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Trace metal seasonal variations in Texas marine sediments

Trace elements in coastal environments are derived from three major sources: (1) the bordering watershed; (2) the offshore marine environment; and (3) industrial and/or urban effluent. The site of deposition, however, is controlled by physical and chemical processes in the coastal zone. In many cases, these processes are controlled by climate and can vary seasonally. In the harbor at Corpus Christi, Texas, the summer climate creates an oxygen-poor environment in the water column near the sediment-water interface. This causes chalcophilic metals to precipitate from the water, resulting in high concentrations in the sediments near the source. During the winter, turbulence created by strong winds causes the entire water mass to become aerated and oxidizing, and remobilization of some metals results. In addition, this turbulence accelerates circulation which transports the metal-enriched waters from the harbor. On the outer continental shelf of south Texas, the infaunal activity varies seasonally with bottom water temperatures. As this infaunal activity has an effect on the chemical environment within the sediment near the sediment-water interface, the observed trace metal content at the interface also appears to change with the seasons.

Texas

Growth and defense characteristics of whitebark pine (Pinus albicaulis) and lodgepole pine (Pinus contorta var latifolia) in a high-elevation, disturbance-prone mixed-conifer forest in northwestern Montana, USA

Recent, widespread tree mortality in the western U.S. resulting from changes in climate, pathogens, insect activity, and forest management practices has led to concerns for many ecologically and culturally important species. Within conifers, resin-based defenses have long been recognized as a primary defense mechanism against a variety of insects and pathogens. Oleoresin produced by trees contain complex mixtures of terpenoids that have numerous insecticidal and fungicidal properties. Research has also identified links between resin duct characteristics and increased probability of survival during bark beetle outbreaks. Whitebark pine ( Pinus albicaulis ) is a culturally significant high elevation species that provides numerous ecological services within subalpine and alpine ecosystems. Whitebark pine has co-evolved with a suite of biotic and abiotic disturbances. Individual trees allocate resources towards growth and resin-based defenses, making it a good candidate species to evaluate growth and defense relationships and tradeoffs. In this study we compared constitutive resin chemistry, tree growth and resin duct anatomy between similarly aged whitebark and lodgepole pine ( P. contorta var latifolia ) growing in proximity within a disturbance-prone, mixed-conifer forest in northwestern Montana. These two host species have varying degrees of historical exposure to mountain pine beetle. Our research yields four important findings. First, we did not find evidence of a tradeoff between tree growth and tree defenses (resin duct morphology and resin chemistry). This suggests that trees growing under favorable field conditions can experience high growth rates and still allocate ample resources towards defense. Second, we found that resin ducts and constitutive mono- and sesqui- terpenes were not correlated in lodgepole pine while duct production and area were positively related to constitutive monoterpenes, and duct size and area were positively related to constitutive sesquiterpenes, in whitebark pine. The lack of distinct, consistent relationships between these defensive features suggests that both whitebark and lodgepole pine trees present beetles with numerous, complex combinations of resin-based defenses. Third, based on constitutive terpene profiles, bark beetles are more likely to enter lodgepole pine but more likely to successfully elicit mass attacks in whitebark pine, which agrees with beetle attack and success patterns observed in the field. Fourth, overstory competition, particularly by Engelmann spruce ( Picea engelmannii ), can influence tree defenses, specifically by reducing constitutive terpene concentrations in lodgepole and whitebark pine. Competitive tree interactions could lead to altered bark beetle-conifer interactions as host and nonhost species migrate in response to changing climate. Our results suggest that strategies designed to support whitebark pine populations can benefit from better understanding interactions among growth, competition and physical and chemical defenses in response to multiple disturbance.

Montana

Water and sediment chemistry of selected existing and potential habitats of the Mohave tui chub, Mojave National Preserve, California, 2018

The Mohave tui chub ( Siphateles bicolor mohavensis ) was nearly extirpated from the Mojave River drainage in California by the mid-twentieth century and was listed as endangered in 1970. A source population of Mohave tui chub exists at MC Spring in Zzyzx, California, and has been used for several re-establishment efforts in previous decades. Two potential habitats in the Mojave National Preserve with perennial sources of water were identified by the National Park Service as candidates for additional Mohave tui chub re-establishment: West Pond and Rainbow Wells Pond. West Pond, an artificial pond at Zzyzx near MC Spring, contained a population of Mohave tui chub that died off in 1985 because of changes in water quality. The pond was rehabilitated in the past several years through re-excavation and by pumping fresh groundwater into the pond. Rainbow Wells Pond is an abandoned excavated mine site in the Cima Dome area. The bottom of the excavation intersects the water table, forming a pond. In cooperation with the National Park Service, the U.S. Geological Survey monitored water-quality conditions at West Pond and Rainbow Wells Pond for 1 year to characterize the suitability of spring habitat for re-establishment of Mohave tui chub populations. Data were also collected at three existing Mohave tui chub habitats in Mojave National Preserve to provide further information on the range of acceptable physical and chemical conditions. Initial water-quality results at West Pond indicate the pond has similar water quality as existing Mohave tui chub habitats. Initial water-quality results at Rainbow Wells Pond indicate the dissolved oxygen concentrations and springtime water temperatures are less than the long-term tolerable ranges for Mohave tui chub.

California

Age and source of water in springs associated with the Jacksonville Thrust Fault Complex, Calhoun County, Alabama

Water from wells and springs accounts for more than 90 percent of the public water supply in Calhoun County, Alabama. Springs associated with the Jacksonville Thrust Fault Complex are used for public water supply for the cities of Anniston and Jacksonville. The largest ground-water supply is Coldwater Spring, the primary source of water for Anniston, Alabama. The average discharge of Coldwater Spring is about 32 million gallons per day, and the variability of discharge is about 75 percent. Water-quality samples were collected from 6 springs and 15 wells in Calhoun County from November 2001 to January 2003. The pH of the ground water typically was greater than 6.0, and specific conductance was less than 300 microsiemens per centimeter. The water chemistry was dominated by calcium, carbonate, and bicarbonate ions. The hydrogen and oxygen isotopic composition of the water samples indicates the occurrence of a low-temperature, water-rock weathering reaction known as silicate hydrolysis. The residence time of the ground water, or ground-water age, was estimated by using analysis of chlorofluorocarbon, sulfur hexafluoride, and regression modeling. Estimated ground-water ages ranged from less than 10 to approximately 40 years, with a median age of about 18 years. The Spearman rho test was used to identify statistically significant covariance among selected physical properties and constituents in the ground water. The alkalinity, specific conductance, and dissolved solids increased as age increased; these correlations reflect common changes in ground-water quality that occur with increasing residence time and support the accuracy of the age estimates. The concentration of sodium and chloride increased as age increased; the correlation of these constituents is interpreted to indicate natural sources for chloride and sodium. The concentration of silica increased as the concentration of potassium increased; this correlation, in addition to the isotopic data, is evidence that silicate hydrolysis of clay minerals occurred. The geochemical modeling program NETPATH was used to investigate possible mixing scenarios that could yield the chemical composition of water collected from springs associated with the Jacksonville Thrust Fault Complex. The results of NETPATH modeling suggest that the primary source of water in Coldwater Spring is a deep aquifer, and only small amounts of rainwater from nearby sources are discharged from the spring. Starting with Piedmont Sports Spring and moving southwest along a conceptual ground-water flow path that parallels the Jacksonville Thrust Fault Complex, NETPATH simulated the observed water quality of each spring, in succession, by mixing rainwater and water from the spring just to the northeast of the spring being modeled. The percentage of rainwater and ground water needed to simulate the quality of water flowing from the springs ranged from 1 to 25 percent rainwater and 75 to 99 percent ground water.

Scientific Investigations Report

Physical and chemical characteristics of Terrace Reservoir, Conejos County, Colorado, May 1994 through May 1995

Terrace Reservoir receives drainage of low-pH, metal-enriched water from mineralized areas, including the Summitville Mine, within the Alamosa River Basin. Drainage from the Summitville Mine has contributed a substantial part of the metal load to Terrace Reservoir. From May 1994 through May 1995, a study was done by the U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency, to evaluate the physical and chemical characteristics of Terrace Reservoir. Terrace Reservoir was thermally stratified from about mid-May through August 1994. Thermal stratification was absent from September\x111994through March 1995. During periods of stratification, underflow of the Alamosa River was predominant, and residence times of the underflow were shortened by 40 to 75\x11percent of the theoretical residence times for a well-mixed reservoir. Transport and deposition of suspended solids in Terrace Reservoir varied spatially and temporally. Most of the suspended solids were deposited in Terrace Reservoir. The concentration of dissolved oxygen in the reservoir varied little spatially or temporally and generally was within a few tenths of the dissolved-oxygen concentration of the inflow. The pH of water in the reservoir generally ranged from about 4.0 to about 7.0, depending on date, depth, and location. The largest pH values were measured during May. A markeddecrease of about 1.5\x11pH units occurred at site T5 in the reservoir about mid-June. The pH of the reservoir remained at or below 5.5 from mid-June through November. Dissolved-metal concentrations varied spatially and temporally in response to several factors, which included inflow characteristics, reservoir stratification and mixing, inflow-routing and flow-through patterns, residence times, sedimentation, dissolved oxygen, and pH.Inflow chemistry is the dominant controlling factor of metal chemistry within Terrace Reservoir.During periods of stratification, large vertical variations in metal concentrations occurred. The highest metal concentrations in the reservoir generally were measured in the hypolimnion between June and August. During June, epilimnetic water of the reservoir had pH values greater than 6.0, and metal concentrations were lower than hypolimnetic concentrations. In the hypolimnion, pH values were less than 5.5. The difference between the chemistry of the epilimnion and the hypolimnion was due to differences in flow routing and residence times of water in those respective layers. The dissolved-metal concentrations were larger during July and August than during June.During September, small vertical variations in metalconcentrations occurred, and the dissolved-metal concentrations were nearly equivalent to the average August metal concentrations, indicatingthat the metal concentrations measured during September resulted largely from reservoir mixing.During March, the largest metal concentrationsoccurred in the epilimnion, where pH was about 5.5; in the hypolimnion, where the pH was about 6.0, dissolved-metal concentrations were substantially lower and reflected inflow concentrations.

Colorado

Physical and chemical characteristics of Terrace Reservoir, Conejos County, Colorado, May 1994 through May 1995; interim report

Terrace Reservoir receives drainage of low-pH, metal-enriched water from mineralized areas, including the Summitville Mine, within the Alamosa River Basin. Drainage from the Summitville Mine has contributed a substantial part of the metal load to Terrace Reservoir. From May 1994 through May 1995, a study was done by the U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency, to evaluate the physical and chemical characteristics of Terrace Reservoir. Terrace Reservoir was thermally stratified from about mid-May through August 1994. Thermal stratification was absent from September\x111994through March 1995. During periods of stratification, underflow of the Alamosa River was predominant, and residence times of the underflow were shortened by 40 to 75\x11percent of the theoretical residence times for a well-mixed reservoir. Transport and deposition of suspended solids in Terrace Reservoir varied spatially and temporally. Most of the suspended solids were deposited in Terrace Reservoir. The concentration of dissolved oxygen in the reservoir varied little spatially or temporally and generally was within a few tenths of the dissolved-oxygen concentration of the inflow. The pH of water in the reservoir generally ranged from about 4.0 to about 7.0, depending on date, depth, and location. The largest pH values were measured during May. A markeddecrease of about 1.5\x11pH units occurred at site T5 in the reservoir about mid-June. The pH of the reservoir remained at or below 5.5 from mid-June through November. Dissolved-metal concentrations varied spatially and temporally in response to several factors, which included inflow characteristics, reservoir stratification and mixing, inflow-routing and flow-through patterns, residence times, sedimentation, dissolved oxygen, and pH. Inflow chemistry is the dominant controlling factor of metal chemistry within Terrace Reservoir. During periods of stratification, large vertical variations in metal concentrations occurred. The highest metal concentrations in the reservoir generally were measured in the hypolimnion between June and August. During June, epilimnetic water of the reservoir had pH values greater than 6.0, and metal concentrations were lower than hypolimnetic concentrations. In the hypolimnion, pH values were less than 5.5. The difference between the chemistry of the epilimnion and the hypolimnion was due to differences in flow routing and residence times of water in those respective layers. The dissolved-metal concentrations were larger during July and August than during June. During September, small vertical variations in metal concentrations occurred, and the dissolved-metal concentrations were nearly equivalent to the average August metal concentrations, indicatingthat the metal concentrations measured during September resulted largely from reservoir mixing.During March, the largest metal concentrationsoccurred in the epilimnion, where pH was about 5.5; in the hypolimnion, where the pH was about 6.0, dissolved-metal concentrations were substantially lower and reflected inflow concentrations.

Colorado

A crystal-chemical classification of borate structures with emphasis on hydrated borates

The rules governing formation of hydrated borate polyanions that were proposed by C.L. Christ in 1960 are critically reviewed and new rules added on the basis of recent crystal structure determinations. Principles and classifications previously published by others are also critically reviewed briefly. The fundamental building blocks from which borate polyanions can be constructed are defined on the basis of the number n of boron atoms, and the fully hydrated polyanions are illustrated. Known structures are grouped accordingly, and a shorthand notation using n and symbols ?? = triangle, T = tetrahedron is introduced so that the polyanions can be easily characterized. For example, 3:??+2T describes [B3O3(OH)5]2-. Correct structural formulas are assigned borates with known structures whereas borates of unknown structure are grouped separately. ?? 1977 Springer-Verlag.

Physics and Chemistry of Minerals

Soil and geomorphic patterns within relict charcoal hearths could represent unique ecosystem niches

Hearths used for 19th and 20th century charcoal manufacturing have been found to have unique plant communities or to produce unique growth characteristics for some species but not others. Given known differences in hearth morphology, within hearth physical and chemical differences may exist and result in unique ecologic niches. We examined soil stratigraphy across 8 relict charcoal hearths (RCH) and control soils on different landforms near a 19th century furnace complex (Greenwood Furnace, northcentral Appalachians USA). Soils were analyzed for particle size, total and trace elements, and fertility. Platform creation resulted in soils from upslope RCH positions mixed with subsurface materials on the downslope side to create a stabilized platform. The thin, uniform thickness of charcoal surface horizons (Ac) suggests that RCHs were not used more than once for charcoal manufacturing or that charcoal was always removed very efficiently. While rubification of soil or rock from high heat was seen in 6 of 8 sites sampled, it was not extensive across sampled areas of any one hearth, which suggests hearth use may not have frequent, hot enough, or spatially disparate. Soil fertility characteristics change within RCHs but also by landscape position. Downslope RCH positions are enriched in some parameters compared to control soils (total C, Mehlich 3 Mg, Ca, and Aquia Regia digestion Mn) and that enrichment often is from the surface downward. Downslope enrichment within RCH soils may have occurred from charcoal and released ions, slope erosion and accumulation, or transportation of constructed materials during RCH creation. Landscape position may accentuate or mute soil chemistry differences. Greenwood Furnace RCHs have unique patterns of chemistry, which could result in unique niches for flora and maybe fauna within RCH. Future research should more closely investigate whether hearths support unique species assemblages and how they may play a role in enhancing today’s forest biodiversity.

Pennsylvania

Processes affecting transport of uranium in a suboxic aquifer

At the Naturita site in Colorado, USA, groundwaters were sampled and analyzed for chemical composition and by culture and culture-independent microbiological techniques. In addition, sediments were extracted with a dilute sodium carbonate solution to determine quantities of labile uranium within the sediments. Samples from the upgradient portion of the contaminated aquifer , where very little dissolved Fe(II) is found in the groundwater, have uranium content that is controlled by U(VI) adsorption and few metal-reducing bacteria are observed. In the extreme downgradient portion of the aquifer, where dissolved Fe(II) is observed, uranium content of the sediments includes significant quantities of reduced U(IV) and diverse populations of Fe(III)-reducing bacteria were present in the subsurface with the potential of reducing U(VI) to U(IV).

Physics and Chemistry of the Earth

Variation in the terrestrial isotopic composition and atomic weight of argon

The isotopic composition and atomic weight of argon (Ar) are variable in terrestrial materials. Those variations are a source of uncertainty in the assignment of standard properties for Ar, but they provide useful information in many areas of science. Variations in the stable isotopic composition and atomic weight of Ar are caused by several different processes, including (1) isotope production from other elements by radioactive decay (radiogenic isotopes) or other nuclear transformations (e.g., nucleogenic isotopes), and (2) isotopic fractionation by physical-chemical processes such as diffusion or phase equilibria. Physical-chemical processes cause correlated mass-dependent variations in the Ar isotope-amount ratios ( 40 Ar/ 36 Ar, 38 Ar/ 36 Ar), whereas nuclear transformation processes cause non-mass-dependent variations. While atmospheric Ar can serve as an abundant and homogeneous isotopic reference, deviations from the atmospheric isotopic ratios in other Ar occurrences limit the precision with which a standard atomic weight can be given for Ar. Published data indicate variation of Ar atomic weights in normal terrestrial materials between about 39.7931 and 39.9624. The upper bound of this interval is given by the atomic mass of 40 Ar, as some samples contain almost pure radiogenic 40 Ar. The lower bound is derived from analyses of pitchblende (uranium mineral) containing large amounts of nucleogenic 36 Ar and 38 Ar. Within this interval, measurements of different isotope ratios ( 40 Ar/ 36 Ar or 38 Ar/ 36 Ar) at various levels of precision are widely used for studies in geochronology, water–rock interaction, atmospheric evolution, and other fields.

Pure and Applied Chemistry

Hydrothermal contamination of public supply wells in Napa and Sonoma Valleys, California

Groundwater chemistry and isotope data from 44 public supply wells in the Napa and Sonoma Valleys, California were determined to investigate mixing of relatively shallow groundwater with deeper hydrothermal fluids. Multivariate analyses including Cluster Analyses, Multidimensional Scaling (MDS), Principal Components Analyses (PCA), Analysis of Similarities (ANOSIM), and Similarity Percentage Analyses (SIMPER) were used to elucidate constituent distribution patterns, determine which constituents are significantly associated with these hydrothermal systems, and investigate hydrothermal contamination of local groundwater used for drinking water. Multivariate statistical analyses were essential to this study because traditional methods, such as mixing tests involving single species (e.g. Cl or SiO 2 ) were incapable of quantifying component proportions due to mixing of multiple water types. Based on these analyses, water samples collected from the wells were broadly classified as fresh groundwater, saline waters, hydrothermal fluids, or mixed hydrothermal fluids/meteoric water wells. The Multivariate Mixing and Mass-balance (M3) model was applied in order to determine the proportion of hydrothermal fluids, saline water, and fresh groundwater in each sample. Major ions, isotopes, and physical parameters of the waters were used to characterize the hydrothermal fluids as Na–Cl type, with significant enrichment in the trace elements As, B, F and Li. Five of the wells from this study were classified as hydrothermal, 28 as fresh groundwater, two as saline water, and nine as mixed hydrothermal fluids/meteoric water wells. The M3 mixing-model results indicated that the nine mixed wells contained between 14% and 30% hydrothermal fluids. Further, the chemical analyses show that several of these mixed-water wells have concentrations of As, F and B that exceed drinking-water standards or notification levels due to contamination by hydrothermal fluids.

California

Water-quality assessment of the Ozark Plateaus study unit, Arkansas, Kansas, Missouri, and Oklahoma- fish communities in streams of the Ozark Plateaus and their relations to selected environmental factors

Fish communities from 22 reaches at 18 stations in the Ozark Plateaus were sampled in 1993, 1994, and 1995. The 18 stations were chosen to represent selected combinations of major environmental factors (geology/physiographic area, land use, and basin size). Additional physical, chemical, and biological factors also were measured for each of the 22 reaches and the influence of these factors upon the fish communities was investigated. Fish community samples collected at the 22 reaches identified differences in these communities that can be attributed to differences in land use and related water-quality and habitat characteristics. Communities from agriculture reaches tended to have more species, increased relative abundance of stonerollers and members of the sucker family, and decreased relative abundance of members of the sunfish and darter families. Several groups of environmental factors (concentrations of nutrients, organic carbon, suspended sediment, and dissolved oxygen; measures related to ionic strength; measures related to riparian vegetation; measures related to substrate; and measures related to stream size) appear to be related to land-use differences and fish community differences. Three multivariate analysis techniques (two ordination techniques and a classification technique) yielded similar results when applied to the fish community data. Fish communities from reaches with more similar land use in their basins and with similar drainage areas generally were grouped closer together in the analysis. Water quality, substrate, stream morphology, and riparian measures appear to be affecting fish communities at these reaches. The relations between land use, stream size, and fish communities have implications for water quality assessments of Ozark streams. Compared to other parts of the United States, many fish species live in the Ozark Plateaus. At least 19 of these species are endemic to the Ozarks area. Many of these species are intolerant of habitat or water chemistry degradation. This characteristic makes fish a useful tool for assessing water-chemistry and other habitat conditions of streams. Several environmental factors can contribute to differences in fish communities. Elevated nutrient concentrations and greater canopy angles can increase periphyton production. Greater canopy angles can raise water temperatures and, if they reflect less woody vegetation along the banks of streams, can be associated with greater streambank erosion. Elevated suspended sediment concentrations and finer and more embedded substrates can reduce benthic macroinvertebrate populations, decrease spawning success of many fish species, and decrease protection of benthic fish from water velocities and predators.

Arkansas, Kansas, Missouri, Oklahoma

Hydrology of Crater, East and Davis Lakes, Oregon; with section on Chemistry of the Lakes

Crater, East, and Davis Lakes are small bodies of fresh water that occupy topographically closed basins in Holocene volcanic terrane. Because the annual water supply exceeds annual evaporation, water must be lost by seepage from each lake. The seepage rates vary widely both in volume and in percentage of the total water supply. Crater Lake loses about 89 cfs (cubic feet per second), equivalent to about 72 percent of its average annual supply. East Lake loses about 2.3 cfs, or about 44 percent of its estimated supply. Davis Lake seepage varies greatly with lake level, but the average loss is about 150 cfs, more than 90 percent of its total supply. The destination of the seepage loss is not definitely known for any of the lakes. An approximate water budget was computed for stationary level for each lake, by using estimates 'by the writer to supplement the hydrologic data available. The three lake waters are dilute. Crater Lake contains about 80 ppm, (parts per million) of dissolved solids---mostly silica, sodium, and bicarbonate, and lesser amounts of calcium, sulfate, and chloride. Much of the dissolved-solids content of Crater Lake---especially the sulfate and chloride---may be related to fumarole and thermal-spring activity that presumably followed the collapse of Mount Mazama. Although Grater Lake loses an estimated 7,000 tons of its 1.5million-ton salt content each year by leakage, the chemical character of the lake did not change appreciably between 1912 and 1964. East Lake contains 200 ppm of dissolved solids, which includes major proportions of calcium, sodium, bicarbonate, and sulfate, but almost no chloride. The lake apparently receives much of its dissolved solids from subsurface thermal springs. Annual solute loss from East Lake by leakage is about 450 tons, or 3 percent of the lake's 15,000-ton estimated solute content. Davis Lake contains only 48 ppm of dissolved solids, much of which is silica and bicarbonate; chloride is almost completely absent. Approximate physical and hydrologic data for the lakes are summarized in the following table. [Table]

Water Supply Paper

Formation of natural gas hydrates in marine sediments 1. Conceptual model of gas hydrate growth conditioned by host sediment properties

The stability of submarine gas hydrates is largely dictated by pressure and temperature, gas composition, and pore water salinity. However, the physical properties and surface chemistry of deep marine sediments may also affect the thermodynamic state, growth kinetics, spatial distributions, and growth forms of clathrates. Our conceptual model presumes that gas hydrate behaves in a way analogous to ice in a freezing soil. Hydrate growth is inhibited within fine-grained sediments by a combination of reduced pore water activity in the vicinity of hydrophilic mineral surfaces, and the excess internal energy of small crystals confined in pores. The excess energy can be thought of as a "capillary pressure" in the hydrate crystal, related to the pore size distribution and the state of stress in the sediment framework. The base of gas hydrate stability in a sequence of fine sediments is predicted by our model to occur at a lower temperature (nearer to the seabed) than would be calculated from bulk thermodynamic equilibrium. Capillary effects or a build up of salt in the system can expand the phase boundary between hydrate and free gas into a divariant field extending over a finite depth range dictated by total methane content and pore-size distribution. Hysteresis between the temperatures of crystallization and dissociation of the clathrate is also predicted. Growth forms commonly observed in hydrate samples recovered from marine sediments (nodules, and lenses in muds; cements in sands) can largely be explained by capillary effects, but kinetics of nucleation and growth are also important. The formation of concentrated gas hydrates in a partially closed system with respect to material transport, or where gas can flush through the system, may lead to water depletion in the host sediment. This "freeze-drying" may be detectable through physical changes to the sediment (low water content and overconsolidation) and/or chemical anomalies in the pore waters and metastable presence of free gas within the normal zone of hydrate stability.

Journal of Geophysical Research B: Solid Earth

Magnetic susceptibility and triangular exchange coupling in the tourmaline mineral group

Magnetic susceptibilities of three iron-rich tourmaline crystals from Mexquitic (Mexico), Pierpont (New York), and Madagascar with different and known chemical compositions have been studied from 8° to 300°K. The iron atoms in the tourmaline crystal structure, space group R3m , a∼15·9, c∼7·2 , are situated at the three corners of an equilateral triangle and are close enough for magnetic exchange interaction. For buergerite, the Mexquitic sample, the susceptibility data lead to an exchange constant J/k of 7·5°K. Although the amount of aluminum would be sufficient to fill point position 18(c) exactly, the magnetic data are consistent with some substitution of ferric iron for aluminum, as previously determined from X-ray and neutron diffraction studies. Some aluminum thus replaces iron in position 9(b). Exchange constants were also estimated for the other two magnesium-iron specimens, of which the madagascar sample is aluminum deficient. The results agree with the evidence from optical spectra that there is considerable deviation from octahedral symmetry in the oxygen coordination polyhedra about the 9(b) and 18(c) point positions.

New York

Chemical characterization of sediments and pore water from the upper Clark Fork River and Milltown Reservoir, Montana

The upper Clark Fork River basin in western Montana is widely contaminated by metals from past mining, milling, and smelting activities As part of a comprehensive ecological risk assessment for the upper Clark Fork River, we measured physical and chemical characteristics of surficial sediment samples that were collected from depositional zones for subsequent toxicity evaluations Sampling stations included five locations along the upper 200 km of the river, six locations in or near Milltown Reservoir (about 205 km from the river origin), and two tributary reference sites Concentrations of As, Cd, Cu, Mn, Pb, and Zn decreased from the upper stations to the downstream stations in the Clark Fork River but then increased in all Milltown Reservoir stations to levels similar to uppermost river stations Large percentages (50 to 90%) of the total Cd, Cu, Pb, and Zn were extractable by dilute (3 n) HCl for all samples Copper and zinc accounted for greater than 95% of extractable metals on a molar basis Acid-volatile sulfide (AVS) concentrations were typically moderate (0 6 to 23 μmol/g) in grab sediment samples and appeared to regulate dissolved (filterable) concentrations of Cd, Cu, and Zn in sediment pore waters Acid volatile sulfide is important in controlling metal solubility in the depositional areas of the Clark Fork River and should be monitored in any future studies Spatial variability within a sampling station was high for Cu, Zn, and AVS, therefore, the potential for toxicity to sediment dwelling organisms may be highly localized.

Environmental Toxicology and Chemistry

Volcanogenic Sulfur on Earth and Io: Composition and Spectroscopy

The causes of Io's variegated surface, especially the roles of sulfur, and the geochemical history of sulfur compounds on Io are not well understood. Suspecting that minor impurities in sulfur might be important, we have investigated the major and trace element chemistry and spectroscopic reflectance of natural sulfur from a variety of terrestrial volcanic-hydrothermal environments. Evidence suggests that Io may be substantially coated with impure sulfur. On Earth, a few tenths of a percent to a few percent of chalcophile trace elements (e.g., As and Se) comonly occur in sulfur and appear to stabilize material of yellow, brown, orange, and red hues, which may persist even at low temperatures. Percentage levels of chalcophile impurities are reasonably expected to occur on Io in vapor sublimate deposits and flows derived from such deposits. Such impurities join a host of other mechanisms that might explain Io's reds and yellows. Two-tenths to two percent opaque crystalline impurities, particularly pyrite (FeS2), commonly produces green, gray, and black volcanic sulfur on Earth and might explain areas of Io having deposits of these colors. Pyrite produces a broad absorption near 1 ??m that gradually diminishes out to 1.6 ??m - similar but not identical to the spectrum of Io seen in Galileo NIMS data. Percentage amounts of carbonaceous impurities and tens of percent SiO2 (as silicates) also strongly affect the spectral properties of Earth's sulfur. Io's broad absorption between 0.52 and 0.64 ??m remains unexplained by these data but could be due to sodium sulfides, as suggested previously by others, or to As, Se, or other impurities. These impurities and others, such as P and Cl (which could exist on Io's surface in amounts over 1% that of sulfur), greatly alter the molecular structure of molten and solid sulfur. Minor impurities could impact Io's geology, such as the morphology of sulfur lava flows and the ability of sulfur to sustain high relief. We have not found any natural sulfur containing significant Na beyond that attributable to silicate inclusions. In sum, the unique physical-chemical properties of S-rich systems and the strong affinity of certain elements for S may have broad implications for the appearance, spectroscopic interpretation, and geologic processes of Io. Identification of impurities in sulfur may be helpful in tracing the geochemical evolution of surface deposits on Io. Perhaps foretelling of new areas of investigation, Cl has recently been reported in the Io torus (M. Kueppers and N. M. Schneider 1999, Eos Trans.80, 5207), suggesting the presence on Io of either salts, such as halite, or sulfur chlorides. Further evidence of minor iogenic impurities should be sought in Io's neutral cloud and plasma torus as well as in further scrutiny of Io's reflectance spectra. ?? 1999 Academic Press.

Icarus

Applied Geochemistry Special Issue on Environmental geochemistry of modern mining

Environmental geochemistry is an integral part of the mine-life cycle, particularly for modern mining. The critical importance of environmental geochemistry begins with pre-mining baseline characterization and the assessment of environmental risks related to mining, continues through active mining especially in water and waste management practices, and culminates in mine closure. The enhanced significance of environmental geochemistry to modern mining has arisen from an increased knowledge of the impacts that historical and active mining can have on the environment, and from new regulations meant to guard against these impacts. New regulations are commonly motivated by advances in the scientific understanding of the environmental impacts of past mining. The impacts can be physical, chemical, and biological in nature. The physical challenges typically fall within the purview of engineers, whereas the chemical and biological challenges typically require a multidisciplinary array of expertise including geologists, geochemists, hydrologists, microbiologists, and biologists. The modern mine-permitting process throughout most of the world now requires that potential risks be assessed prior to the start of mining. The strategies for this risk assessment include a thorough characterization of pre-mining baseline conditions and the identification of risks specifically related to the manner in which the ore will be mined and processed, how water and waste products will be managed, and what the final configuration of the post-mining landscape will be. In the Fall 2010, the Society of Economic Geologists held a short course in conjunction with the annual meeting of the Geological Society of America in Denver, Colorado (USA) to examine the environmental geochemistry of modern mining. The intent was to focus on issues that are pertinent to current and future mines, as opposed to abandoned mines, which have been the focus of numerous previous short courses. The geochemical challenges of current and future mines share similarities with abandoned mines, but differences also exist. Mining and ore processing techniques have changed; the environmental footprint of waste materials has changed; environmental protection has become a more integral part of the mine planning process; and most historical mining was done with limited regard for the environment. The 17 papers in this special issue evolved from the Society of Economic Geologists’ short course. The relevant geochemical processes encompass the source, transport, and fate of contaminants related to the life cycle of a mine. Contaminants include metals and other inorganic species derived from geologic sources such as ore and solid mine waste, and substances brought to the site for ore processing, such as cyanide to leach gold. Factors, such as mine-waste mineralogy, hydrologic setting, mine-drainage chemistry, and microbial activity, that affect the hydrochemical risks from mining are reviewed by Nordstrom et al. In another paper, Nordstrom discusses baseline characterization at mine sites in a regulatory framework, and emphasizes the influence of mineral deposits in producing naturally elevated concentrations of many trace elements in surface water and groundwater. Surface water quality in mineralized watersheds is influenced by a number of processes that act on daily (diel) cycles and can produce dramatic variations in trace element concentrations as described by Gammons et al. Pre-mining baseline characterization studies should strive to capture the magnitude of these diel variations. Desbarats et al., using a case study of mine drainage from a gold mine, illustrate how elements that commonly occur as negatively charged species (anions) in solution, such as arsenic as arsenate, behave in an opposite fashion than most metals, which occur as positively charged species (cations). Significant improvement in the understanding of factors that influence the toxicity of metals to aquatic organisms in surface water has highlighted the importance of aqueous chemistry, particularly dissolved organic carbon, as described by Smith et al. Stream sediment contamination is another important pathway for affecting aquatic organisms, as reviewed by Besser et al. Understanding and predicting environmental consequences from mining begins with knowing the mineralogy and mineral reactivity of the ore, the wastes, and of secondary minerals formed later. Jamieson et al. review the importance of mineralogical studies in mine planning and remediation. A number of types of site-specific studies are needed to identify environmental risks related to individual mines. Lapakko reviews the general framework of mine waste characterization studies that are integral to the mine planning process. Hageman et al. present a comparative study of several static tests commonly used to characterize mine waste. The mining and ore processing practices employed at a specific mine site will vary on the basis of the commodities being targeted, the geology of the deposit, the geometry of the deposit, and the mining and ore processing methods used. Thus, these factors, in addition to the waste management practices used, can result in a variety of end-member mine waste features, each of which has its own set of challenges. Open pit mines and underground mines require waste rock to be removed to access ore. Waste rock presents unique problems because the rock is commonly mineralized at sub-economic grades and has not been processed to remove potentially problematic minerals, such as pyrite. Amos et al. examine the salient aspects of the geochemistry of waste rock. Mill tailings – the waste material after ore minerals have been removed – are a volumetrically important solid waste at many mine sites. Their fine grain size and the options for their management make their behavior in the environment distinct from that of waste rock. Lindsay et al. describe some of these differences through three case-study examples. Subaqueous disposal of tailings is another option described by Moncur et al. Cyanide leaching for gold extraction is a common method throughout the world. Johnson describes environmental aspects of cyanidation. Uranium mining presents unique environmental challenges, particularly since in-situ recovery has seen widespread use. Campbell et al. review the environmental geochemistry of uranium mining and current research on bioremediation. Ore concentrates from many types of metal mining undergo a pyrometallurgical technique known as smelting to extract the metal. Slag is the result of smelting, and it may be an environmental liability or a valuable byproduct, as described by Piatak et al. Finally, the open pits that result from surface mining commonly reach below the water table. At the end of mining, these pits may fill to form lakes that become part of the legacy of the mine. Castendyk et al., in two papers, review theoretical aspects of the environmental limnology of pit lakes. They also describe approaches that have been used to model pit lake water balance, wall-rock contributions to pit lake chemistry, pit lake water quality, and limnological processes, such as vertical mixing, through the use of three case studies.

Applied Geochemistry