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Physical, chemical, and biological characteristics of selected headwater streams along the Allegheny Front, Blair County, Pennsylvania, July 2011–September 2013

The Altoona Water Authority (AWA) obtains all of its water supply from headwater streams that drain western Blair County, an area underlain in part by black shale of the Marcellus Formation. Development of the shale-gas reservoirs will require new access roads, stream crossing, drill-pad construction, and pipeline installation, activities that have the potential to alter existing stream channel morphology, increase runoff and sediment supply, alter streamwater chemistry, and affect aquatic habitat. The U.S. Geological Survey, in cooperation with Altoona Water Authority and Blair County Conservation District, investigated the water quality of 12 headwater streams and biotic health of 10 headwater streams. Channel morphology was characterized at 10 of 12 stream sites using 500-foot (minimum) longitudinal profiles, four cross-sections each, and pebble counts. Channel slopes ranged from 0.008 in Poplar Run near Newry to 0.045 in Mill Run. In general, streams draining watersheds of 5 square miles or less and at higher elevation had the steepest slopes. On the basis of the median particle size, determined during pebble counts, the streambed substrate can be characterized as cobble (Mill Run, Bells Gap Run, Tipton Run, and Sink Run), a mix of gravel and cobble (South Poplar Run, Dry Gap Run, Glenwhite Run, Sugar Run, Blair Gap Run), and gravel (Poplar Run, Newry). Daily mean values of gage height were determined, and continuous (30-minute interval) data consisting of specific conductance and water temperature were collected, at four sites; each site showed typical seasonal fluctuations and the effects of precipitation. Streamflow affected discrete water-quality. Dissolved oxygen always increased with increased streamflow. Most cations (including barium and strontium), along with pH, specific conductance, and total dissolved solids, decreased with greater streamflow, reflecting the dilution effect of moderately acidic surface runoff and precipitation on groundwater discharge (base flow) into the stream channels. Concentrations of trace elements varied by constituent and streamflow. On the basis of the results of water-quality analyses for the selected constituents, the water quality in 9 of the 12 streams can be considered fair or attaining with no measured constituent exceeding a U.S. Environmental Protection Agency maximum or secondary contaminant level. Abandoned mine drainage (AMD) affects Glenwhite Run, Blair Gap Run, and Sugar Run. For Sugar Run, the AMD is reflected in the elevated iron concentration (greater than 300 micrograms per liter). Manganese concentrations greater than 50 micrograms per liter were measured in Glenwhite Run, Sugar Run, and Blair Gap Run. A mixing curve based upon chloride/bromide ratios for two end points—precipitation and deicing salts—indicate that deicing salt is migrating to the streams. A similar curve representative of late-emerging flowback water from Marcellus gas wells indicated that the surface-water samples had not been influenced by such brines. On the basis of the concentration of major ions, the streams in the study area generally had mixed cation and anion compositions. Calcium is the dominant cation in one stream. Carbonate and bicarbonate are the dominant anions for two streams, and sulfate is dominant in three streams. The remaining six streams do not have a dominant ion. Biotic health was characterized at 10 of 12 stream sites; the two sites excluded were established late in the study period (May 2013) for refinement of water quality in the headwaters of Poplar Run and the location of Marcellus Formation gas wells. On the basis of the Maryland Index of Biotic Integrity (MdIBI) for fish assemblages, 8 of 10 streams can be considered in fair health. Tipton Run had the highest MdIBI score (3.75) and the greatest number of native species. South Poplar Run had the lowest MdIBI score (1.75); pollution tolerant blacknose dace was dominant. On the basis of the Pennsylvania Department of Environmental Protection macroinvertebrate index of biotic integrity, 9 of 10 streams were characterized as attaining, with scores as high as 88.9 at Tipton Run. Only Sugar Run was characterized as impaired, with a score of 40.4.

Pennsylvania

Tampa Bay Ocean and Coastal Acidification Monitoring Quality Assurance Project Plan

Coastal acidification caused by eutrophication, freshwater inflow, and upwelling is already affecting many estuaries worldwide and can be exacerbated by ocean acidification that is caused by increasing carbon dioxide in the atmosphere. Effective management, mitigation, and (or) adaptation to the effects of coastal and ocean acidification require careful monitoring of the resulting changes in seawater chemistry. Local, regional, and national agencies and institutions organizing acidification-monitoring and research efforts work toward standardizing data collection and reporting protocols so that data can be shared and compared across regions and synthesized into national assessments. This document describes a Quality Assurance Project Plan for the collection and reporting of seawater chemical and physical data using standardized methods and published best practices relevant for monitoring coastal and ocean acidification. The plan specifically addresses procedures for a joint partnership, the Tampa Bay Ocean and Coastal Acidification Monitoring project, conducted by the U.S. Geological Survey, the U.S. Environmental Protection Agency, and the Tampa Bay Estuary Program in the Tampa Bay estuary, Florida. The plan describes recommended procedures for project organization, sampling process design and methods, data-quality objectives and criteria, data validation and management procedures, and project deliverables.

Florida

Chapter B. Physical, Chemical, and Biological Responses of Streams to Increasing Watershed Urbanization in the Piedmont Ecoregion of Georgia and Alabama, 2003

As part of the U.S. Geological Survey National Water-Quality Assessment Program?s effort to assess the physical, chemical, and biological responses of streams to urbanization, 30 wadable streams were sampled near Atlanta, Ga., during 2002?2003. Watersheds were selected to minimize natural factors such as geology, altitude, and climate while representing a range of urban development. A multimetric urban intensity index was calculated using watershed land use, land cover, infrastructure, and socioeconomic variables that are highly correlated with population density. The index was used to select sites along a gradient from low to high urban intensity. Response variables measured include stream hydrology and water temperature, instream habitat, field properties (pH, conductivity, dissolved oxygen, turbidity), nutrients, pesticides, suspended sediment, sulfate, chloride, Escherichia coli (E. coli) concentrations, and characterization of algal, invertebrate and fish communities. In addition, semipermeablemembrane devices (SPMDs)?passive samplers that concentrate hydrophobic organic contaminants such as polycyclicaromatic hydrocarbons (PAHs)?were used to evaluate water-quality conditions during the 4 weeks prior to biological sampling. Changes in physical, chemical, and biological conditions were evaluated using both nonparametric correlation analysis and nonmetric multidimensional scaling (MDS) ordinations and associated comparisons of dataset similarity matrices. Many of the commonly reported effects of watershed urbanization on streams were observed in this study, such as altered hydrology and increases in some chemical constituent levels. Analysis of water-chemistry data showed that specific conductance, chloride, sulfate, and pesticides increased as urbanization increased. Nutrient concentrations were not directly correlated to increases in development, but were inversely correlated to percent forest in the watershed. Analyses of SPMD-derived data showed that bioassays and certain chemical constituents such as pyrene and benzophenanthrene, both PAHs found in coal tar, were strongly correlated with measures of watershed urbanization. Hydrologic variability metrics indicated that as urban development increased, streams became flashier, with characteristic high flows having shorter duration. The hydrologic effects associated with urbanization were greatest during the fall and least apparent during the winter. No correlations were observed between increasing urbanization and stream temperature or changes in stream habitat. Algal, invertebrate, and fish communities exhibited statistically significant changes as watersheds became increasingly urban, with the strongest responses observed in the invertebrate community followed by fishes, then algal diatom communities. Invertebrate communities were the most responsive to increasing urbanization with Ephemeroptera, Plecoptera, and Tricoptera taxa, especially Plecoptera (stoneflies) responding negatively and most strongly to increasing urbanization. Invertebrate communities were influenced more significantly by water quality, although significant responses to altered hydrology also were noted. In terms of the fish community, the percentage of cyprinids present in the stream was the only Index of Biotic Integrity metric that responded negatively to increases in watershed urbanization. Fish community response to urbanization was intermediate relative to algae and invertebrates with respect to significant metric responses as well as the overall community response to increasing urbanization. Measures of hydrologic variability were the most influential environmental variables affecting the algal community. Although sites were originally chosen to represent a gradient of increasing urbanization, a cluster analysis performed on the component metrics of the urban index categorized sites into four distinct groups. Multivariate analysis based on nonmetric MDS and related analyses of data ma

Alabama, Georgia

K1-95-HW: Cruise report 1995 - Preliminary results, phase III: Sediment chemistry and biological sampling survey

Mamala Bay, off the south shore of the island of Oahu, has been used as a repository of dredged material primarily from Pearl and Honolulu Harbors for over a century. The U.S. Geological Survey, U.S. Army Corps of Engineers, and the U.S. Environmental Protection Agency are conducting an integrated study on the distribution and character of dredged materials as well as the effects of dredged material on the marine environment. A three phase study is providing information to evaluate the effects on seafloor substrate and the benthic fauna. The studies include geophysical profiling and imaging, bottom photography, sampling, chemical and physical analyses of sediment, and evaluations of the benthic population, population density, and adverse impacts to the benthic fauna. Phase 1, conducted in 1993, inventoried the seafloor via remote sensing. Sidescan sonar and subbottom profilers characterized the seafloor in and around the disposal sites, and the resulting products reveal the character and extent of the dredged material. These data were used to plan Phase 2 in 1994, a sampling program that employed subbottom profilers, video and still photography, and seafloor sampling to ground truth the sonar mosaic and identify the seafloor substrates responsible for the various acoustic signatures on the sonar images and subbottom profiles. Box coring provided the samples necessary to distinguish dredged material from native sediment, and for the chemical analyses used to determine contaminant concentrations. Phase 3 studies conducted in June of 1995 consisted of box core sampling for chemical and biological analyses. Specific studies include: infaunal taxonomy and population density, bioassay/bioaccumulation, sediment chemistry, and post-disposal resuspension and transport. The 1995 survey, conducted June 14 through 17, resulted in the collection of 39 box cores from 20 different stations. Multiple box cores were composited at 7 different locations occupied in 1994, to provide the material required for the 7 bioassay and bioaccumulation analyses currently underway (Figure 1). Seventeen of the 20 stations occupied provided the biological samples for the benthic infaunal identification and population density study conducted by Dr. Julie Brock of the University of Hawaii, and the sediment chemistry analyses conducted (and completed) by Quanterra Environmental Laboratories (Figure 1). Seven of the 20 stations occupied in 1995 were occupied in 1994, and provide the data for direct comparison of sediment chemistry at the same sites from two consecutive years. The sum total of the data collected from all three phases of the monitoring program will provide the U.S. Army Corps of Engineers and the U.S. Environmental Protection Agency with the information required to make informed decisions as to the management of the South Oahu disposal site in Mamala Bay.

Hawai'i

Passive sampling of groundwater wells for determination of water chemistry

Introduction Passive groundwater sampling is defined as the collection of a water sample from a well without the use of purging by a pump or retrieval by a bailer (Interstate Technology and Regulatory Council [ITRC], 2006; American Society for Testing and Materials [ASTM], 2014). No purging means that advection of water is not involved in collecting the water sample from the well. Passive samplers rely on diffusion as the primary process that drives their collection of chemical constituents. Diffusion is the transport of chemicals caused by the presence of a chemical gradient. Chemicals tend to move or diffuse from areas of higher concentration to areas of lower concentration to reach an average or equilibrium concentration. Passive sampling of groundwater relies on the ambient exchange of groundwater in the formation with water in the screened or open interval of a well. In this report, the term formation is used to describe all saturated hydrogeologic units that yield water to a well. If the well opening is unclogged and free of a film of deposits from physical turbidity or chemical precipitation, then the exchange of groundwater is likely adequate, and the water in the open interval will be representative of water in the formation. In some cases, the passive sample from the well opening can be more representative of groundwater from the formation than a sample collected by pumping if pumping induces mixing of water in the open interval with stagnant casing water that has undergone chemical alteration (Harte and others, 2018). In most cases, passive sampling will better represent the ambient groundwater chemistry flowing through the open interval of a well because pumping may capture water of different chemistry from downgradient or lateral areas that would not normally pass through the well. Three basic types of passive samplers are discussed in this report. The first type of passive sampler is the equilibrium-membrane type, which includes a semi-permeable membrane through which chemicals diffuse or permeate. Permeation is simply the process of water or chemicals moving through openings in the membrane. The authors contend that permeation is dominated by diffusion for many of the passive samplers discussed in this report. Some passive equilibrium-membrane-type samplers allow most types of chemical constituents through, whereas others allow the diffusion of only selected groups of chemicals. Once the chemical constituents are inside the membrane, they are retained by the equilibration of concentrations inside the sampler with those outside the sampler. The second type of passive sampler is an equilibrium-thief type, which has no semi-permeable membrane. Chemical constituents simply move through the openings in the body of the sampler either initially through advection and dispersion or over time primarily by diffusion. Chemical constituents reach equilibrium between the water in the sampler and the water in the well and are captured in the sampler when the sampler is closed. The third type of passive sampler is an accumulation-type sampler that contains sorptive media. Selected chemical constituents are sorbed onto the media that the sampler contains for later extraction and analysis. Although passive samplers have been available for more than 15 years (from present [2020]), their use by U.S. Geological Survey (USGS) hydrologists and hydrologic technicians to monitor groundwater quality largely has been limited to selected research studies. The authors believe that this may be the result of (1) a lack of exposure of most USGS personnel to passive samplers and the uses of these samplers and (2) the lack of a USGS-approved protocol for the proper use of these samplers by USGS personnel. This report is an effort to fill those two needs. The focus of this report is on hydraulic, hydrologic, and chemical considerations in the application of passive samplers and interpretation of groundwater chemistry results obtained using passive samplers in wells. This report describes the differences between purging and passive sampling methods in groundwater and explains how and why passive samplers work. The report points out the advantages and limitations of passive samplers in general and for each particular type of passive sampler. Important considerations to be taken into account prior to the use of passive samplers are discussed, such as defining the data-quality objectives, the water-quality constituents to be sampled, sample volumes required for analysis, well construction of the sampling network, and the geologic formations that will be sampled. Potential applications of passive samplers also are discussed, such as chemical-vertical profiling of wells. A general field protocol for the deployment, recovery, and sample collection using these devices is described, and some overall guidance for the practitioner with application examples is given. Comparison methods used to evaluate results from passive sampling versus purge sampling also are discussed.

Techniques and Methods

Chemical variations in Yellowknife Bay formation sedimentary rocks analyzed by ChemCam on board the Curiosity rover on Mars

The Yellowknife Bay formation represents a ~5 m thick stratigraphic section of lithified fluvial and lacustrine sediments analyzed by the Curiosity rover in Gale crater, Mars. Previous works have mainly focused on the mudstones that were drilled by the rover at two locations. The present study focuses on the sedimentary rocks stratigraphically above the mudstones by studying their chemical variations in parallel with rock textures. Results show that differences in composition correlate with textures and both manifest subtle but significant variations through the stratigraphic column. Though the chemistry of the sediments does not vary much in the lower part of the stratigraphy, the variations in alkali elements indicate variations in the source material and/or physical sorting, as shown by the identification of alkali feldspars. The sandstones contain similar relative proportions of hydrogen to the mudstones below, suggesting the presence of hydrous minerals that may have contributed to their cementation. Slight variations in magnesium correlate with changes in textures suggesting that diagenesis through cementation and dissolution modified the initial rock composition and texture simultaneously. The upper part of the stratigraphy (~1 m thick) displays rocks with different compositions suggesting a strong change in the depositional system. The presence of float rocks with similar compositions found along the rover traverse suggests that some of these outcrops extend further away in the nearby hummocky plains.

Journal of Geophysical Research E: Planets

Veneers, rinds, and fracture fills: Relatively late alteration of sedimentary rocks at Meridiani Planum, Mars

Veneers and thicker rinds that coat outcrop surfaces and partially cemented fracture fills formed perpendicular to bedding document relatively late stage alteration of ancient sedimentary rocks at Meridiani Planum, Mars. The chemistry of submillimeter thick, buff-colored veneers reflects multiple processes at work since the establishment of the current plains surface. Veneer composition is dominated by the mixing of silicate-rich dust and sulfate-rich outcrop surface, but it has also been influenced by mineral precipitation, including NaCl, and possibly by limited physical or chemical weathering of sulfate minerals. Competing processes of chemical alteration (perhaps mediated by thin films of water or water vapor beneath blanketing soils) and sandblasting of exposed outcrop surfaces determine the current distribution of veneers. Dark-toned rinds several millimeters thick reflect more extensive surface alteration but also indicate combined dust admixture, halite precipitation, and possible minor sulfate removal. Cemented fracture fills that are differentially resistant to erosion occur along the margins of linear fracture systems possibly related to impact. These appear to reflect limited groundwater activity along the margins of fractures, cementing mechanically introduced fill derived principally from outcrop rocks. The limited thickness and spatial distribution of these three features suggest that aqueous activity has been rare and transient or has operated at exceedingly low rates during the protracted interval since outcropping Meridiani strata were exposed on the plains surface.

Journal of Geophysical Research E: Planets

Evolving magma storage conditions beneath Mount St. Helens inferred from chemical variations in melt inclusions from the 1980-1986 and current (2004-2006) eruptions

Major element, trace element, and volatile concentrations in 187 glassy melt inclusions and 25 groundmass glasses from the 1980-86 eruption of Mount St. Helens are presented, together with 103 analyses of touching FE-Ti oxide pairs from the same samples. These data are used to evaluate the temporal evolution of the magmatic plumbing system beneath the volcano during 1980-86 and so provide a framework in which to interpret analyses of melt inclusions from the current (2004-2006) eruption. Major and trace element concentrations of all melt inclusions lie at the high SiO 2 end of the data array defined by eruptive products of the late Quaternary age from Mount St. Helens. For several major and trace elements, the glasses define a trend that is oblique to the whole-rock trend, indicating that different mineral assemblages were responsible for the two trends. The whole-rock trend can be ascribed to differentiation of hydrous basaltic parents in a deep-seated magma reservoir, probably at depths great enough to stabilize garnet. In contrast, the glass trends were generated by closed-system crystallization of the phenocryst and microlite mineral assemblages at low pressures. The dissolved H 2 O content of the melt inclusions from 1980-86, as measured by the ion microprobe, ranges from 0 to 6.7 wt. percent, with the highest values obtained from the plinian phase of May 18, 1980. Water contents decrease with increasing SiO 2 , consistent with decompression-driven crystallization. Preliminary data for dissolved CO 2 in melt inclusions from the May 18 plinian phase from August 7, 1980, indicate that X H 2 O in a vapor phase was approximately constant at 0.80, irrespective of H 2 O content, suggestive of closed-system degassing with a high bubble fraction or gas streaming through the subvolcanic system. Temperature and f O 2 estimates for touching Fe-Ti oxides show evidence for heating during crystallization owing to release of latent heat. Consequently, magmas with the highest microlite crystallinities record the highest temperatures. Magmas also become progressively reduced during ascent and degassing, probably as a result of redox equilibria between exsolving S-bearing gases and magmas. The lowest temperature oxides have f O 2 ≈ NNO, similar to high-temperature fumarole gases from the volcano. The temperature and f O 2 of the magma tapped by the plinian phase of May 18, 1980, are 870-875°C and NNO+0.8, respectively. The dissolved volatile contents of the melt inclusions have been used to calculate sealing pressures; that is, the pressure at which chemical exchange between inclusion and matrix melt ceased. These are greatest for the May 18 plinian magma (120 to 320 MPa); lower pressures are recorded by samples of the preplinian cryptodome and by all post-May 18 magmas. Magma crystallinity, calculated from melt-inclusion Rb contents, is negatively correlated with sealing pressure, consistent with decompression crystallization. Elevated contents of Li in melt inclusions from the cryptodome and post-May 18 samples are consistent with transfer of Li in a magmatic vapor phase from deeper parts of the magma system to magma stored at shallower levels. The Li enrichment attains its maximum extent at ~150 MPa, which is ascribed to separation of a single vapor phase into H 2 O-rich gas and dense Li-rich brine at the top of the magma column. There are striking correlations between melt-inclusion chemistry and monitoring data for the 1980-86 eruption. Dissolved SO 2 contents of melt inclusions from any given event, multiplied by the mass of magma erupted during that event, correlate with the measured flux of SO 2 at the surface, suggesting that magma degassing and melt-inclusion sealing are closely related in time and space. Textural and chemical evidence indicates that melt inclusions became effectively sealed (physically or kinetically) shortly before eruption. Thus by converting pressure to depth using a density model and edifice-loading algorithm for the volcano, changing depths of magma extraction with time can be tracked and compared to the seismic record. The plinian eruption of May 18, 1980, involved magma stored 5-11 km below sea level; this is inferred to be the subvolcanic magma chamber. The preceding eruptions, including the May 18, 1980, blast, involved magma withdrawal from the cryptodome and conduit down to 5 km below sea level. Subsequent 1980 eruptions tapped magma down to depths of ≤10 km below sea level. Tapping of magma stored deeper than 2 km below sea level stopped abruptly at the end of 1980, coincident with the onset of extensive shallow seismicity and a change from explosive to effusive eruption style from 1981 to 1986. Overall, the 1980-86 eruption is consistent with the evisceration of a thin, vertically extensive body of magma extending from 5 to at least 11 km below sea level and connected to the surface by a thin conduit. In the absence of sustained high magma-supply rates from depth, decompression crystallization of magma ascending through the system leads eventually to plugging of the conduit. The current eruption of Mount St. Helens shares some similarities with the 1981-86 dome-building phase of the previous eruption, in that there is extensive shallow seismicity and extrusion of highly crystalline material in the form of a sequence of flows and spines. Melt inclusions from the current eruption have low H 2 O contents, consistent with magma extraction from shallow depths. Highly enriched Li in melt inclusions suggests that vapor transport of Li is a characteristic feature of Mount St. Helens. Melt inclusions from the current eruption have subtly different trace-element chemistry from all but one of the 1980-86 melt inclusions, with steeper rareearth-element (REE) patterns and low U, Th, and high-fieldstrength elements (HFSE), indicating addition of a new melt component to the magma system. It is anticipated that increasing involvement of the new melt component will be evident as the current eruption proceeds.

Washington

Relations between basin characteristics and stream water chemistry in alpine/subalpine basins in Rocky Mountain National Park, Colorado

Relations between stream water chemistry and topographic, vegetative, and geologic characteristics of basins were evaluated for nine alpine/subalpine basins in Rocky Mountain National Park, Colorado, to identify controlling parameters and to better understand processes governing patterns in stream water chemistry. Fractional amounts of steep slopes (≥30°), unvegetated terrain, and young surficial debris within each basin were positively correlated to each other. These terrain features, which commonly occur on steep valley side slopes underlain by talus, were negatively correlated with concentrations of base cations, silica, and alkalinity and were positively correlated with nitrate, acidity, and runoff. These relations might result from the short residence times of water and limited soil development in the talus environment, which limit chemical weathering and nitrogen uptake. Steep, unvegetated terrains also tend to promote high Ca/Na ratios in stream water, probably because physical weathering rates in those areas are high. Physical weathering exposes fresh bedrock that contains interstitial calcite, which weathers relatively quickly. The fractional amounts of subalpine meadow and, to a lesser extent, old surficial debris in the basins were positively correlated to concentrations of weathering products and were negatively correlated to nitrate and acidity. These relations may reflect more opportunities for silicate weathering and nitrogen uptake in the lower‐energy environments of the valley floor, where soils are finer‐grained, older, and better developed and slopes are relatively flat. These results indicate that in alpine/subalpine basins, slope, vegetation (or lack thereof), and distribution and age of surficial materials are interrelated and can have major effects on stream water chemistry.

Colorado

Mineralogic and compositional properties of Martian soil and dust: results from Mars Pathfinder

Mars Pathfinder obtained multispectral, elemental, magnetic, and physical measurements of soil and dust at the Sagan Memorial Station during the course of its 83 sol mission. We describe initial results from these measurements, concentrating on multispectral and elemental data, and use these data, along with previous Viking, SNC meteorite, and telescopic results, to help constrain the origin and evolution of Martian soil and dust. We find that soils and dust can be divided into at least eight distinct spectral units, based on parameterization of Imager for Mars Pathfinder (IMP) 400 to 1000 nm multispectral images. The most distinctive spectral parameters for soils and dust are the reflectivity in the red, the red/blue reflectivity ratio, the near-IR spectral slope, and the strength of the 800 to 1000 nm absorption feature. Most of the Pathfinder spectra are consistent with the presence of poorly crystalline or nanophase ferric oxide(s), sometimes mixed with small but varying degrees of well-crystalline ferric and ferrous phases. Darker soil units appear to be coarser-grained, compacted, and/or mixed with a larger amount of dark ferrous materials relative to bright soils. Nanophase goethite, akaganeite, schwertmannite, and maghemite are leading candidates for the origin of the absorption centered near 900 nm in IMP spectra. The ferrous component in the soil cannot be well-constrained based on IMP data. Alpha proton X-ray spectrometer (APXS) measurements of six soil units show little variability within the landing site and show remarkable overall similarity to the average Viking-derived soil elemental composition. Differences exist between Viking and Pathfinder soils, however, including significantly higher S and Cl abundances and lower Si abundances in Viking soils and the lack of a correlation between Ti and Fe in Pathfinder soils. No significant linear correlations were observed between IMP spectral properties and APXS elemental chemistry. Attempts at constraining the mineralogy of soils and dust using normative calculations involving mixtures of smectites and silicate and oxide minerals did not yield physically acceptable solutions. We attempted to use the Pathfinder results to constrain a number of putative soil and dust formation scenarios, including palagonitization and acid-fog weathering. While the Pathfinder soils cannot be chemically linked to the Pathfinder rocks by palagonitization, this study and McSween et al. [1999] suggest that palagonitic alteration of a Martian basaltic rock, plus mixture with a minor component of locally derived andesitic rock fragments, could be consistent with the observed soil APXS and IMP properties.

Journal of Geophysical Research E: Planets

Stable isotope deltas: Tiny, yet robust signatures in nature

Although most of them are relatively small, stable isotope deltas of naturally occurring substances are robust and enable workers in anthropology, atmospheric sciences, biology, chemistry, environmental sciences, food and drug authentication, forensic science, geochemistry, geology, oceanography, and paleoclimatology to study a variety of topics. Two fundamental processes explain the stable isotope deltas measured in most terrestrial systems: isotopic fractionation and isotope mixing. Isotopic fractionation is the result of equilibrium or kinetic physicochemical processes that fractionate isotopes because of small differences in physical or chemical properties of molecular species having different isotopes. It is shown that the mixing of radioactive and stable isotope end members can be modelled to provide information on many natural processes, including 14C abundances in the modern atmosphere and the stable hydrogen and oxygen isotopic compositions of the oceans during glacial and interglacial times. The calculation of mixing fractions using isotope balance equations with isotope deltas can be substantially in error when substances with high concentrations of heavy isotopes (e.g. 13C, 2H, and 18O ) are mixed. In such cases, calculations using mole fractions are preferred as they produce accurate mixing fractions. Isotope deltas are dimensionless quantities. In the International System of Units (SI), these quantities have the unit 1 and the usual list of prefixes is not applicable. To overcome traditional limitations with expressing orders of magnitude differences in isotope deltas, we propose the term urey (symbol Ur), after Harold C. Urey, for the unit 1. In such a manner, an isotope delta value expressed traditionally as−25 per mil can be written as−25 mUr (or−2.5 cUr or−0.25 dUr; the use of any SI prefix is possible). Likewise, very small isotopic differences often expressed in per meg ‘units’ are easily included (e.g. either+0.015 ‰ or+15 per meg can be written as+15 μUr.

Isotopes in Environmental and Health Studies

Effects of urbanization on stream ecosystems in the Willamette River basin and surrounding area, Oregon and Washington

This report describes the effects of urbanization on physical, chemical, and biological characteristics of stream ecosystems in 28 watersheds along a gradient of urbanization in the Willamette River basin and surrounding area, Oregon and Washington, from 2003 through 2005. The study that generated the report is one of several urban-effects studies completed nationally by the U.S. Geological Survey National Water-Quality Assessment Program. Watersheds were selected to minimize natural variability caused by factors such as geology, elevation, and climate, and to maximize coverage of different stages of urban development among watersheds. Because land use or population density alone often are not a complete measure of urbanization, a combination of land use, land cover, infrastructure, and socioeconomic variables were integrated into a multimetric urban intensity index (UII) to represent the degree of urban development in each watershed. Physical characteristics studied include stream hydrology, stream temperature, and habitat; chemical characteristics studied include sulfate, chloride, nutrients, pesticides, dissolved and particulate organic and inorganic carbon, and suspended sediment; and biological characteristics studied include algal, macroinvertebrate, and fish assemblages. Semipermeable membrane devices, passive samplers that concentrate trace levels of hydrophobic organic contaminants such as polycyclic aromatic hydrocarbons and polychlorinated biphenyls, also were used. The objectives of the study were to (1) examine physical, chemical, and biological responses along the gradient of urbanization and (2) determine the major physical, chemical, and landscape variables affecting the structure of aquatic communities. Common effects documented in the literature of urbanization on instream physical, chemical, and biological characteristics, such as increased contaminants, increased streamflow flashiness, increased concentrations of chemicals, and changes in aquatic community structure toward a more tolerant community associated with organically enriched conditions, generally were observed in this study. The strongest correlations to the UII and to many of the algal, macroinvertebrate, and fish assemblage metrics and community ordination involved water-chemistry metrics including the total pesticide concentration, toxic equivalents (extract assay from semipermeable membrane devices), and dissolved oxygen. Hydrologic variability metrics, such as flashiness, that normally are considered to be one of the main processes of urban disturbance had a strong association to the algal and fish assemblages in this study; however, the hydrologic variables for macroinvertebrates were secondary to the water-chemistry metrics mentioned above. Generally, the high urban intensity sites had high abundances of eutrophic and lower dissolved oxygen-indicating diatoms, high abundances of noninsects and tolerant insects, and high abundances of nonnative fish species. On the other hand, the low urban intensity sites had higher abundances of pollution sensitive diatoms, larger numbers of the sensitive macroinvertebrate EPT taxa (Ephemeroptera, Plecoptera and Trichoptera Orders), and fish assemblages with higher abundances of sensitive salmonids. The percent salmonid and macroinvertebrate EPT richness metrics plotted against the UII indicated a possible threshold response at about 25 on the UII, which is equivalent to an impervious surface value of about 5 percent. However, due to the added agricultural land use at sites within the 25 to 60 UII range, this possible threshold probably is not solely due to urbanization, but a combination of urban and agricultural land use. The effects of agricultural and urban land use could not be distinguished from each other, yet combined they provide a good assessment of overall watershed disturbance.

Oregon, Washington

Desert potholes: Ephemeral aquatic microsystems

An enigma of the Colorado Plateau high desert is the "pothole", which ranges from shallow ephemeral puddles to deeply carved pools. The existence of prokaryotic to eukaryotic organisms within these pools is largely controlled by the presence of collected rainwater. Multivariate statistical analysis of physical and chemical limnologic data variables measured from potholes indicates spatial and temporal variations, particularly in water depth, manganese, iron, nitrate and sulfate concentrations and salinity. Variation in water depth and salinity are likely related to the amount of time since the last precipitation, whereas the other variables may be related to redox potential. The spatial and temporal variations in water chemistry affect the distribution of organisms, which must adapt to daily and seasonal extremes of fluctuating temperature (0-60 ??C), pH changes of as much as 5 units over 12 days, and desiccation. For example, many species become dormant when potholes dry, in order to endure intense heat, UV radiation, desiccation and freezing, only to flourish again upon rehydration. But the pothole organisms also have a profound impact on the potholes. Through photosynthesis and respiration, pothole organisms affect redox potential, and indirectly alter the water chemistry. Laboratory examination of dried biofilm from the potholes revealed that within 2 weeks of hydration, the surface of the desiccated, black biofilm became green from cyanobacterial growth, which supported significant growth in heterotrophic bacterial populations. This complex biofilm is persumably responsible for dissolving the cement between the sandstone grains, allowing the potholes to enlarge, and for sealing the potholes, enabling them to retain water longer than the surrounding sandstone. Despite the remarkable ability of life in potholes to persist, desert potholes may be extremely sensitive to anthropogenic effects. The unique limnology and ecology of Utah potholes holds great scientific value for understanding water-rock-biological interactions with possible applications to life on other planetary bodies. ?? Springer 2005.

Aquatic Geochemistry

Ground water to surface water: Chemistry of thermal outflows in Yellowstone National Park

Geothermal waters in the earth’s subsurface boil with steam separation and may mix with dilute ground waters (that may or may not contain sulfuric acid from sulfur oxidation), resulting in a wide range of compositions when they discharge and emerge at the surface. As they discharge onto the ground surface they undergo evaporative cooling, degassing, oxidation, and mineral precipitation. Within this aquatic environment of rapidly changing physical and chemical parameters, numerous microbial communities develop—some of which affect oxidation and mineral precipitation. Microbes are responsible for rapid oxidation of iron and arsenic in thermal outflows, and for catalyzing the production of sulfuric acid from the oxidation of elemental sulfur. The attractive visual display of colors observed in Yellowstone’s geothermal waters reflects this interplay of physical, chemical, and biological phenomena. Oxidation of dissolved sulfide to thiosulfate occurs abiotically, and thiosulfate can be found in many of Yellowstone’s thermal waters—at any pH, temperature, and composition. Polythionates, on the other hand, are rarely found in Yellowstone waters but are associated with sulfur hydrolysis in Cinder Pool. Oxidation rates of iron and arsenic in overflows have been estimated at 1-3 mM/h and 0.04-0.1 mM/h, respectively—orders of magnitude faster than the abiotic rate. The abiotic production of thiosulfate from oxidation of dissolved sulfi de at Angel Terrace and Ojo Caliente is about 3-30 µM/min, faster by 2-3 orders of magnitude than the laboratory rate at 25°C. The partitioning of dissolved sulfide between that volatilized to the air and that oxidized to thiosulfate has been estimated at Angel Terrace and at Ojo Caliente. For the pH range of 6-8 and the temperature range of 50-93°C, 67-86% of the dissolved sulfide is lost to the atmosphere and 10-33% is oxidized to thiosulfate. Only a very small percentage, if any, forms elemental sulfur under these conditions.

Wyoming

Small anthropogenic landforms from past charcoal production control moisture dynamics and chemistry in northcentral Appalachian soils

Throughout the northeastern United States (U.S.) and Europe, relict charcoal hearths (RCHs) are regularly being discovered in proximity to furnaces once used for the extraction of metal from ore or quick-lime production; charcoal produced in hearths was used as a furnace fuel. Given previous research has shown that topographic and subsurface disturbance can be great when a hearth is constructed, we hypothesize that hearth construction alters surface hydrology and soil chemistry in environments in and near hearths. We used a landscape classification process to identify 6,758 hearths near furnaces at Greenwood and Pine Grove Furnace State Park, central and southcentral Pennsylvania, U.S. Two types of digital elevation model wetness indexes were used to quantify surface hydrology effects in and around hearths. Modeled wetness conditions were compared to field soil volumetric water content in RCHs near Greenwood Furnace State Park. Modeled wetness indexes indicate that RCH interiors are significantly wetter than RCH rim areas; RCHs are acting as a landscape moisture sink. Results also indicate that RCHs on slopes result in downslope drier conditions below RCHs. Field measured volumetric water content indicates that as distance from the center of the hearth increases, soil moisture significantly decreases. Geomorphic position was found to not be related to RCH wetness. Soil from RCHs, compared to nearby native soils, has significantly higher total C, a lower Mehlich 3 extractable acidity, higher Ca and P. No trend was evident with RCH soil chemistry and geomorphic position. The high frequency of RCH occurrence, in proximity to the furnace’s RCHs supported, suggests that RCHs today could locally be an important niche for understory flora and fauna. Further research could explore how RCHs might be affecting surrounding plant populations and how within RCH patterns, especially on hillslopes, might represent a distinctly different scale of physical and chemical variability.

Pennsylvania

Groundwater, surface-water, and water-chemistry data from C-aquifer monitoring program, northeastern Arizona, 2005-11

The C aquifer is a regionally extensive multiple-aquifer system supplying water for municipal, agricultural, and industrial use in northeastern Arizona, northwestern New Mexico, and southeastern Utah. An increase in groundwater withdrawals from the C aquifer coupled with ongoing drought conditions in the study area increase the potential for drawdown within the aquifer. A decrease in the water table and potentiometric surface of C aquifer is illustrated locally by the drying up of Obed Meadows, a natural peat deposit, and Hugo Meadows, a natural wetland, both south of Joseph City, Arizona. Continual increase in water use from the C aquifer, including a planned increase in pumpage by the City of Flagstaff, is justification for continued monitoring of the C-aquifer system in order to quantify physical and chemical responses to pumping stresses. Fifteen of the 35 C-aquifer wells analyzed had water-level data sufficient for percentage difference calculation for 2005–11. Change in water level as a percentage of the initial water-level measurement for these 15 wells ranged from about -0.2 to about -0.5 percent. For historical water-level data, changes in water levels were greatest around pumping centers, as indicated by a -97.0 feet (percentage difference of -16.5 percent) change over the period of record (1962–2005) for the Lake Mary 1 Well near Flagstaff, Arizona. In more rural areas of the C aquifer, water levels showed less change for both the temporal focus of this report (2005–11) and for historical values. Continuous records of surface-water discharge from 2005 to 2007 for three discontinued streamflow-gaging stations (Clear Creek near Winslow, AZ, 09399000; Clear Creek below McHood Lake near Winslow, AZ, 09399100; and Chevelon Creek near Winslow, AZ, 09398000) were tabulated. For the period of record, Clear Creek near Winslow, AZ, and Chevelon Creek near Winslow, AZ, showed seasonal discharge distributions indicative of natural streams in the southwestern United States. Clear Creek below McHood Lake near Winslow, AZ, showed discharge distribution indicative of perennial spring flow with little variation annually. Physical and chemical data collected during four baseflow investigations (summer 2005, summer 2006, summer 2008, and winter 2010) conducted on Clear Creek, Chevelon Creek, and a portion of the Little Colorado River were compiled and analyzed. Data from 7 sampling sites established on the Little Colorado River, 11 sites along Chevelon Creek, and 14 sites along Clear Creek were included. For the four baseflow investigations presented, a 2,000–3,000 microsiemens per centimeter increase in specific conductance was measured in Chevelon Creek from near its headwaters to the confluence with the Little Colorado River because of the contribution of highly conductive spring discharge. Clear Creek showed a less consistent pattern of increase in specific conductance with distance, but still exhibited changes on the order of 5,000 microsiemens per centimeter over just a few river miles. Water-chemistry data for selected wells and baseflow investigations sites are presented. No well samples analyzed exceeded the U.S. Environmental Protection Agency Maximum Contaminant Level standards for drinking water, but several samples exceeded Secondary Maximum Contaminant Level standards for chloride, fluoride, sulfate, iron, and total dissolved solids.

Arizona

Hydrogeologic framework and occurrence, movement, and chemical characterization of groundwater in Dixie Valley, west-central Nevada

Dixie Valley, a primarily undeveloped basin in west-central Nevada, is being considered for groundwater exportation. Proposed pumping would occur from the basin-fill aquifer. In response to proposed exportation, the U.S. Geological Survey, in cooperation with the Bureau of Reclamation and Churchill County, conducted a study to improve the understanding of groundwater resources in Dixie Valley. The objective of this report is to characterize the hydrogeologic framework, the occurrence and movement of groundwater, the general water quality of the basin-fill aquifer, and the potential mixing between basin-fill and geothermal aquifers in Dixie Valley. Various types of geologic, hydrologic, and geochemical data were compiled from previous studies and collected in support of this study. Hydrogeologic units in Dixie Valley were defined to characterize rocks and sediments with similar lithologies and hydraulic properties influencing groundwater flow. Hydraulic properties of the basin-fill deposits were characterized by transmissivity estimated from aquifer tests and specific-capacity tests. Groundwater-level measurements and hydrogeologic-unit data were combined to create a potentiometric surface map and to characterize groundwater occurrence and movement. Subsurface inflow from adjacent valleys into Dixie Valley through the basin-fill aquifer was evaluated using hydraulic gradients and Darcy flux computations. The chemical signature and groundwater quality of the Dixie Valley basin-fill aquifer, and potential mixing between basin-fill and geothermal aquifers, were evaluated using chemical data collected from wells and springs during the current study and from previous investigations. Dixie Valley is the terminus of the Dixie Valley flow system, which includes Pleasant, Jersey, Fairview, Stingaree, Cowkick, and Eastgate Valleys. The freshwater aquifer in the study area is composed of unconsolidated basin-fill deposits of Quaternary age. The basin-fill hydrogeologic unit can be several orders of magnitude more transmissive than surrounding and underlying consolidated rocks and Dixie Valley playa deposits. Transmissivity estimates in the basin fill throughout Dixie Valley ranged from 30 to 45,500 feet squared per day; however, a single transmissivity value of 0.1 foot squared per day was estimated for playa deposits. Groundwater generally flows from the mountain range uplands toward the central valley lowlands and eventually discharges near the playa edge. Potentiometric contours east and west of the playa indicate that groundwater is moving eastward from the Stillwater Range and westward from the Clan Alpine Mountains toward the playa. Similarly, groundwater flows from the southern and northern basin boundaries toward the basin center. Subsurface groundwater flow likely enters Dixie Valley from Fairview and Stingaree Valleys in the south and from Jersey and Pleasant Valleys in the north, but groundwater connections through basin-fill deposits were present only across the Fairview and Jersey Valley divides. Annual subsurface inflow from Fairview and Jersey Valleys ranges from 700 to 1,300 acre-feet per year and from 1,800 to 2,300 acre-feet per year, respectively. Groundwater flow between Dixie, Stingaree, and Pleasant Valleys could occur through less transmissive consolidated rocks, but only flow through basin fill was estimated in this study. Groundwater in the playa is distinct from the freshwater, basin-fill aquifer. Groundwater mixing between basin-fill and playa groundwater systems is physically limited by transmissivity contrasts of about four orders of magnitude. Total dissolved solids in playa deposit groundwater are nearly 440 times greater than total dissolved solids in the basin-fill groundwater. These distinctive physical and chemical flow restrictions indicate that groundwater interaction between the basin fill and playa sediments was minimal during this study period (water years 2009–11). Groundwater in Dixie Valley generally can be characterized as a sodium bicarbonate type, with greater proportions of chloride north of the Dixie Valley playa, and greater proportions of sulfate south of the playa. Analysis of major ion water chemistry data sampled during the study period indicates that groundwater north and south of Township 22N differ chemically. Dixie Valley groundwater quality is marginal when compared with national primary and secondary drinking-water standards. Arsenic and fluoride concentrations exceed primary drinking water standards, and total dissolved solids and manganese concentrations exceed secondary drinking water standards in samples collected during this study. High concentrations of boron and tungsten also were observed. Chemical comparisons between basin-fill and geothermal aquifer water indicate that most basin-fill groundwater sampled could contain 10–20 percent geothermal water. Geothermal indicators such as high temperature, lithium, boron, chloride, and silica suggest that mixing occurs in many wells that tap the basin-fill aquifer, particularly on the north, south, and west sides of the basin. Magnesium-lithium geothermometers indicate that some basin-fill aquifer water sampled for the current study likely originates from water that was heated above background mountain-block recharge temperatures (between 3 and 15 degrees Celsius), highlighting the influence of mixing with warm water that was possibly derived from geothermal sources.

Nevada

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