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Graphite

Graphite is a form of pure carbon that normally occurs as black crystal flakes and masses. It has important properties, such as chemical inertness, thermal stability, high electrical conductivity, and lubricity (slipperiness) that make it suitable for many industrial applications, including electronics, lubricants, metallurgy, and steelmaking. For some of these uses, no suitable substitutes are available. Steelmaking and refractory applications in metallurgy use the largest amount of produced graphite; however, emerging technology uses in large-scale fuel cell, battery, and lightweight high-strength composite applications could substantially increase world demand for graphite. Graphite ores are classified as “amorphous” (microcrystalline), and “crystalline” (“flake” or “lump or chip”) based on the ore’s crystallinity, grain-size, and morphology. All graphite deposits mined today formed from metamorphism of carbonaceous sedimentary rocks, and the ore type is determined by the geologic setting. Thermally metamorphosed coal is the usual source of amorphous graphite. Disseminated crystalline flake graphite is mined from carbonaceous metamorphic rocks, and lump or chip graphite is mined from veins in high-grade metamorphic regions. Because graphite is chemically inert and nontoxic, the main environmental concerns associated with graphite mining are inhalation of fine-grained dusts, including silicate and sulfide mineral particles, and hydrocarbon vapors produced during the mining and processing of ore. Synthetic graphite is manufactured from hydrocarbon sources using high-temperature heat treatment, and it is more expensive to produce than natural graphite. Production of natural graphite is dominated by China, India, and Brazil, which export graphite worldwide. China provides approximately 67 percent of worldwide output of natural graphite, and, as the dominant exporter, has the ability to set world prices. China has significant graphite reserves, and China’s graphite production is expected to increase, although rising labor costs and some mine production problems are developing. China is expected to continue to be the dominant exporter for the near future. Mexico and Canada export graphite mainly to the United States, which has not had domestic production of natural graphite since the 1950s. Most graphite deposits in the United States are too small, low-grade, or remote to be of commercial value in the near future, and the likelihood of discovering larger, higher-grade, or favorably located domestic deposits is unlikely. The United States is a major producer of synthetic graphite.

Professional Paper

The history and development of FETAX (ASTM standard guide, E-1439 on conducting the frog embryo teratogenesis Assay-Xenopus)

The energy crisis of the 1970's and 1980's prompted the search for alternative sources of fuel. With development of alternate sources of energy, concerns for biological resources potentially adversely impacted by these alternative technologies also heightened. For example, few biological tests were available at the time to study toxic effects of effluents on surface waters likely to serve as receiving streams for energy-production facilities; hence, we began to use Xenopus laevis embryos as test organisms to examine potential toxic effects associated with these effluents upon entering aquatic systems. As studies focused on potential adverse effects on aquatic systems continued, a test procedure was developed that led to the initial standardization of FETAX. Other .than a limited number of aquatic toxicity tests that used fathead minnows and cold-water fishes such as rainbow trout, X. laevis represented the only other aquatic vertebrate test system readily available to evaluate complex effluents. With numerous laboratories collaborating, the test with X. laevis was refined, improved, and developed as ASTM E-1439, Standard Guide for the Conducting Frog Embryo Teratogenesis Assay-Xenopus (FETAX). Collabrative work in the 1990s yielded procedural enhancements, for example, development of standard test solutions and exposure methods to handle volatile organics and hydrophobic compounds. As part of the ASTM process, a collaborative interlaboratory study was performed to determine the repeatability and reliability of FETAX. Parallel to these efforts, methods were also developed to test sediments and soils, and in situ test methods were developed to address "lab-to-field extrapolation errors" that could influence the method's use in ecological risk assessments. Additionally, a metabolic activation system composed of rat liver microsomes was developed which made FETAX more relevant to mammalian studies.

Conference Paper

Guidelines for the use of the semipermeable membrane device (SPMD) and the polar organic chemical integrative sampler (POCIS) in environmental monitoring studies

The success of an environmental monitoring study using passive samplers, or any sampling method, begins in the office or laboratory. Regardless of the specific methods used, the general steps include the formulation of a sampling plan, training of personnel, performing the field (sampling) work, processing the collected samples to recover chemicals of interest, analysis of the enriched extracts, and interpretation of the data. Each of these areas will be discussed in the following sections with emphasis on specific considerations with the use of passive samplers. Water is an extremely heterogeneous matrix both spatially and temporally (Keith, 1991). The mixing and distribution of dissolved organic chemicals in a water body are controlled by the hydrodynamics of the water, the sorption partition coefficients of the chemicals, and the amount of organic matter (suspended sediments, colloids, and dissolved organic carbon) present. In lakes and oceans, stratification because of changes in temperature, water movement, and water composition can occur resulting in dramatic changes in chemical concentrations with depth (Keith, 1991). Additional complications related to episodic events, such as surface runoff, spills, and other point source contamination, can result in isolated or short-lived pulses of contaminants in the water. The application of passive sampling technologies for the monitoring of legacy and emerging organic chemicals in the environment is becoming widely accepted worldwide. The primary use of passive sampling methods for environmental studies is in the area of surface-water monitoring; however, these techniques have been applied to air and groundwater monitoring studies. Although these samplers have no mechanical or moving parts, electrical or fuel needs which require regular monitoring, there are still considerations that need to be understood in order to have a successful study. Two of the most commonly used passive samplers for organic contaminants are the semipermeable membrane device (SPMD) and the polar organic chemical integrative sampler (POCIS). The tips given in this document focus on these two samplers but are applicable to most types of passive sampling devices. The information in this guide is heavily weighted towards the sampling of water; however, information specific to the use of SPMDs for air sampling will also be covered.

Techniques and Methods

Widespread potential for microbial MTBE degradation in surface-water sediments

Microorganisms indigenous to stream and lake bed sediments, collected from 11 sites throughout the United States, demonstrated significant mineralization of the fuel oxygenate, methyl-tert-butyl ether (MTBE). Mineralization of [U-14C]MTBE to 14CO2 ranged from 15 to 66% over 50 days and did not differ significantly between sediments collected from MTBE contaminated sites and from sites with no history of MTBE exposure. This result suggests that even the microbial communities indigenous to newly contaminated surface water systems will exhibit some innate ability to attenuate MTBE under aerobic conditions. The magnitude of MTBE mineralization was related to the sediment grain size distribution. A pronounced, inverse correlation (p < 0.001; r2 = 0.73) was observed between the final recovery of 14CO2 and the percentage content of silt and clay sized grains (grain diameter < 0.125 mm). The results of this study indicate that the microorganisms that inhabit the bed sediments of streams and lakes can degrade MTBE efficiently and that this capability is widespread in the environment. Thus aerobic bed sediment microbial processes may provide a significant environmental sink for MTBE in surface water systems throughout the United States and may contribute to the reported transience of MTBE in some surface waters.

Environmental Science & Technology

Airborne remote sensing for geology and the environment; present and future

In 1988, a group of leading experts from government, academia, and industry attended a workshop on airborne remote sensing sponsored by the U.S. Geological Survey (USGS) and hosted by the Branch of Geophysics. The purpose of the workshop was to examine the scientific rationale for airborne remote sensing in support of government earth science in the next decade. This report has arranged the six resulting working-group reports under two main headings: (1) Geologic Remote Sensing, for the reports on geologic mapping, mineral resources, and fossil fuels and geothermal resources; and (2) Environmental Remote Sensing, for the reports on environmental geology, geologic hazards, and water resources. The intent of the workshop was to provide an evaluation of demonstrated capabilities, their direct extensions, and possible future applications, and this was the organizational format used for the geologic remote sensing reports. The working groups in environmental remote sensing chose to present their reports in a somewhat modified version of this format. A final section examines future advances and limitations in the field. There is a large, complex, and often bewildering array of remote sensing data available. Early remote sensing studies were based on data collected from airborne platforms. Much of that technology was later extended to satellites. The original 80-m-resolution Landsat Multispectral Scanner System (MSS) has now been largely superseded by the 30-m-resolution Thematic Mapper (TM) system that has additional spectral channels. The French satellite SPOT provides higher spatial resolution for channels equivalent to MSS. Low-resolution (1 km) data are available from the National Oceanographic and Atmospheric Administration's AVHRR system, which acquires reflectance and day and night thermal data daily. Several experimental satellites have acquired limited data, and there are extensive plans for future satellites including those of Japan (JERS), Europe (ESA), Canada (Radarsat), and the United States (EOS). There are currently two national airborne remote sensing programs (photography, radar) with data archived at the USGS' EROS Data Center. Airborne broadband multispectral data (comparable to Landsat MSS and TM but involving several more channels) for limited geographic areas also are available for digital processing and analysis. Narrow-band imaging spectrometer data are available for some NASA experiment sites and can be acquired for other locations commercially. Remote sensing data and derivative images, because of the uniform spatial coverage, availability at different resolutions, and digital format, are becoming important data sets for geographic information system (GIS) analyses. Examples range from overlaying digitized geologic maps on remote sensing images and draping these over topography, to maps of mineral distribution and inferred abundance. A large variety of remote sensing data sets are available, with costs ranging from a few dollars per square mile for satellite digital data to a few hundred dollars per square mile for airborne imaging spectrometry. Computer processing and analysis costs routinely surpass these expenses because of the equipment and expertise necessary for information extraction and interpretation. Effective use requires both an understanding of the current methodology and an appreciation of the most cost-effective solution.

Bulletin

Comparison of Eh and H2 measurements for delineating redox processes in a contaminated aquifer

Measurements of oxidation-reduction potential ( E h ) and concentrations of dissolved hydrogen (H 2 ) were made in a shallow groundwater system contaminated with solvents and jet fuel to delineate the zonation of redox processes. E h measurements ranged from +69 to -158 mV in a cross section of the contaminated plume and accurately delineated oxic from anoxic groundwater. Plotting measured E h and pH values on an equilibrium stability diagram indicated that Fe(III) reduction was the predominant redox process in the anoxic zone and did not indicate the presence of methanogenesis and sulfate reduction. In contrast, measurements of H 2 concentrations indicated that methanogenesis predominated in heavily contaminated sediments near the water table surface (H 2 ∼ 7.0 nM) and that the methanogenic zone was surrounded by distinct sulfate-reducing (H 2 ∼ 1-4 nM) and Fe(III)-reducing (H 2 ∼ 0.1-0.8 nM) zones. The presence of methanogenesis, sulfate reduction, and Fe(III) reduction was confirmed by the distribution of dissolved oxygen, sulfate, Fe(II), and methane in groundwater. These results show that H 2 concentrations were more useful for identifying anoxic redox processes than E h measurements in this groundwater system. However, H 2 -based redox zone delineations are more reliable when H 2 concentrations are interpreted in the context of electron-acceptor (oxygen, nitrate, sulfate) availability and the presence of final products [Fe(II), sulfide, methane] of microbial metabolism.

Environmental Science & Technology

Rates of As and trace-element mobilization caused by Fe reduction in mixed BTEX–ethanol experimental plumes

Biodegradation of organic matter, including petroleum-based fuels and biofuels, can create undesired secondary water-quality effects. Trace elements, especially arsenic (As), have strong adsorption affinities for Fe(III) (oxyhydr)-oxides and can be released to groundwater during Fe-reducing biodegradation. We investigated the mobilization of naturally occurring As, cobalt (Co), chromium (Cr), and nickel (Ni) from wetland sediments caused by the introduction of benzene, toluene, ethylbenzene, and xylenes (BTEX) and ethanol mixtures under iron- and nitrate-reducing conditions, using in situ push–pull tests. When BTEX alone was added, results showed simultaneous onset and similar rates of Fe reduction and As mobilization. In the presence of ethanol, the maximum rates of As release and Fe reduction were higher, the time to onset of reaction was decreased, and the rates occurred in multiple stages that reflected additional processes. The concentration of As increased from <1 μg/L to a maximum of 99 μg/L, exceeding the 10 μg/L limit for drinking water. Mobilization of Co, Cr, and Ni was observed in association with ethanol biodegradation but not with BTEX. These results demonstrate the potential for trace-element contamination of drinking water during biodegradation and highlight the importance of monitoring trace elements at natural and enhanced attenuation sites.

Environmental Science & Technology

Hydrologic and microbiological factors affecting persistence and migration of petroleum hydrocarbons spilled in a continuous-permafrost region

Fuel spills, totaling about 1300 m3, occurred between 1976 and 1978 adjacent to Imikpuk Lake, a drinking water source near Barrow, AK. Substantial contamination of soils and groundwater near the lake persists. We examined the magnitude and direction of groundwater flux and the microbial activity at this site to understand the persistence of contamination and its effect on the lake. We found that groundwater flux is small due to shallow permafrost, which restricts the cross-sectional area available for flow, and to the short annual thaw season (ca. 90 days). The small flux and limited depth also constrain contaminant transport and dispersion, resulting in persistent, shallow contamination. The numbers of hydrocarbon-oxidizing microorganisms and their laboratory mineralization potentials for benzene (at 10 ??C) were higher in samples from contaminated areas than in reference samples. Benzene mineralization potentials in groundwater samples were comparable to more temperate systems (0.1-0.5 mg of benzene mineralized L-1 day-1) and were stimulated by nutrient additions. Field measurements of dissolved oxygen, nitrate, ferrous iron, and sulfide in groundwater provided evidence that biodegradation of petroleum hydrocarbons is occurring in situ. Despite evidence of an active microbial population, microbial processes, like contaminant transport, are likely limited at this site by the short annual thaw season.

Environmental Science & Technology

Generation of ethylene tracer by noncatalytic pyrolysis of natural gas at elevated pressure

There is a critical need within the pipeline gas industry for an inexpensive and reliable technology to generate an identification tag or tracer that can be added to pipeline gas to identify gas that may escape and improve the deliverability and management of gas in underground storage fields. Ethylene is an ideal tracer, because it does not exist naturally in the pipeline gas, and because its physical properties are similar to the pipeline gas components. A pyrolysis process, known as the Tragen process, has been developed to continuously convert the ???2%-4% ethane component present in pipeline gas into ethylene at common pipeline pressures of 800 psi. In our studies of the Tragen process, pyrolysis without steam addition achieved a maximum ethylene yield of 28%-35% at a temperature range of 700-775 ??C, corresponding to an ethylene concentration of 4600-5800 ppm in the product gas. Coke deposition was determined to occur at a significant rate in the pyrolysis reactor without steam addition. The ?? 13C isotopic analysis of gas components showed a ?? 13C value of ethylene similar to ethane in the pipeline gas, indicating that most of the ethylene was generated from decomposition of the ethane in the raw gas. However, ?? 13C isotopic analysis of the deposited coke showed that coke was primarily produced from methane, rather than from ethane or other heavier hydrocarbons. No coke deposition was observed with the addition of steam at concentrations of > 20% by volume. The dilution with steam also improved the ethylene yield. ?? 2005 American Chemical Society.

Energy and Fuels

Biogenic coal-to-methane conversion can be enhanced with small additions of algal amendment in field-relevant upflow column reactors

ubsurface coal environments, where biogenic coal-to-methane conversion occurs, are difficult to access, resulting in inherent challenges and expenses for in situ experiments. Previous batch reactor studies provided insights into specific processes, pathways, kinetics, and engineering strategies, but field-relevance is restricted due to limited substrate availability or byproduct accumulation that may influence reactions or metabolisms. In this study, continuous-flow column reactors were used to overcome some batch limitations, improve the understanding of in situ conditions, and increase field-relevance for subsurface engineering technology development. The bench-scale reactor system was constructed to investigate the addition of algal amendment for enhancing microbial coal-to-methane conversion previously developed in batch systems. Four reactor columns were packed with coal and inoculated with a microbial consortium from the same Flowers-Goodale coal bed. Two reactors were amended with 13 C-labeled algal amendment on day 0, and two were unamended. On day 61, one previously amended and one previously unamended reactor were re-amended. Produced gases were captured in a gas trap, and CH 4 and CO 2 were quantified. The reactor amended twice produced 1712.6 µmol CH 4 (4.6% as 13 CH 4 ). The reactor amended only on day 0 produced 1485.5 µmol CH 4 (2.6% as 13 CH 4 ). The reactor amended only on day 61 produced 278.9 µmol CH 4 (3.9% as 13 CH 4 ). The reactor with no amendment produced no measurable gases for the duration of the 172-day experiment. Amendment increased the rate of coal-to-methane conversion and total gas production; most of the produced gases were due to coal conversion with only small contributions (<7%) from amendment conversion.

Fuel

Subsurface fate of spilled petroleum hydrocarbons in continuous permafrost

Accidental releases of approximately 2000 m3 of fuel have resulted in subsurface contamination adjacent to Imikpuk Lake, a drinking-water source near Barrow, AK. This paper presents a conceptual model of the distribution and transport of subsurface free-phase hydrocarbons at this site. The mean annual temperature in Barrow is -13 ??C, and average monthly temperatures exceed 0 ??C only during the months of June, July, and August. As a result, the region is underlain by areally continuous permafrost that extends to depths of up to 300 m and constrains subsurface hydrologic processes to a shallow zone that temporarily thaws each summer. During the 1993 and 1994 thaw seasons, the measured depth of thaw varied across the site from approximately 0.5 to 2 m. However, exploratory borings in 1995 showed that free-phase hydrocarbons were present at depths greater than 3 m, indicating that permafrost at this site is not a barrier to the vertical migration of nonaqueous-phase liquids. In 1996, a subsurface containment barrier was installed to prevent lateral movement of contaminated water to Imikpuk Lake, and a recovery trench was excavated upgradient of the barrier to facilitate removal of free-phase hydrocarbons. Free-phase hydrocarbons were recovered from the trench during 1996, 1997, and 1998. Recovery rates diminished over this time, and in 1999, no further product was recovered and the recovery operation was halted. Subsequent exploratory borings in 2001 and 2002 have revealed that some product remains in the subsurface. Data indicate that this remaining product exists in small discrete pockets or very thin layers of hydrocarbon floating on brine. These small reservoirs appear to be isolated from one another by relatively impermeable permafrost. Published by Elsevier B.V.

Cold Regions Science and Technology

Iron-ore resources of the United States including Alaska and Puerto Rico, 1955

The importance of iron ore, the basic raw material of steel, as a fundamental mineral, resource is shown by the fact that about 100 million long tons of steel is used annually in the economy of the United States, as compared with a combined total of about 5 million long tons of copper, lead, zinc, and aluminum. Satisfying this annual demand for steel requires about 110 million tons of iron ore and 70 million tons of scrap iron and steel. The average annual consumption of iron ore in the United States from 1951 to 1955, inclusive, was about 110 million long tons, which is about twice the annual average from 1900 to 1930. Production of iron ore in the United States in this 5-year period averaged approximately 100 million long tons annually, divided by regions as follows (in percent): Lake Superior, 84.1; southeastern, 6.7; western, 6.7; northeastern, 1.4; and central and gulf, 1.1. Mining of iron ore began in the American Colonies about 1619, and for 225 years it was limited to eastern United States where fuel and markets were readily available. Production of iron ore from the Lake Superior region began in 1846; the region became the leading domestic source by 1890, and the Mesabi range in Minnesota has been the world's most productive area since 1896. Proximity of raw materials, water transportation, and markets has resulted in centralization of the country's iron and steel industry in the lower Great Lakes area. Increased imports of iron ore being delivered to eastern United States as well as demands for steel in nearby markets have given impetus to expansion in the steel-making capacity in this area. The four chief iron-ore minerals - hematite, liminite, magnetite, and siderite - are widely distributed but only locally form deposits of sufficient tonnage and grade to be commercially valuable at the present time. The iron content of these minerals, of which hematite is the most important, ranges from 48 percent in siderite to 72 percent in magnetite, but as these minerals are associated with other rock-forming minerals, the iron content of marketable ore has a lower range from 30 to 67 percent. Chemical constituents other than iron also are important in determining the marketability of iron ore. Although some iron ores can be used in the blast furnace as mined, others must first be improved either chemically by reduction of undesirable constituents, or physically by aggregation. Phosphorus and sulfur particularly are common deleterious elements; excessive silica is also undesirable but within certain limits can be controlled by additional flux. Lime and magnesia are beneficial in specified amounts because of their fluxing qualities, and a small amount of alumina improves the fluidity of slag. Manganese is especially desirable as a deoxidizing and desulfurizing agent. Titanium, chromium, and nickel must also be considered in the use of ore containing these elements. The principal iron-ore deposits in the United States have been formed by three processes. Hematite-bearing bedded deposits such as those at Birmingham, Ala., are marine sedimentary rocks which, except for weathering along the outcrop, have remained practically unaltered since deposition. Deposits of the Lake Superior region, also in sedimentary strata, originally had a slightly lower iron content than those at-Birmingham, but ore bodies of hematite and limonite were formed by removal of other constituents in solution after deposition of the beds, with a relative increase of iron content in the material remaining. Limestone adjacent to igneous intrusions has been replaced by magnetite deposits at Cornwall, Pa., and by hematite-magnetite deposits near Cedar City, Utah. Magnetite deposits in New Jersey and in the Adirondack Mountains of New York are generally believed to have been formed by replacement of grains of other minerals in metamorphic rocks. Iron-ore resources are made up of reserves of iron ore, material usable under existing economic and technologic conditions; and potential ore, material likely to become usable under more favorable conditions. The tonnage and grade of material of combined reserves and potential ore in each of the deposits known or believed to contain at least 200,000 long tons of iron-ore resources are tabulated in this report, and numerous sources of additional information are given in a selected bibliography. The total domestic iron-ore resources are estimated at approximately 75,000 million long tons of crude ore. About 10,000 million tons of the resources is reserves of crude ore that will probably yield 5,500 million tons of concentrates and direct-shipping ore. About 65,000 million tons is potential ore and may yield 25,000 million tons of concentrates and some direct-shipping ore.

Bulletin