and adjacent to the East Everglades are also given. The parameters analyzed include macronutrients, major ions, and trace elements. The period of record for these stations is October 1977 through April 1980. Bottom material at the canal and marsh stations was collected twice during the investigation. These data include analyses for macronutrients, trace elements, and chlorinated-hydrocarbon insecticides.

Florida↗

USGS2005

Water-quality assessment of part of the Upper Mississippi River Basin, Minnesota and Wisconsin — Ground-water quality along a flow system in the Twin Cities metropolitan area, Minnesota, 1997-98

As part of a national analysis of the effects of land use on ground-water quality for the National Water-Quality Assessment Program, the U.S. Geological Survey sampled wells along a flow system in surficial glacial aquifers in the northwestern part of the Twin Cities metropolitan area during 1997 and 1998. In addition, a reconnaissance steady-state ground-water model was developed to estimate flowpaths and dates of ground-water recharge using a particle-tracking routine. Sediment samples collected during drilling had high horizontal hydraulic conductivities (ranging from about 3.1 to about 190 feet per day, based on sediment-size analysis of well cuttings), small organic carbon concentrations (ranging from less than 0.2 to 160 grams per kilogram), and pH values that were mostly alkaline (ranging from 4.9 to 8.2). Water samples were analyzed for physical properties, major ions, iron, manganese, nutrients, organic carbon, radon, pesticides, volatile organic compounds (VOCs), chlorofluorocarbons, tritium, and isotopes of nitrogen, hydrogen, and oxygen. Most of the water samples had small dissolved-oxygen concentrations (less than 1 milligram per liter). Calcium, magnesium, sodium, bicarbonate, sulfate, and chloride were the primary dissolved constituents in water samples. Nitrite plus nitrate as nitrogen (nitrate) concentrations were less than the U.S. Environmental Protection Agency (USEPA) Maximum Contaminant Level of 10 mg/L. Nitrogen isotope ratios indicated that the sources of nitrate primarily were soils, animal waste, or denitrification that increased nitrogen isotope ratios in nitrate. Small concentrations of pesticides were detected in the shallow parts of the aquifer. The herbicide prometon was the most frequently detected pesticide. Herbicides applied to control grasses and weeds in corn (atrazine, simazine, and metolachlor) also were frequently detected in water samples. All pesticide and VOCs detected were below USEPA Maximum Contaminant Levels or Health Advisory Limits. Chlorofluorocarbon compounds and tritium concentrations were used to estimate dates of recharge of ground-water samples. In general, shallower ground-water samples were more recently recharged although most water sampled from the aquifer was recharged after 1955. Although land use had substantial effects on ground-water quality, the distribution of contaminants in the aquifer also is affected by complex combinations of factors and processes that include sources of natural and anthropogenic contaminants, three-dimensional advective flow, physical and hydrologic settings, age and evolution of ground water, and transformation of chemical compounds along the flow system. Compounds such as nitrate and dissolved oxygen were greatest in water samples from the upgradient end of the flow system and near the water table. Specific conductance and dissolved solids increased along the flow system and with depth due to increase in residence time in the flow system and dissolution of aquifer materials.

Minnesota↗

USGS2007

Influence of Locally Derived Recharge on the Water Quality and Temperature of Springs in Hot Springs National Park, Arkansas

The hot springs of Hot Springs National Park consist of a mixture of water from two recharge components: a primary hot-water component and a secondary cold-water component. Widespread distribution of fractures enables mixing of the hot- and cold-water components of flow near the discharge area for the springs. Urbanization in the area near the hot springs of Hot Springs National Park has increased the potential for degradation of the quality of surface-water runoff and locally derived ground-water recharge to the hot springs. Previous studies by the U.S. Geological Survey have indicated that water from some cold-water springs and wells in the vicinity of Hot Springs, Arkansas, showed evidence of contamination and that water from locally derived cold-water recharge might contribute 25 percent of the total flow to the hot springs after storms. Water samples were collected during base-flow conditions at nine hot springs and two cold-water springs in September 2000. Nine hot springs and one cold-water spring were resampled in October 2001 after a storm that resulted in a measurable decrease in water temperature in selected hot springs. Water samples were analyzed for a variety of dissolved chemical constituents (nutrients, major ions, trace elements, pesticides, semivolatile compounds, isotopes, and radiochemicals), physical properties, field measurements, and bacteria. Comparison of analyses of samples collected during base-flow conditions from the springs in 2000 and during a storm event in 2001 with the results from earlier studies dating back to the late 1800's indicates that little change in major, minor, and trace constituent chemistry has occurred and that the water continues to be of excellent quality. Water-quality data show distinguishable differences in water chemistry of the springs during base-flow and stormflow conditions, indicating changing input of cold-water recharge relative to hot-water recharge. Silica, total dissolved solids, strontium, barium, and sulfate show statistically significant differences between the median values of base-flow and stormflow samples. While variations in these constituents do not degrade water quality, the differences do provide evidence of variability in the factors controlling water quality of the hot springs and show that water quality is influenced by the locally derived, cold-water component of flow to the springs. Water temperature was measured continuously (3-minute intervals) between August 2000 and October 2002 at four hot springs. Continuous water-temperature data at the springs provide no indication of persistent long-term change in water temperature through time. Short time-scale water-temperature decreases occur in response to mixing of hot-springs water with locally derived recharge after storm events; the magnitude of these decreases varied inversely with the amount of rainfall. Maximum decreases in water temperature for specific storms had a non-linear relation with the amount of precipitation measured for the events. Response time for water temperature to begin decreasing from baseline temperature as a result of storm recharge was highly variable. Some springs began decreasing from baseline temperature as quickly as 1 hour after the beginning of a storm; one spring had an 8-hour minimum response time to show a storm-related temperature decrease. Water-quality, water-temperature, isotopic, and radiochemical data provide multiple lines of evidence supporting the importance of the contribution of cold-water recharge to hot springs. All the springs sampled indicated some measure of influence from local recharge. Binary mixing models using silica and total dissolved solids indicate that cold-water recharge from stormflow contributes an estimated 10 to 31 percent of the flow of hot springs. Models using water temperature indicate that cold-water recharge from stormflow contributes an estimated 1 to 35 percent of the flow of the various hot springs. Alth

Scientific Investigations Report↗

USGS1984

The concept of electron activity and its relation to redox potentials in aqueous geochemical systems

The definition of a formal thermodynamic activity of electrons in redox reactions appears in the literature of the 1920's. The concept of pe as -log (electron activity) was introduced by Jorgensen in 1945 and popularized in the geochemical literature by Sillen, who considered pe and pH as master variables in geochemical reactions. The physical significance of the concept of electron activity was challenged as early as 1928. However, only in the last two decades have sufficient thermodynamic data become available to examine this question quantitatively. The chemical nature of hydrated electrons differs greatly from that of hydrated protons, and thermodynamic data show that hydrated electrons cannot exist at physically meaningful equilibrium concentrations under natural conditions. This has important consequences for the understanding of redox processes in natural waters. These are: (1) the analogy between pe and pH as master variables is generally carried much further than is justified; (2) a thermodynamically meaningful value of redox potential cannot be assigned to disequilibrium systems; (3) the most useful approach to the study of redox characteristics is the analysis and study of multiple redox couples in the system; and (4) for all practical purposes, thermodynamically defined redox potentials do not exist (and thus cannot be measured) in natural waters. The overall implication for natural systems is that, in terms of redox reactions, each case must be considered on an individual and detailed basis. Field studies would appear to be a mandatory part of any site-specific study; conclusions regarding redox processes cannot be based solely on electrode measurements or thermodynamic stability calculations. (USGS)

Open-File Report↗

USGS2017

Optimal hydrograph separation using a recursive digital filter constrained by chemical mass balance, with application to selected Chesapeake Bay watersheds

Quantitative estimates of base flow are necessary to address questions concerning the vulnerability and response of the Nation’s water supply to natural and human-induced change in environmental conditions. An objective of the U.S. Geological Survey National Water-Quality Assessment Project is to determine how hydrologic systems are affected by watershed characteristics, including land use, land cover, water use, climate, and natural characteristics (geology, soil type, and topography). An important component of any hydrologic system is base flow, generally described as the part of streamflow that is sustained between precipitation events, fed to stream channels by delayed (usually subsurface) pathways, and more specifically as the volumetric discharge of water, estimated at a measurement site or gage at the watershed scale, which represents groundwater that discharges directly or indirectly to stream reaches and is then routed to the measurement point. Hydrograph separation using a recursive digital filter was applied to 225 sites in the Chesapeake Bay watershed. The recursive digital filter was chosen for the following reasons: it is based in part on the assumption that groundwater acts as a linear reservoir, and so has a physical basis; it has only two adjustable parameters (alpha, obtained directly from recession analysis, and beta, the maximum value of the base-flow index that can be modeled by the filter), which can be determined objectively and with the same physical basis of groundwater reservoir linearity, or that can be optimized by applying a chemical-mass-balance constraint. Base-flow estimates from the recursive digital filter were compared with those from five other hydrograph-separation methods with respect to two metrics: the long-term average fraction of streamflow that is base flow, or base-flow index, and the fraction of days where streamflow is entirely base flow. There was generally good correlation between the methods, with some biased slightly high and some biased slightly low compared to the recursive digital filter. There were notable differences between the days at base flow estimated by the different methods, with the recursive digital filter having a smaller range of values. This was attributed to how the different methods determine cessation of quickflow (the part of streamflow which is not base flow). For 109 Chesapeake Bay watershed sites with available specific conductance data, the parameters of the filter were optimized using a chemical-mass-balance constraint and two different models for the time-dependence of base-flow specific conductance. Sixty-seven models were deemed acceptable and the results compared well with non-optimized results. There are a number of limitations to the optimal hydrograph-separation approach resulting from the assumptions implicit in the conceptual model, the mathematical model, and the approach taken to impose chemical mass balance (including tracer choice). These limitations may be evidenced by poor model results; conversely, poor model fit may provide an indication that two-component separation does not adequately describe the hydrologic system’s runoff response. The results of this study may be used to address a number of questions regarding the role of groundwater in understanding past changes in stream-water quality and forecasting possible future changes, such as the timing and magnitude of land-use and management practice effects on stream and groundwater quality. Ongoing and future modeling efforts may benefit from the estimates of base flow as calibration targets or as a means to filter chemical data to model base-flow loads and trends. Ultimately, base-flow estimation might provide the basis for future work aimed at improving the ability to quantify groundwater discharge, not only at the scale of a gaged watershed, but at the scale of individual reaches as well.

Scientific Investigations Report↗