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Understanding processes affecting mineral deposits in humid environments

Recent interdisciplinary studies by the U.S. Geological Survey have resulted in substantial progress toward understanding the influence that climate and hydrology have on the geochemical signatures of mineral deposits and the resulting mine wastes in the eastern United States. Specific areas of focus include the release, transport, and fate of acid, metals, and associated elements from inactive mines in temperate coastal areas and of metals from unmined mineral deposits in tropical to subtropical areas; the influence of climate, geology, and hydrology on remediation options for abandoned mines; and the application of radiogenic isotopes to uniquely apportion source contributions that distinguish natural from mining sources and extent of metal transport. The environmental effects of abandoned mines and unmined mineral deposits result from a complex interaction of a variety of chemical and physical factors. These include the geology of the mineral deposit, the hydrologic setting of the mineral deposit and associated mine wastes, the chemistry of waters interacting with the deposit and associated waste material, the engineering of a mine as it relates to the reactivity of mine wastes, and climate, which affects such factors as temperature and the amounts of precipitation and evapotranspiration; these factors, in turn, influence the environmental behavior of mineral deposits. The role of climate is becoming increasingly important in environmental investigations of mineral deposits because of the growing concerns about climate change.

Fact Sheet

Magnetic susceptibilities of minerals

Magnetic separation of minerals is a topic that is seldom reported in the literature for two reasons. First, separation data generally are byproducts of other projects; and second, this study requires a large amount of patience and is unusually tedious. Indeed, we suspect that most minerals probably are never investigated for this property. These data are timesaving for mineralogists who concentrate mono-mineralic fractions for chemical analysis, age dating, and for other purposes. The data can certainly be used in the ore-beneficiation industries. In some instances, magnetic-susceptibility data may help in mineral identification, where other information is insufficient. In past studies of magnetic separation of minerals, (Gaudin and Spedden, 1943; Tille and Kirkpatrick, 1956; Rosenblum, 1958; Rubinstein and others, 1958; Flinter, 1959; Hess, 1959; Baker, 1962; Meric and Peyre, 1963; Rojas and others, 1965; and Duchesne, 1966), the emphasis has been on the ferromagnetic and paramagnetic ranges of extraction. For readers interested in the history of magnetic separation of minerals, Krumbein and Pettijohn (1938, p. 344-346) indicated nine references back to 1848. The primary purpose of this paper is to report the magnetic-susceptibility data on as many minerals as possible, similar to tables of hardness, specific gravity, refractive indices, and other basic physical properties of minerals. A secondary purpose is to demonstrate that the total and best extraction ranges are influenced by the chemistry of the minerals. The following notes are offered to help avoid problems in separating a desired mineral concentrate from mixtures of mineral grains.

Open-File Report

U.S. Geological Survey Karst Interest Group Proceedings, Bowling Green, Kentucky, May 27-29, 2008

*INTRODUCTION AND ACKNOWLEDGMENTS* Karst aquifer systems are present throughout parts of the United States and some of its territories. The complex depositional environments that form carbonate rocks combined with post-depositional tectonic events and the diverse climatic regimes under which these rocks were formed result in unique hydrologic systems. The dissolution of calcium carbonate and the subsequent development of distinct and beautiful landscapes, caverns, and springs have resulted in some karst areas of the United States being designated as national or state parks and commercial caverns. Karst aquifers and landscapes that form in tropical areas, such as the north coast of Puerto Rico, differ greatly from karst areas in more arid climates, such as central Texas or western South Dakota. Many of these public and private lands contain unique flora and fauna associated with the hydrologic systems in these karst areas. As a result, multiple Federal, State, and local agencies have an interest in the study of karst terrains. Carbonate sediments and rocks (limestone and dolomite) are composed of greater than 50 percent carbonate minerals and the predominant carbonate mineral is calcium carbonate or limestone (CaCO3). Unlike terrigenous clastic sedimentation, the depositional processes that produce carbonate rocks are complex, involving both biological and physical processes. These depositional processes impact greatly the development of permeability of the sediments. Carbonate minerals readily dissolve or precipitate depending on the chemistry of the water flowing through the rock, thus the study of both marine and meteoric diagenesis of carbonate sediments is multidisciplinary. Even with a better understanding of the depositional environment and subsequent diagenesis, the dual porosity nature of karst aquifers presents challenges to scientists attempting to study ground-water flow and contaminant transport. Many of the major springs and aquifers in the United States are developed in carbonate rocks and karst areas. These aquifers and the springs that discharge from them, serve as major water-supply sources and as unique biological habitats. Commonly, there is competition for the water resources of karst aquifers, and urban development in karst areas can impact the ecosystem and water quality of these aquifers. The concept for developing a Karst Interest Group evolved from the November 1999 National Ground-Water Meeting of the U.S. Geological Survey (USGS), Water Resources Division. As a result, the Karst Interest Group was formed in 2000. The Karst Interest Group is a loose-knit grass-roots organization of USGS employees devoted to fostering better communication among scientists working on, or interested in, karst hydrology studies. The mission of the Karst Interest Group is to encourage and support interdisciplinary collaboration and technology transfer among USGS scientists working in karst areas. Additionally, the Karst Interest Group encourages cooperative studies between the different disciplines of the USGS and other Department of Interior agencies and university researchers or research institutes. The first Karst Interest Group workshop was held in St. Petersburg, Florida, February 13-16, 2001, in the vicinity of karst features of the Floridan aquifer system. The proceedings of that first meeting, Water-Resources Investigations Report 01-4011 are available online at: http://water.usgs.gov/ogw/karst/ The second Karst Interest Group workshop was held August 20-22, 2002, in Shepherdstown, West Virginia, in close proximity to the carbonate aquifers of the northern Shenandoah Valley. The proceedings of the second workshop were published in Water-Resources Investigations Report 02-4174, which is available online at the previously mentioned website. The third workshop of the Karst Interest Group was held September, 12-15, 2005, in Rapid City, South Dakota, which is in close proximity to karst features

Scientific Investigations Report

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

Editorial: From cold seeps to hydrothermal vents: Geology, chemistry, microbiology, and ecology in marine and coastal environments

This Research Topic compiles contemporary studies on cold seeps, hydrothermal vents, mud volcanoes, and related seafloor features that are associated with focused fluid emissions and the transfer of carbon, other chemical species, and sometimes heat from the geosphere to the ocean. Because these features sometimes tap fluids and gas originating kilometers below the seafloor, they provide an important window into deep processes that are otherwise inaccessible to scientists. At the shallow portion of their journey, migrating fluids nearing the seafloor contribute to a range of unique biological, physical, and chemical processes within the sediments themselves and at the sediment-water interface. Seafloor fluid emissions play a critical role in global biogeochemical cycles, ocean chemistry, and possibly even climate change. Seafloor leakage points often emit hydrocarbon gases (especially methane and CO 2 ) and are sometimes the loci for deposition of seafloor minerals that have economic value. A burgeoning area of research focuses on natural products generated at these features, seeking compounds with potential pharmaceutical or other applications. Multidisciplinary studies have become routine for characterization of seafloor fluid emission sites, attesting to the inseparability of geologic, physical, chemical, and biological processes in these settings. It is increasingly common for researchers to combine in a single research cruise: subbottom imaging and seafloor mapping; porewater and water column geochemistry and gas sampling; sediment retrieval for lithologic, biostratigraphic, and solid phase analyses; and studies of benthic and subseafloor communities at the microbial to macrofaunal scales. This multidisciplinary approach has the advantage of ensuring the spatial and temporal coincidence of surveys and samples, an important factor at highly dynamic seafloor fluid emission sites. In addition, researchers often use remotely operated vehicles (ROVs), autonomous underwater vehicles (AUVs), or human-occupied vehicles (HOVs) to record video of the seafloor, compile photomosaics, collect targeted samples, and survey with high-resolution geophysical near-seafloor systems, providing a degree of detail about seafloor fluid emission sites that is unprecedented compared to most areas of the deep ocean. While rarer, long-term cabled observatories or shorter-term deployments of portable observatories are also used at some loci for seafloor fluid flux and are particularly helpful for capturing temporal variations at these dynamic features. Here we summarize the Research Topic’s contribution to multidisciplinary seafloor emission studies in the categories of cold seeps, mud volcanoes, and hydrothermal vents. Figure 1 shows the geographic distribution of the studies in this Research Topic and key features referred to in this Introduction.

Frontiers in Earth Science

Response curves for phosphorus plume lengths from reactive-solute-transport simulations of onland disposal of wastewater in noncarbonate sand and gravel aquifers

Surface-water resources in Massachusetts often are affected by eutrophication, excessive plant growth, which has resulted in impaired use for a majority of the freshwater ponds and lakes and a substantial number of river-miles in the State. Because supply of phosphorus usually is limiting to plant growth in freshwater systems, control of phosphorus input to surface waters is critical to solving the impairment problem. Wastewater is a substantial source of phosphorus for surface water, and removal of phosphorus before disposal may be necessary. Wastewater disposed onland by infiltration loses phosphorus from the dissolved phase during transport through the subsurface and may be an effective disposal method; quantification of the phosphorus loss can be simulated to determine disposal feasibility. In 2003, the U.S. Geological Survey, in cooperation with the Massachusetts Department of Environmental Protection, initiated a project to simulate distance of phosphorus transport in the subsurface for plausible conditions of onland wastewater disposal and subsurface properties. A coupled one-dimensional unsaturated-zone and three-dimensional saturated-zone reactive-solute-transport model (PHAST) was used to simulate lengths of phosphorus plumes. Knowledge of phosphorus plume length could facilitate estimates of setback distances for wastewater-infiltration sites from surface water that would be sufficient to protect the surface water from eutrophication caused by phosphorus transport through the subsurface and ultimate discharge to surface water. The reactive-solute-transport model PHAST was used to simulate ground-water flow, solute transport, equilibrium chemistry for dissolved and sorbed species, and kinetic regulation of organic carbon decomposition and phosphate mineral formation. The phosphorus plume length was defined for the simulations as the maximum extent of the contour for the 0.015 milligram-per-liter concentration of dissolved phosphorus downgradient from the infiltration bed after disposal cessation. Duration of disposal before cessation was assumed to be 50 years into an infiltration bed of 20,000 square feet at the rate of 3 gallons per square foot per day. Time for the maximum extent of the phosphorus plume to develop is on the order of 100 years after disposal cessation. Simulations indicated that phosphorus transport beyond the extent of the 0.015 milligram-per-liter concentration contour was never more than 0.18 kilogram per year, an amount that would likely not alter the ecology of most surface water. Simulations of phosphorus plume lengths were summarized in a series of response curves. Simulated plume lengths ranged from 200 feet for low phosphorus-concentration effluents (0.25 milligram per liter) and thick (50 feet) unsaturated zones to 3,400 feet for high phosphorus-concentration effluents (14 milligrams per liter) discharged directly into the aquifer (unsaturated-zone thickness of 0 feet). Plume length was nearly independent of unsaturated-zone thickness at phosphorus concentrations in the wastewater that were less than 2 milligrams per liter because little or no phosphorus mineral formed at low phosphorus concentrations. For effluents of high phosphorus concentration, plume length varied from 3,400 feet for unsaturated-zone thickness of 0 to 2,550 feet for unsaturated-zone thickness of 50 feet. Model treatments of flow and equilibrium-controlled chemistry likely were more accurate than rates of kinetically controlled reactions, notably precipitation of iron-phosphate minerals; the kinetics of such reactions are less well known and thus less well defined in the model. Sensitivity analysis indicated that many chemical and physical aquifer properties, such as hydraulic gradient and model width, did not affect the simulated plume length appreciably, but duration of discharge, size of infiltration bed, amount of dispersion, and number of sorption sites on the aquifer sediments did affect plume length appreciably. Because simulation of plume length in carbonate-mineral sediments indicated that the plume would be substantially longer than in noncarbonate-mineral sediments, the application of the response curves in locations with carbonate-mineral sediments would be inappropriate. The effect of carbonate minerals in sediments is to increase pH, which causes decreased sorption of phosphorus on aquifer sediments. Phosphorus removal from solution by precipitation onto aquifer sediments is more efficient at high concentrations of disposed phosphorus than at low concentrations. At very low phosphorus concentrations, the solubility product of phosphorus minerals is not exceeded and no phosphorus mineral forms. An important consequence is that removal of dissolved phosphorus from the plume by processes in the subsurface is decreased the more that removal efforts are applied in treatment before wastewater is disposed. Model simulations indicate that removal of phosphorus from wastewater disposed through septic systems would have the advantage of efficient phosphorus removal in the subsurface because phosphorus concentrations are high in septic-system effluent. Short plume lengths result from wastewater disposal through septic systems because of the efficient phosphorus removal and because of the low volume of wastewater involved. The simulation results for small-volume systems are not quantitative, however, because wastewater-infiltration rates are much lower than those of the higher-volume system that was used to calibrate the model and to create the plume-length response curves. The response curves for phosphorus plume lengths, as defined by the maximum extent of the 0.015 milligram-per-liter concentration contour, is clearly defined in the model simulations, although the relation between simulated plume length and protective setback distance is subject to interpretation. Phosphorus does move beyond the point at which the simulated 0.015 milligram-per-liter concentration contour has stopped, so that a determination of protective setback distance must include a consideration of whether that continued flux, or some other flux amount, is appropriate. Also, simulations indicate that phosphorus plumes do not reach their full extent until 50 to 200 years after disposal cessation, depending on concentration of phosphorus disposed. No phosphorus plume has been monitored for that long after cessation, so there is no way to verify the long-term simulation results.

Massachusetts

Development of soil radiocarbon profiles in a reactive transport framework

Today, there is a greater appreciation for the importance of the physical protection of carbon (C) through interactions with mineral surfaces, isolation from microbes, and the important role of transport in shaping soil properties and controlling moisture limitations on decomposition. As our paradigm for soil organic carbon (SOC) preservation changes, so too should our representation of the underlying processes in soil models. Reactive transport models (RTMs) provide a framework capable of assessing the interactive influence of soil chemistry and transport processes on the accumulation and turnover of SOC. In this study, we present new developments in the isotopically enabled RTM “CrunchTope,” which is capable of explicitly tracking the three isotopes of carbon ( 12 C, 13 C, and 14 C) and their fractionation between multiple coexisting and interacting solid, liquid and gas phases. This modeling framework opens the door to new applications of depth-resolved RTMs models in application to SOC and deeper subsurface carbon reservoirs. Here, we demonstrate SOC accumulation and radiocarbon aging for long-timescale models of soil development in CrunchTope. Our goal is to assess advantages and limitations of such an approach and to identify the type and complexity of reaction networks that are required to adequately apply this model to SOC dynamics. We assess the behavior of this model relative to a high-resolution dataset of SOC content, stable isotope composition, and radiocarbon ages as well as physical and hydrologic data measured from a chronosequence of soils located near Santa Cruz, California. Starting from a previously published model using a simplified reaction network with a single class of carbon, we sequentially incorporate multiple C reservoirs subject to both reactivity and transport pathways. Our results indicate that multiple SOC pools with different mean ages of C do not inherently emerge as a result of including reactions which are conventionally expected to provide a diversity of transit times, i.e., sorption and complexation of SOC on mineral surfaces. Instead, transit times emerge as a result of the timescales of the reactions represented in the reaction network. For mineral associated C, the RTM framework imposes dynamic equilibrium with the fluid phase dissolved organic C, such that no distinction in radiocarbon ages is achieved between these pools. Aged C can be produced by including a solid-phase C reservoir, with a rate-limited solubilization coefficient. Aging of SOC in this way is more akin to selective preservation than to mineral protection and, while such a mechanism may be at play in many soils, mineral protection is thought to be at least as important. As such, our results indicate that additional parameterization is required to reproduce the heterogeneity of carbon transit times that result from organo-mineral interactions. These efforts show the promise of a modeling approach where the varied transit time of soil C emerges from the dynamic physical and hydrologic properties of the model rather than from the a priori assignment of operationally defined pools.

Geochimica et Cosmochimica Acta

Geochemistry of groundwater in the Beaver and Camas Creek drainage basins, eastern Idaho

The U.S. Geological Survey (USGS), in cooperation with the U.S. Department of Energy, is studying the fate and transport of waste solutes in the eastern Snake River Plain (ESRP) aquifer at the Idaho National Laboratory (INL) in eastern Idaho. This effort requires an understanding of the natural and anthropogenic geochemistry of groundwater at the INL and of the important physical and chemical processes controlling the geochemistry. In this study, the USGS applied geochemical modeling to investigate the geochemistry of groundwater in the Beaver and Camas Creek drainage basins, which provide groundwater recharge to the ESRP aquifer underlying the northeastern part of the INL. Data used in this study include petrology and mineralogy from 2 sediment and 3 rock samples, and water-quality analyses from 4 surface-water and 18 groundwater samples. The mineralogy of the sediment and rock samples was analyzed with X-ray diffraction, and the mineralogy and petrology of the rock samples were examined in thin sections. The water samples were analyzed for field parameters, major ions, silica, nutrients, dissolved organic carbon, trace elements, tritium, and the stable isotope ratios of hydrogen, oxygen, carbon, sulfur, and nitrogen. Groundwater geochemistry was influenced by reactions with rocks of the geologic terranes—carbonate rocks, rhyolite, basalt, evaporite deposits, and sediment comprised of all of these rocks. Agricultural practices near and south of Dubois and application of road anti-icing liquids on U.S. Interstate Highway 15 were likely sources of nitrate, chloride, calcium, and magnesium to groundwater. Groundwater geochemistry was successfully modeled in the alluvial aquifer in Camas Meadows and the ESRP fractured basalt aquifer using the geochemical modeling code PHREEQC. The primary geochemical processes appear to be precipitation or dissolution of calcite and dissolution of silicate minerals. Dissolution of evaporite minerals, associated with Pleistocene Lake Terreton, is an important contributor of solutes in the Mud Lake-Dubois area. Oxidation-reduction reactions are important influences on the chemistry of groundwater at Camas Meadows and the Camas National Wildlife Refuge. In addition, mixing of different groundwaters or surface water with groundwater appears to be an important physical process influencing groundwater geochemistry in much of the study area, and evaporation may be an important physical process influencing the groundwater geochemistry of the Camas National Wildlife Refuge. The mass-balance modeling results from this study provide an explanation of the natural geochemistry of groundwater in the ESRP aquifer northeast of the INL, and thus provide a starting point for evaluating the natural and anthropogenic geochemistry of groundwater at the INL.

Idaho

A primer on trace metal-sediment chemistry

In most aquatic systems, concentrations of trace metals in suspended sediment and the top few centimeters of bottom sediment are far greater than concentrations of trace metals dissolved in the water column. Consequently, the distribution, transport, and availability of these constituents can not be intelligently evaluated, nor can their environmental impact be determined or predicted solely through the sampling and analysis of dissolved phases. This Primer is designed to acquaint the reader with the basic principles that govern the concentration and distribution of trace metals associated with bottom and suspended sediments. The sampling and analysis of suspended and bottom sediments are very important for monitoring studies, not only because trace metal concentrations associated with them are orders of magnitude higher than in the dissolved phase, but also because of several other factors. Riverine transport of trace metals is dominated by sediment. In addition, bottom sediments serve as a source for suspended sediment and can provide a historical record of chemical conditions. This record will help establish area baseline metal levels against which existing conditions can be compared. Many physical and chemical factors affect a sediment's capacity to collect and concentrate trace metals. The physical factors include grain size, surface area, surface charge, cation exchange capacity, composition, and so forth. Increases in metal concentrations are strongly correlated with decreasing grain size and increasing surface area, surface charge, cation exchange capacity, and increasing concentrations of iron and manganese oxides, organic matter, and clay minerals. Chemical factors are equally important, especially for differentiating between samples having similar bulk chemistries and for inferring or predicting environmental availability. Chemical factors entail phase associations (with such sedimentary components as interstitial water, sulfides, carbonates, and organic matter) and ways in which the metals are entrained by the sediments (such as adsorption, complexation, and within mineral lattices).

Water Supply Paper

Lithostratigraphic, borehole-geophysical, hydrogeologic, and hydrochemical data from the East Bay Plain, Alameda County, California

The U.S. Geological Survey, in cooperation with the East Bay Municipal Utility District, carried out an investigation of aquifer-system deformation associated with groundwater-level changes at the Bayside Groundwater Project near the modern San Francisco Bay shore in San Lorenzo, California. As a part of the Bayside Groundwater Project, East Bay Municipal Utility District proposed an aquifer storage and recovery program for 1 million gallons of water per day. The potential for aquifer-system compaction and expansion, and related subsidence, uplift, or both, resulting from aquifer storage and recovery activities were investigated and monitored in the Bayside Groundwater Project. In addition, baseline analysis of groundwater and substrata properties were performed to assess the potential effect of such activities. Chemical and physical data, obtained from the subsurface at four sites on the east side of San Francisco Bay in the San Lorenzo and San Leandro areas of the East Bay Plain, Alameda County, California, were collected during the study. The results of the study were provided to the East Bay Municipal Utility District and other agencies to evaluate the chemical and mechanical responses of aquifers underlying the East Bay Plain to the future injection and recovery of imported water from the Sierra Nevada of California. Among 4 sites, 14 piezometers and 2 extensometers were installed in 6 boreholes, which ranged in depth from 460 to 1,040 feet. The lithology of drill cuttings, collected at 5- or 10-foot intervals, was described for grain size and any other noticeable features, such as wood or shell fragments. Borehole geophysical logging was performed at each site in the deepest borehole, immediately following drilling. Drill-core samples, totaling 284 feet, were collected at the Bayside site. The drill-core sediment was subsampled to determine pore-water chemistry, vertical hydraulic conductivity, and physical and mechanical properties at different depths. Depositional environment and age were determined by luminescence geochronology and fossil identification. The elemental composition of the drill-core sediments was determined by inductively coupled plasma mass spectroscopy and instrumental neutron activation by abbreviated count analysis. Mineral composition was determined by X-ray diffraction and scanning electron microscopy analysis. Groundwater samples were collected from all 14 piezometers as part of either the USGS Groundwater Ambient Monitoring and Assessment or the USGS National Water Quality Assessment program for water-quality analyses. Sample analytes included nutrients, major and minor ions, trace elements, isotopic ratios of hydrogen and oxygen in water, carbon-14, and tritium. Water-level and aquifer-system-compaction measurements, which indicated diurnal and seasonal fluctuations, were made at the Bayside Groundwater Project site. Slug tests were performed at the Bayside piezometers and nine pre-existing wells to estimate hydraulic conductivity.

California

Water chemistry at Snowshoe Mountain, Colorado: mixed processes in a common bedrock

At Snowshoe Mountain the primary bedrock is quite homogeneous, but weathering processes vary as waters moves through the soils, vadose zone and phreatic zone of the subsurface. In the thin soil, physical degradation of tuff facilitates preferential dissolution of potassium ion from glass within the rock matrix, while other silicate minerals remain unaltered. In the vadose zone, in the upper few meters of fractured bedrock, dilute water infiltrates during spring snowmelt and summer storms, leading to preferential dissolution of augite exposed on fracture surfaces. Deeper yet, in the phreatic zone of the fractured bedrock, Pleistocene calcite fracture fillings dissolve, and dioctahedral and trioctahedral clays form as penetrative weathering alters feldspar and pyroxene. Alkalinity is generated and silica concentrations are buffered by mineral alteration reactions.

Colorado

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

Iron mineralogy and bioaccessibility of dust generated from soils as determined by reflectance spectroscopy and magnetic and chemical properties--Nellis Dunes recreational area, Nevada

Atmospheric mineral dust exerts many important effects on the Earth system, such as atmospheric temperatures, marine productivity, and melting of snow and ice. Mineral dust also can have detrimental effects on human health through respiration of very small particles and the leaching of metals in various organs. These effects can be better understood through characterization of the physical and chemical properties of dust, including certain iron oxide minerals, for their extraordinary radiative properties and possible effects on lung inflammation. Studies of dust from the Nellis Dunes recreation area near Las Vegas, Nevada, focus on characteristics of radiative properties (capacity of dust to absorb solar radiation), iron oxide mineral type and size, chemistry, and bioaccessibility of metals in fluids that simulate human gastric, lung, and phagolysosomal fluids. In samples of dust from the Nellis Dunes recreation area with median grain sizes of 2.4, 3.1, and 4.3 micrometers, the ferric oxide minerals goethite and hematite, at least some of it nanosized, were identified. In one sample, in vitro bioaccessibility experiments revealed high bioaccessibility of arsenic in all three biofluids and higher leachate concentration and bioaccessibility for copper, uranium, and vanadium in the simulated lung fluid than in the phagolysosomal fluid. The combination of methods used here to characterize mineral dust at the Nellis Dunes recreation area can be applied to global dust and broad issues of public health.

Nevada

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

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

Physical-chemical conditions of ore deposition

Ore deposits form under a wide range of physical and chemical conditions, but those precipitating from hot, aqueous fluids—i.e. the hydrothermal deposits—form generally below 700°C and at pressures of only 1 or 2 kbar or less. Natural aqueous fluids in rocks may extract metal and sulfur from a variety of rock types or may acquire them as a residual heritage from a crystallizing silicate magma. Ore-forming hydrothermal fluids never appear as hot springs (except in deep, submarine situations) because they boil, mix with surface waters, and cool, thereby losing their ore-bearing ability before reaching the surface. Mineral systems function as chemical buffers and indicators just as buffers and indicators function in a chemical laboratory. By reading the record written in the buffer/indicator assemblages of minerals one can reconstruct many aspects of the former chemical environment. By studying the record of changing conditions one may deduce information regarding the processes functioning to create the succession of chemical environments and the ore deposits they represent. The example of the OH vein at Creede, Colorado, shows a pH buffered by the K-feldspar + muscovite + quartz assemblage and the covariation of S 2 and O 2 buffered by the assemblage chlorite + pyrite + quartz. Boiling of the ore fluid led to its oxidation to hematite-bearing assemblages and simultaneously produced an intensely altered, sericitic capping over the vein in response to the condensation of vapors bearing acidic components. The solubility of metals as calculated from experimental and theoretical studies of mineral solubility appears too low by at least one or two powers of ten to explain the mineralization at Creede. In contrast to Creede where the mineral stabilities all point to a relatively consistent chemistry, the Mississippi Valley type deposits present a puzzle of conflicting chemical clues that are impossible to reconcile with any single equilibrium situation. Thus we must seriously consider metastable equilibria; those most likely involve redox disequilibrium among the sulfur species in solution and perhaps also involve organic compounds.

Physics and Chemistry of the Earth

Mineralogy and petrology of the Cretaceous- Tertiary boundary clay bed and adjacent clay-rich rocks, Raton Basin, New Mexico and Colorado.

The Cretaceous-Tertiary (K-T) boundary is preserved in a sequence of coal-bearing, fluvial rocks in the lower part of the Raton Formation (Late Cretaceous and Paleocene) at several sites in the east-central part of the Raton Basin. The K-T boundary occurs at the top of a kaolinitic claystone layer, commonly referred to as the "boundary clay layer," in an interval of coal and carbonaceous shale. The boundary is defined by the disappearance of certain fossil-pollen taxa. The boundary clay layer also contains shocked quartz grains and abundance anomalies of iridium, chromium, and other elements. Each of these characteristics support the hypothesis of an asteroid impact at the end of the Cretaceous. Small goyazite spheres were also found in the boundary clay bed; however, their origin is uncertain. X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and thin-section petrography have shown that the boundary clay bed exhibits unique mineralogic and petrologic characteristics not possessed by other clay-rich beds in coal-bearing rocks of the Raton Basin. The boundary clay bed is composed primarily of well-crystallized kaolinite but also contains subordinate, randomly interstratified, mixed-layer illite/smectite, both of which appear to have been formed by the alteration of vitreous material in a coal-swamp environment. The bulk mineralogy of the boundary clay bed is similar to that of other kaolinite-rich clay beds (tonsteins) that altered in coal swamps from airfall volcanic ash. The alteration process and diagenetic products of the host material in the boundary clay bed, however, differed from those of the tonsteins, resulting in a unique petrographic fabric. The boundary clay bed is characterized by an overall imbricate fabric that may reflect an original vitreous material that included shards, bubbles, and spheres. The original fallout material of the boundary clay bed first altered to "cabbage-like" microspherules, indicating a halloysite or allophane precursor, and then to well-crystallized kaolinite; the well-crystallized kaolinite is the diagenetic stable phase for these rocks at their maximum burial conditions. In comparison, the vitreous components of the tonsteins were altered directly to coarse vermicular and platey kaolinite. Alteration of the original fallout material in the boundary bed was probably rapid, leading to hydrated, disordered, fine-grained clay minerals that formed into curled spherical or tubular shapes. The factors that produced these unique fabrics in the boundary clay bed existed at all K-T sites in the Raton Basin and were much different from those that formed the coarse platey and vermicular fabrics of ordinary tonsteins. The distinctive character of the boundary clay may be due to the unique nature and chemistry of the fallout material and (or) physical or chemical conditions existing shortly after its deposition.

Journal of Sedimentary Petrology