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USGS1978

Redox processes at surfaces of manganese oxide and their effects on aqueous metal ions

Mn oxides precipitated from aerated solutions of Mn2+ by raising the pH are reported in various publications to have the approximate composition Mn3O4 or MnOOH. These oxyhydroxides in turn can disproportionate to Mn2+ and MnO2 resulting in a substantial decrease in equilibrium Mn solubility. The disproportionation can catalyze the oxidation of Mn2+ and other metals by facilitating electron-transfer processes. Diversion of some electron transfers from Mn species to other metal ions can greatly decrease the equilibrium solubility of Co, Pb, Ni and some other elements in the presence of mixed-valence Mn oxides. Some scavenging and coprecipitation effects involving Mn oxides may be attributable to redox processes. Equilibrium solubilities for Mn, Co and Pb are summarized in four graphs. ?? 1978.

Chemical Geology↗

USGS1973

Petrology of some lithic fragments from Luna 20

Microscopic and electron microprobe studies were made of polished thin sections of part of a 30-mg sample of 250–500 μm lunar soil returned by Luna 20 from a point between Mare Fecunditatis and Mare Crisium. Very fine-grained lithic (crystalline) rock fragments, composing about one fifth of the total sample, have mineralogical compositions equivalent to various types of gabbro, anorthositic gabbro, gabbroic anorthosite and troctolite, with minor basalt. The textures now observed in these fragments are in large part metamorphic. Twentyseven electron microprobe analyses of minerals from these fragments are presented, including olivine, plagioclase, pyroxene, spinel, nickel-iron and a Zr-Ti-REE mineral possibly similar to ‘phase B’ of Lovering and Wark (1971). Analyses of seven melt inclusions and twenty-eight defocused beam analyses of lithic fragments are also given. Some of the fragments contain ‘gas’ inclusions which, along with the fine grain size, are believed to indicate final crystallization under low pressure near surface conditions. The almost complete absence of granophyric material in this sample raises the question of whether or not there are at least two distinct magmas for the plagioclase-rich terrae rocks from which this soil sample was derived in part.

Geochimica et Cosmochimica Acta↗

USGS1989

Coprecipitation and redox reactions of manganese oxides with copper and nickel

Open-system, continuous-titration experiments have been done in which a slow flux of ∼0.02 molar solution of Mn 2+ chloride, nitrate, or perchlorate with Cu 2+ or Ni 2+ in lesser concentrations was introduced into an aerated reactor solution held at constant temperature and at constant pH by a pH-stat titrator that added dilute NaOH. The resulting mixtures of metal oxyhydroxides and their native solutions were aged for periods as long as 2 1/2 years. Fresh and aged precipitates were characterized by chemical analysis, oxidation state determinations, X-ray and electron diffraction, and electron microscopy. The precipitates can be described as mixtures of oxide and oxyhydroxide species, using concepts of equilibrium and nonequilibrium chemical thermodynamics. The metal-ion content of the aged precipitates in systems that contained copper is distributed among three principal components. One of these is a mixed oxide Cu 2 Mn 3 O 8 in which all Mn is in the 4+ oxidation state. A major component in all precipitates is feitknechtite, βMnOOH. These forms are supplemented by CuO or by birnessite or ramsdellite forms of MnO 2 where stoichiometry and thermodynamic calculations predict them. In systems that contained nickel and manganese, identifiable components included βMnOOH, Ni(OH) 2 , and the same two forms of MnO 2 . The oxidation number of the precipitated manganese increased during aging, and the pH of the supernatant solution decreased. The maximum Mn oxidation number observed was 3.55 in an Mn + Cu precipitate aged for 18 months. Concentrations of Cu 2+ and Ni 2+ generally decreased to values substantially below those predicted by oxide or hydroxide equilibrium. Scavenging effects of this type are common in natural aqueous systems.

Geochimica et Cosmochimica Acta↗

USGS1960

The crystal structure of cesium biuranyl trisulphate, Cs2(UO2)2(SO4)3

The crystal structure of the new compound Cs(UO 2 ) 2 (SO 4 ) 3 has been determined by X-ray diffraction methods. The compound is tetragonal, space group P 4 2 1 m "> P42 1 m ( D 2 d 3 ), with a = 9·62 ± 0·02, c = 8·13 ± 0·01 A ̊ "> c = 8·13 ± 0·01Å , and Z = 2; s.g. (calc.) = 4·80 ± 0·03, s.g. (obs.) = 4·74 ± 0·05. The compound forms plates parallel to (001) bounded by the form (110). Intensity data were obtained from Buerger precession photographs of the ( hk 0) and (0 kl ) reciprocal lattice nets. No corrections for absorption were made. The co-ordinates of the U and Cs atoms were obtained by interpretation of the Patterson projections normal to (001) and (100) and a plausible structure was derived from electron density projections. The final parameters of the structure were determined from subtraction electron density maps, least squares analysis of the structure factors, and spatial considerations. The compound has a layer structure consisting of (UO 2 ) 2 (SO 4 ) 3 ] n 2 n − sheets paralle to (001), tied together by cesium ions. The UO 2 2+ group is co-ordinated by five sulphate oxygens which form a nearly plane pentagon approximately normal to the uranyl axis. The Cs 2 atom is co-ordinated by twelve oxygen atoms and the Cs 1 atom by eight oxygen atoms. X-ray and optical data are also given for the compound Rb 2 UO 2 (SO 4 ) 2 ·2H 2 O.

Journal of Inorganic and Nuclear Chemistry↗

USGS1993

Enzymatic iron and uranium reduction by sulfate-reducing bacteria

The potential for sulfate-reducing bacteria (SRB) to enzymatically reduce Fe(III) and U(VI) was investigated. Five species of Desulfovibrio as well as Desulfobacterium autotrophicum and Desulfobulbus propionicus reduced Fe(III) chelated with nitrilotriacetic acid as well as insoluble Fe(III) oxide. Fe(III) oxide reduction resulted in the accumulation of magnetite and siderite. Desulfobacter postgatei reduced the chelated Fe(III) but not Fe(III) oxide. Desulfobacter curvatus, Desulfomonile tiedjei , and Desulfotomaculum acetoxidans did not reduce Fe(III). Only Desulfovibrio species reduced U(VI). U(VI) reduction resulted in the precipitation of uraninite. None of the SRB that reduced Fe(III) or U(VI) appeared to conserve enough energy to support growth from this reaction. However, Desulfovibrio desulfuricans metabolized H 2 down to lower concentrations with Fe(III) or U(VI) as the electron acceptor than with sulfate, suggesting that these metals may be preferred electron acceptors at the low H 2 concentrations present in most marine sediments. Molybdate did not inhibit Fe(III) reduction by D. desulfuricans . This indicates that the inability of molybdate to inhibit Fe(III) reduction in marine sediments does not rule out the possibility that SRB are important catalysts for Fe(III) reduction. The results demonstrate that although SRB were previously considered to reduce Fe(III) and U(VI) indirectly through the production of sulfide, they may also directly reduce Fe(III) and U(VI) through enzymatic mechanisms. These findings, as well as our recent discovery that the S o -reducing microorganism Desulfuromonas acetoxidans can reduce Fe(III), demonstrate that there are close links between the microbial sulfur, iron, and uranium cycles in anaerobic marine sediments.

Marine Geology↗

USGS1981

Trace elemental analysis of bituminuos coals using the Heidelberg proton microprobe

Trace elements in coal can occur as components of either the organic constituents (macerals) or the inorganic constituents (minerals). Studies of the concentrations and distribution of the trace elements are vital to understanding the geochemical millieu in which the coal was formed and in evaluating the attempts to recover rare but technologically valuable metals. In addition, information on the trace element concentrations is important in predicting the environmental impact of burning particular coals, as many countries move toward greater utilization of coal reserves for energy production. Traditionally, the optical and the electron microscopes and more recently the electron microprobe have been used in studying the components of coal. The proton-induced X-ray emission (PIXE) microprobe offers a new complementary approach with an order of magnitude or more better minimum detection limit. We present the first measurements with a PIXE microprobe of the trace element concentrations of bituminous coal samples. Elemental analyses of the coal macerals-vitrinite, exinite, and inertinite-are discussed for three coal samples from the Eastern U.S.A., three samples from the Western U.S.A., and one sample from the Peoples Republic of China. ?? 1981.

Nuclear Instruments and Methods↗

USGS1996

A geochemical study of macerals from a Miocene lignite and an Eocene bituminous coal, Indonesia

Optical and chemical studies of maceral concentrates from a Miocene lignite and an Eocene high-volatile bituminous C coal from southeastern Kalimantan, Indonesia were undertaken using pyro-Lysis, optical, electron microprobe and FTIR techniques Pyrolysis products of vitrinite from bituminous coal were dominated by straight-chain aliphatics and phenols. The huminite of the Miocene lignite produced mostly phenolic compounds upon pyrolysis. Differences in the pyrolysis products between the huminite and vitrinite samples reflect both maturation related and paleobotanical differences. An undefined aliphatic source and/or bacterial biomass were the likely contributors of n-alkyl moieties to the vitrinite. The resinite fraction in the lignite yielded dammar-derived pyrolysis products, as well as aliphatics and phenols as the products of admixed huminite and other liptinites. The optically defined resinite-rich fraction of the bituminous coal from Kalimantan produced abundant n-aliphatic moieties upon pyrolysis, but only two major resin markers (cadalene and 1,6-dimethylnaphthalene). This phenomenon is likely due to the fact that Eocene resins were not dammar-related. Data from the electron microprobe and Fourier transform infrared spectrometry strongly support the results obtained by Py GC MS and microscopy.

Organic Geochemistry↗

USGS1982

Recommended procedures and techniques for the petrographic description of bituminous coals

Modern coal petrology requires rapid and precise description of great numbers of coal core or bench samples in order to acquire the information required to understand and predict vertical and lateral variation of coal quality for correlation with coal-bed thickness, depositional environment, suitability for technological uses, etc. Procedures for coal description vary in accordance with the objectives of the description. To achieve our aim of acquiring the maximum amount of quantitative information within the shortest period of time, we have adopted a combined megascopic-microscopic procedure. Megascopic analysis is used to identify the distinctive lithologies present, and microscopic analysis is required only to describe representative examples of the mixed lithologies observed. This procedure greatly decreases the number of microscopic analyses needed for adequate description of a sample. For quantitative megascopic description of coal microlithotypes, microlithotype assemblages, and lithotypes, we use (V) for vitrite or vitrain, (E) for liptite, (I) for inertite or fusain, (M) for mineral layers or lenses other than iron sulfide, (S) for iron sulfide, and (X 1 ), (X 2 ), etc. for mixed lithologies. Microscopic description is expressed in terms of V representing the vitrinite maceral group, E the exinite group, I the inertinite group, and M mineral components. volume percentages are expressed as subscripts. Thus (V) 20 (V 80 E 10 I 5 M 5 ) 80 indicates a lithotype or assemblage of microlithotypes consisting of 20 vol. % vitrite and 80% of a mixed lithology having a modal maceral composition V 80 E 10 I 5 M 5 . This bulk composition can alternatively be recalculated and described as V 84 E 8 I 4 M 4 . To generate these quantitative data rapidly and accurately, we utilize an automated image analysis system (AIAS). Plots of VEIM data on easily constructed ternary diagrams provide readily comprehended illustrations of the range of modal composition of the lithologic units making up a given coal bed. The use of bulk-specific-gravity determinations is alo recommended for identification and characterization of the distinctive lithologic units. The availability of an AIAS also enhances the capability to acquire textural information. Ranges of size of maceral and mineral grains can be quickly and precisely determined by use of an AIAS. We assume that shape characteristics of coal particles can also be readily evaluated by automated image analysis, although this evaluation has not yet been attempted in our laboratory. Definitive data on the particulate mineral content of coal constitute another important segment of petrographic description. Characterization of mineral content may be accomplished by optical identification, electron microprobe analysis, X-ray diffraction, and scanning and transmission electron microscopy. Individual mineral grains in place in polished blocks or polished this sections, or separated from the coal matrix by sink-float methods are studied by analytical techniques appropriate to the conditions of sampling.

International Journal of Coal Geology↗

USGS1984

Resin rodlets in shale and coal (Lower Cretaceous), Baltimore Canyon Trough

Rodlets, occurring in shale and coal (uppermost Berriasian to middle Aptian, Lower Cretaceous), were identified from drill cuttings taken from depths between 9330 ft (2844 m) and 11, 460 ft (3493 m) in the Texaco et al., Federal Block 598, No. 2 well, in the Baltimore Canyon Trough. Under the binocular microscope, most of the rodlets appear black, but a few are reddish brown, or brownish and translucent on thin edges. They range in diameter from about 0.4 to 1.7 mm and are commonly flattened. The rodlets break with a conchoidal fracture, and some show an apparent cellular cast on their longitudinal surfaces. When polished and viewed in reflected light, the rodlets appear dark gray and have an average random reflectance of less than 0.1% whereas mean maximum reflectances are 0.48–0.55% for vitrinite in the associated shale and coal. These vitrinite reflectances indicate either subbituminous A or high-volatile C bituminous coal. The rodlets fluoresce dull gray yellow to dull yellow. The scanning electron microscope (SEM) and light microscope reveal the presence of swirl-like features in the rodlet interiors. Minerals associated with the rodlets occur as sand-size grains attached to the outer surface, as finely disseminated interior grains, and as fracture fillings. Electron microprobe and SEM-energy-dispersive X-ray (EDX) anlayses indicate that the minerals are dominantly clays (probably illite and chlorite) and iron disulfide; calcium carbonate, silicon dioxide, potassium aluminum silicate (feldspar), titanium dioxide, zinc sulfide, and iron sulfate minerals have been also identified. The rodlets were analyzed directly for C, H, N, O, and total S and are interpreted as true resins on the basis of C and H contents that range from 75.6 to 80.3 and from 7.4 to 8.7 wt. % (dry, ash-free basis), respectively. Elemental and infrared data support a composition similar to that of resinite from bituminous coal. Elements determined to be organically associated in the rodlets include S (0.2–0.5 wt.%), Cl (0.03–0.1 wt.%), and Si (0.05–0.08 wt.%). The ash content of the resin rodlets ranges from 4 to 24 wt.% and averages 12 wt.%. Total sulfur contents range from 1.7 to 3.6 wt.%. Resins of fossil plants are known to have little or no sulfur and ash; therefore, these data and the presence of minerals in fractures indicate that most of the sulfur and mineral matter were introduced into the resin partly or wholly after the time of brittle fracture of the resin. The probable source of the resin rodlets is fossil pinaceous conifer cones, which are known to have resin canals as much as 2400 μm in diameter.

International Journal of Coal Geology↗

USGS1981

Ne matrix spectra of the sym-C6Br3F3+ radical cation

The electronic absorption and laser excited, wavelength resolved fluorescence spectra of the title cation have been observed in solid Ne matrix and vibrationally analysed. The vibrational structure of the excited B2A2??? state shows close similarity to the parent compound. The X2E??? ground state structure is strongly perturbed and irregular owing to a large Jahn-Teller distortion. The data are analysed in terms of a recently developed, sophisticated multimode Jahn-Teller theoretical model. We have generated the sym-C6Br3F3+ cations in solid Ne matrix and obtained their wavelength resolved emission and absorption spectra. T ground electronic X2E??? state exhibits an irregular and strongly perturbed vibrational structure, which can be successfully modeled using sophisticated multimode Jahn-Teller theory. ?? 1981.

Chemical Physics↗

USGS1994

Helping the public find information the U.S. Government Information Locator Service (GILS)

As part of the National Information Infrastructure, the U.S. federal government is establishing a Government Information Locator Service (GILS). GILS will identify and describe public information resources throughout the federal government and provide assistance in obtaining the information. It will be decentralized and will supplement other agency and commercial information dissemination mechanisms. The public will use GILS directly or through intermediaries, including the Government Printing Office and the National Technical Information Service, as well as federal depository libraries, other public libraries, and private sector information services. Direct users will have access to a GILS Core accessible on the Internet without charge. Intermediate access may include kiosks, 800 numbers, electronic mail, bulletin boards, FAX, and offline media such as floppy disks, CD-ROM, and printed works. GILS will use network technology and the American National Standards Institute Z39.50 standard for information search and retrieval so that information can be retrieved in a variety of ways. Direct users may have access to many other major federal and nonfederal information resources, linkages to data systems, and electronic delivery of information products. An Office of Management and Budget Bulletin in 1994 will provide implementing guidance to agencies. The National Institute of Standards and Technology will also establish a Federal Information Processing Standard specifying a GILS Profile and its application for agencies establishing information locators.

Journal of Government Information↗

USGS2021

Monitoring volcanic deformation

Deformation signals recorded at volcanoes have long been used to infer the processes behind subsurface magma intrusions. Monitoring strategies vary greatly depending on several factors such as the activity of the individual volcano, access, available personnel, and funding. Certain geodetic monitoring methods, such as Electronic Distance Measurements, are inexpensive but require that scientists be dangerously close to active areas. Other techniques, such as telemetered geodetic measurements (Electronic Tiltmeters and Global Navigation Satellite System), or deformation images from Interferometric Synthetic Aperture Radar, can be collected remotely and with less risk. Observed surface deformation can be fit to the predictions of mathematical source models to obtain quantitative estimates of their parameters (e.g., location, depth, volume change and more). Combined deformation and gravity change measurements can be used to infer the density of subsurface intrusions and better constrain the source of unrest. To be effective, geodetic monitoring must be done before, during, and after eruptions and must be integrated with other monitoring techniques (e.g., seismology, geochemistry, physical volcanology, remote sensing). It requires the long-term commitment of time and resources. Done effectively, geodetic monitoring not only can provide timely warnings of escalating volcano hazards but may also lead to improved understanding of how volcanoes work. Even when a volcano is not active, monitoring generates baseline information against which changes in volcano behavior can be compared. Preserving the integrity and accessibility of geodetic data archives is thus essential if future volcanologists are to benefit from the decades-long records of geodetic data gathered by volcano observatories.

Book chapter↗

USGS2004

Geochemistry of shallow ground water in coastal plain environments in the southeastern United States: Implications for aquifer susceptibility

Ground-water chemistry data from coastal plain environments have been examined to determine the geochemical conditions and processes that occur in these areas and assess their implications for aquifer susceptibility. Two distinct geochemical environments were studied to represent a range of conditions: an inner coastal plain setting having more well-drained soils and lower organic carbon (C) content and an outer coastal plain environment that has more poorly drained soils and high organic C content. Higher concentrations of most major ions and dissolved inorganic and organic C in the outer coastal plain setting indicate a greater degree of mineral dissolution and organic matter oxidation. Accordingly, outer coastal plain waters are more reducing than inner coastal plain waters. Low dissolved oxygen (O2) and nitrate (NO 3-) concentrations and high iron (Fe) concentrations indicate that ferric iron (Fe (III)) is an important electron acceptor in this setting, while dissolved O2 is the most common terminal electron acceptor in the inner coastal plain setting. The presence of a wide range of redox conditions in the shallow aquifer system examined here underscores the importance of providing a detailed geochemical characterization of ground water when assessing the intrinsic susceptibility of coastal plain settings. The greater prevalence of aerobic conditions in the inner coastal plain setting makes this region more susceptible to contamination by constituents that are more stable under these conditions and is consistent with the significantly (p<0.05) higher concentrations of NO3- found in this setting. Herbicides and their transformation products were frequently detected (36% of wells sampled), however concentrations were typically low (<0.1 ??g/L). Shallow water table depths often found in coastal plain settings may result in an increased risk of the detection of pesticides (e.g., alachlor) that degrade rapidly in the unsaturated zone.

Applied Geochemistry↗

USGS2015

Arsenic and antimony geochemistry of mine wastes, associated waters and sediments at the Giant Mine, Yellowknife, Northwest Territories, Canada

Elevated levels of arsenic (As) and antimony (Sb) in water and sediments are legacy residues found downstream from gold-mining activities at the Giant Mine in Yellowknife, Northwest Territories (NWT), Canada. To track the transport and fate of As and Sb, samples of mine-waste from the mill, and surface water, sediment, pore-water, and vegetation downstream of the mine were collected. Mine waste, pore-water, and sediment samples were analyzed for bulk chemistry, and aqueous and solid-state speciation. Sediment and vegetation chemistry were evaluated using scanning electron microscope imaging, synchrotron-based element mapping and electron microprobe analysis. The distributions of As and Sb in sediments were similar, yet their distributions in the corresponding pore-waters were mostly dissimilar, and the mobility of As was greater than that of Sb. Competition for sorption sites is the most likely cause of elevated Sb concentrations in relatively oxidized pore-water and surface water. The aqueous and solid-state speciation of As and Sb also differed. In pore-water, As(V) dominated in oxidizing environments and As(III) in reducing environments. In contrast, the Sb(V) species dominated in all but one pore-water sample, even under reducing conditions. Antimony(III) appears to preferentially precipitate or adsorb onto sulfides as evidenced by the prevalence of an Sb(III)-S secondary solid-phase and the lack of Sb(III)(aq) in the deeper zones. The As(V)–O solid phase became depleted with depth below the sediment–water interface, and the Sb(V)–O phase persisted under relatively reducing conditions. In the surficial zone at a site populated by Equisetum fluviatile (common horsetail), As and Sb were associated with organic material and appeared mobile in the root zone. In the zone below active plant growth, As and Sb were associated primarily with inorganic phases suggesting a release and reprecipitation of these elements upon plant death. The co-existence of reduced and oxidized As and Sb species, instability of some phases under changing redox conditions, and plant uptake and release pose challenges for remediation efforts at the mine.

Northwest Territories↗

USGS2009

Respiratory arsenate reductase as a bidirectional enzyme

The haloalkaliphilic bacterium Alkalilimnicola ehrlichii is capable of anaerobic chemolithoautotrophic growth by coupling the oxidation of arsenite (As(III)) to the reduction of nitrate and carbon dioxide. Analysis of its complete genome indicates that it lacks a conventional arsenite oxidase (Aox), but instead possesses two operons that each encode a putative respiratory arsenate reductase (Arr). Here we show that one homolog is expressed under chemolithoautotrophic conditions and exhibits both arsenite oxidase and arsenate reductase activity. We also demonstrate that Arr from two arsenate respiring bacteria, Alkaliphilus oremlandii and Shewanella sp. strain ANA-3, is also biochemically reversible. Thus Arr can function as a reductase or oxidase. Its physiological role in a specific organism, however, may depend on the electron potentials of the molybdenum center and [Fe–S] clusters, additional subunits, or constitution of the electron transfer chain. This versatility further underscores the ubiquity and antiquity of microbial arsenic metabolism.

Biochemical and Biophysical Research Communication↗

USGS2005

Secondary sulfate minerals associated with acid drainage in the eastern US: Recycling of metals and acidity in surficial environments

Weathering of metal-sulfide minerals produces suites of variably soluble efflorescent sulfate salts at a number of localities in the eastern United States. The salts, which are present on mine wastes, tailings piles, and outcrops, include minerals that incorporate heavy metals in solid solution, primarily the highly soluble members of the melanterite, rozenite, epsomite, halotrichite, and copiapite groups. The minerals were identified by a combination of powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and electron-microprobe. Base-metal salts are rare at these localities, and Cu, Zn, and Co are commonly sequestered as solid solutions within Fe- and Fe-Al sulfate minerals. Salt dissolution affects the surface-water chemistry at abandoned mines that exploited the massive sulfide deposits in the Vermont copper belt, the Mineral district of central Virginia, the Copper Basin (Ducktown) mining district of Tennessee, and where sulfide-bearing metamorphic rocks undisturbed by mining are exposed in Great Smoky Mountains National Park in North Carolina and Tennessee. Dissolution experiments on composite salt samples from three minesites and two outcrops of metamorphic rock showed that, in all cases, the pH of the leachates rapidly declined from 6.9 to <3.7, and specific conductance increased gradually over 24 h. Leachates analyzed after 24-h dissolution experiments indicated that all of the salts provided ready sources of dissolved Al (>30 mg L-1), Fe (>47 mg L-1), sulfate (>1000 mg L-1), and base metals (>1000 mg L-1 for minesites, and 2 mg L-1 for other sites). Geochemical modeling of surface waters, mine-waste leachates, and salt leachates using PHREEQC software predicted saturation in the observed ochre minerals, but significant concentration by evaporation would be needed to reach saturation in most of the sulfate salts. Periodic surface-water monitoring at Vermont minesites indicated peak annual metal loads during spring runoff. At the Virginia site, where no winter-long snowpack develops, metal loads were highest during summer months when salts were dissolved periodically by rainstorms following sustained evaporation during dry spells. Despite the relatively humid climate of the eastern United States, where precipitation typically exceeds evaporation, salts form intermittently in open areas, persist in protected areas when temperature and relative humidity are appropriate, and contribute to metal loadings and acidity in surface waters upon dissolution, thereby causing short-term perturbations in water quality.

Chemical Geology↗

USGS2012

Minor element distribution in iron disulfides in coal: a geochemical review

Electron beam microanalysis of coal samples in U.S. Geological Survey (USGS) labs confirms that As is the most abundant minor constituent in Fe disulfides in coal and that Se, Ni, and other minor constituents are present less commonly and at lower concentrations than those for As. In nearly all cases, Hg occurs in Fe disulfides in coal at concentrations below detection by electron beam instruments. Its presence is shown by laser ablation ICP-MS, by selective leaching studies of bulk coal, and by correlation with Fe disulfide proxies such as total Fe and pyritic sulfur. Multiple generations of Fe disulfides are present in coal. These commonly show grain-to-grain and within-grain minor- or trace element compositional variation that is a function of the early diagenetic, coalification, and post-coalification history of the coal. Framboidal pyrite is almost always the earliest Fe disulfide generation, as shown by overgrowths of later Fe disulfides which may include pyrite or marcasite. Cleat- (or vein) pyrite (or marcasite) is typically the latest Fe disulfide generation, as shown by cross-cutting relations. Cleat pyrite forms by fluid migration within a coal basin and consequently may be enriched in elements such as As by deposition from compaction-driven fluids, metal enriched basinal brines or hydrothermal fluids. In some cases, framboidal pyrite shows preferential Ni enrichment with respect to co-occurring pyrite forms. This is consistent with bacterial complexing of metals in anoxic sediments and derivation of framboidal pyrite from greigite (Fe 3 S 4 ), an Fe monosulfide precursor to framboidal pyrite having the thio-spinel structure which accommodates transition metals. Elements such as As, Se, and Sb substitute for S in the pyrite structure whereas metals, including transition metals, Hg and Pb, are thought to substitute for Fe. Understanding the distribution of minor and trace elements in Fe disulfides in coal has important implications for their availability to the environment through coal mining and use, as well as for potential reduction by coal preparation, and for delineating diagenetic compositional changes throughout and after coal formation.

International Journal of Coal Geology↗

USGS2022

Evaluating aromatization of solid bitumen generated in the presence and absence of water: Implications for solid bitumen reflectance as a thermal proxy

Geological models for petroleum generation suggest thermal conversion of oil-prone sedimentary organic matter in the presence of water promotes increased liquid saturate yield, whereas absence of water causes formation of an aromatic, cross-linked solid bitumen residue. To test the influence of hydrogen from water, organic-rich (22 wt% total organic carbon , TOC) mudrock samples from the Eocene lacustrine Green River Formation Mahogany zone oil shale were pyrolyzed under hydrous and anhydrous conditions in closed system batch reactors at temperatures between 300 and 370 °C for 72 h. Pre- and post-pyrolysis samples were characterized using petrographic approaches including optical microscopy , reflectance, Raman spectroscopy , and scanning electron and transmission electron microscopy to quantify differences in relative appearance, abundance, and composition of solid bitumen newly generated during the pyrolysis experiments. Petrographic analyses were supplemented by geochemical screening measurements (TOC content and programmed temperature pyrolysis). Results show post-hydrous pyrolysis residues contain lower TOC, are comprised of solid bitumen with greater aromaticity , and have textures indicative of lower viscosities, relative to anhydrous residues from the same temperature pyrolysis conditions. These observations suggest solid bitumen forming from thermal conversion of oil-prone sedimentary organic matter under anhydrous conditions may be less aromatic, although more cross-linked, than solid bitumen forming under hydrous conditions at the same time-temperature combination. To explain these results, we suggest that a radical disproportionation mechanism is favored in the presence of hydrogen donated from water, and that this disproportionation promotes aromatization in the solid residue with concomitant expulsion of saturated hydrocarbons.

International Journal of Coal Geology↗