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F.T. Dulong

Publications and source records attributed to F.T. Dulong.

At least 19 recordsLinked to original sources
USGS2002

Combustion and leaching behavior of elements in the argonne premium coal samples

Eight Argonne Premium Coal samples and two other coal samples were used to observe the effects of combustion and leaching on 30 elements. The results were used to infer the modes of occurrence of these elements. Instrumental neutron activation analysis indicates that the effects of combustion and leaching on many elements varied markedly among the samples. As much as 90% of the selenium and bromine is volatilized from the bituminous coal samples, but substantially less is volatilized from the low-rank coals. We interpret the combustion and leaching behavior of these elements to indicate that they are associated with the organic fraction. Sodium, although nonvolatile, is ion-exchangeable in most samples, particularly in the low-rank coal samples where it is likely to be associated with the organic constituents. Potassium is primarily in an ion-exchangeable form in the Wypdak coal but is in HF-soluble phases (probably silicates) in most other samples. Cesium is in an unidentified HNO3-soluble phase in most samples. Virtually all the strontium and barium in the low-rank coal samples is removed by NH4OAc followed by HCl, indicating that these elements probably occur in both organic and inorganic phases. Most tungsten and tantalum are in insoluble phases, perhaps as oxides or in organic association. Hafnium is generally insoluble, but as much as 65% is HF soluble, perhaps due to the presence of very fine grained or metamict zircon. We interpret the leaching behavior of uranium to indicate its occurrence in chelates and its association with silicates and with zircon. Most of the rare-earth elements (REE) and thorium appear to be associated with phosphates. Differences in textural relationships may account for some of the differences in leaching behavior of the REE among samples. Zinc occurs predominantly in sphalerite. Either the remaining elements occur in several different modes of occurrence (scandium, iron), or the leaching data are equivocal (arsenic, antimony, chromium, cobalt, and nickel). The results of these combustion and leaching experiments indicate that some previously held assumptions concerning modes of occurrence of elements in coal should be reconsidered.

Energy & Fuels↗
USGS1998

Influence of an igneous intrusion on the inorganic geochemistry of a bituminous coal from Pitkin County, Colorado

Although the effects of igneous dikes on the organic matter in coal have been observed at many localities there is virtually no information on the effects of the intrusions of the inorganic constituents in the coal. Such a study may help to elucidate the behavior of trace elements during in situ gasification of coal and may provide insights into the resources potential for coal and coke affected by the intrusion. To determine the effects of an igneous intrusion on the inorganic chemistry of a coal we used a series of 11 samples of coal and natural coke that had been collected at intervals from 3 to 106 cm from a dike that intruded the bituminous Dutch Creek coal in Pitkin, CO. The samples were chemically analyzed for 66 elements. SEM-EDX and X-ray diffraction analysis were performed on selected samples. Volatile elements such as F, Cl, Hg, and Se are not depleted in the samples (coke and coal) nearest the dike that were exposed to the highest temperatures. Their presence in these samples is likely due to secondary enrichment following volatilization of the elements inherent in the coal. Equilibration with ground water may account for the uniform distribution of Na, B, and Cl. High concentrations of Ca, Mg, Fe, Mn, Sr, and CO2 in the coke region are attributed to the reaction of CO and CO2 generated during the coking of the coal with fluids from the intrusion, resulting in the precipitation of carbonates. Similarly, precipitation of sulfide minerals in the coke zone may account for the relatively high concentrations of Ag, Hg, Cu, Zn, and Fe. Most elements are concentrated at the juncture of the fluidized coke and the thermally metamorphosed coal. Many of the elements enriched in this region (for example, Ga, Ge, Mo, Rb, U, La, Ce, Al, K, and Si) may have been adsorbed on either the clays or the organic matter or on both.Although the effects of igneous dikes on the organic matter in coal have been observed at many localities there is virtually no information on the effects of the intrusions on the inorganic constituents in the coal. Such a study may help to elucidate the behavior of trace elements during in situ gasification of coal and may provide insights into the resource potential of coal and coke affected by the intrusion. To determine the effects of an igneous intrusion on the inorganic chemistry of a coal we used a series of 11 samples of coal and natural coke that had been collected at intervals from 3 to 106 cm from a dike that intruded the bituminous Dutch Creek coal in Pitkin, CO. The samples were chemically analyzed for 66 elements. SEM-EDX and X-ray diffraction analysis were performed on selected samples. Volatile elements such as F, Cl, Hg, and Se are not depleted in the samples (coke and coal) nearest the dike that were exposed to the highest temperatures. Their presence in these samples is likely due to secondary enrichment following volatilization of the elements inherent in the coal. Equilibration with ground water may account for the uniform distribution of Na, B, and Cl. High concentrations of Ca, Mg, Fe, Mn, Sr, and CO2 in the coke region are attributed to the reaction of CO and CO2 generated during the coking of the coal with fluids from the intrusion, resulting in the precipitation of carbonates. Similarly, precipitation of sulfide minerals in the coke zone may account for the relatively high concentrations of Ag, Hg, Cu, Zn, and Fe. Most elements are concentrated at the juncture of the fluidized coke and the thermally metamorphosed coal. Many of the elements enriched in this region (for example, Ga, Ge, Mo, Rb, U, La, Ce, Al, K, and Si) may have been adsorbed on either the clays or the organic matter or on both.

International Journal of Coal Geology↗
USGS1998

Change in the magnetic properties of bituminous coal intruded by an igneous dike, Dutch Creek Mine, Pitkin County, Colorado

Magnetization measurements have been made on natural coke-coal samples collected at various distances from a felsic porphyry dike in a coal seam in Dutch Creek Mine, Colorado to help characterize the nature and distribution of the iron-bearing phases. The magnetization passes through a maximum at the coke-to-coal transition about 31 cm from the dike contact. The magnetic measurements support the geochemical data indicating that magmatic fluids along with a high-temperature gas pulse moved into the coal bed. Interaction of the magmatic fluids with the coal diminished the reducing power of the thermal gas pulse from the dike to a point about 24 cm into the coal. The hot reducing gas penetrated further and produced a high temperature (~400-525??C) zone (at about 31 cm) just ahead of the magmatic fluids. Metallic iron found in this zone is the principal cause of the observed high magnetization. Beyond this zone, the temperature was too low to alter the coal significantly.Magnetization measurements have been made on natural coke-coal samples collected at various distances from a felsic porphyry dike in a coal seam in Dutch Creek Mine, Colorado to help characterize the nature and distribution of the iron-bearing phases. The magnetization passes through a maximum at the coke-to-coal transition about 31 cm from the dike contact. The magnetic measurements support the geochemical data indicating that magmatic fluids along with a high-temperature gas pulse moved into the coal bed. Interaction of the magmatic fluids with the coal diminished the reducing power of the thermal gas pulse from the dike to a point about 24 cm into the coal. The hot reducing gas penetrated further and produced a high temperature (approximately 400-525 ??C) zone (at about 31 cm) just ahead of the magmatic fluids. Metallic iron found in this zone is the principal cause of the observed high magnetization. Beyond this zone, the temperature was too low to alter the coal significantly.

International Journal of Coal Geology↗
USGS1991

Effects of detrital influx in the Pennsylvanian Upper Freeport peat swamp

Quartz cathodoluminescence properties and mineralogy of three sets of samples and vegetal and/ or miospore data from two sets of samples from the Upper Freeport coal bed, west-central Pennsylvania, show that detrital influence from a penecontemporaneous channel is limited to an area less than three km from the channel. The sets of samples examined include localities of the coal bed where (1) the coal is thin, split by partings, and near a penecontemporaneous fluvial channel, (2) the coal is relatively thick and located approximately three km from the channel, and (3) the coal is thick and located approximately 12 km from the channel. Samples from locality 1 (nearest the channel) have relatively high-ash yields (low-temperature ash average = 27.3% on a pyrite- and calcite-free basis) and high proportions of quartz and clay minerals. The quartz is primarily detrital, as determined by cathodoluminescent properties, and the ratio of kaolinite to illite is low. In addition, most of the plant remains and miospores indicate peat-forming plants that required low nutrient levels for growth. In contrast, samples from localities 2 and 3, from the more interior parts of the bed, contained predominantly authigenic quartz grains nd yielded low-temperature ash values of less than 14% on a pyrite- and calcite-free basis. The low-temperature ash contains low concentrations of quartz and clay minerals and the ratio of kaolinite to illite is relatively high. Although intact core was not available for paleobotanical analyses, another core collected within 1 km from locality 3 contained plant types interpreted to have required high nutrient levels for growth. These data indicate that mineral formation is dominated by authigenic processes in interior parts of the coal body. Some of the authigenic quartz may have been derived from herbaceous ferns as indicated by patterns in the palynological and paleobotanical data. In contrast, detrital processes appeared to be limited to in areas directly adjacent to the penecontemporaneous channel where the coal bed is high in ash, split by mineral-rich partings, and of little or no economic value.

International Journal of Coal Geology↗
USGS1990

The laser microprobe mass analyser for determining partitioning of minor and trace elements among intimately associated macerals: An example from the Swallow Wood coal bed, Yorkshire, UK

A study of the elemental composition of intimately associated coal macerals in the English Swallow Wood coal bed was conducted using a laser microprobe mass analyser, and indicated a similar trace and minor elemental chemistry in the vitrinite and cutinite and a different elemental signature in the fusinite. Three to six sites were analysed within each maceral during the study by laser micro mass spectrometry (LAMMS). Al, Ba, Ca, Cl, Cr, Dy, F, Fe, Ga, K, Li, Mg, Na, S, Si, Sr, Ti, V, and Y were detected by LAMMS in all three macerals but not necessarily at each site analysed. The signal intensities of major isotopic peaks were normalized to the signal intensity of the m z "> mz 85 peak (C 7 H) to determine the relative minor- and trace-element concentrations among the three dominant macerals. The vitrinite and the cutinite were depleted in Ba, Ca, Dy, Li, Mg, Sr, and Y relative to their concentrations observed in the fusinite. The cutinite was distinguished over vitrinite by less Ti, V, Cr and Ca, and K Ca $ ̆ 1 "> KCa$1 (relative signal intensities). The fusinite, relative to the cutinite and vitrinite, was relatively depleted in Cr, Sc, Ti, and V. The fusinite, as compared with both the cutinite and vitrinite, was relatively enriched in Ba, Ca, Dy, Li, Mg, Sr, and Y, and also showed the most intense m z "> mz 64, 65, 66 signals (possibly S 2 + , HS 2 + , H 2 S 2 + , respectively). The LAMMS data indicate a common source for most elements and selective loss from the maceral precursors in the peat or entrapment of certain elements as mineral matter, most likely during the peat stage or during early diagenesis. The relatively high amounts of Ba, Ca, Dy, Li, Mg, Sr, and Y in the fusinite are consistent with micron and submicron mineral-matter inclusions such as carbonates and Ca-Al phosphates (probably crandallite group minerals). Mineralogical data on the whole coal, the LAMMS chemistry of the vitrinite and cutinite, and scanning electron microscopy/energy dispersive X-ray analysis (SEM/EDAX) of the elements in the macerals are consistent with the presence of micron and submicron inclusions of clays such as kaolinite, illite, and Ca-rich or Ca-bearing minerals (e.g. calcite, Ca-Al phosphates, and illite) which are different in kind and proportions in the three macerals. The variance as measured by the F -statistic for all three macerals indicates generally a nonuniform distribution of minor and trace elements in all three macerals, thus supporting a mineral-matter (inorganic) origin of the elements analysed. Exceptions are Al, K, Fe, Ga, and Sr in the vitrinite and cutinite, which is consistent with organic complexing or a uniform distribution of micron or submicron mineral matter such as illite and phosphate(s).

Yorkshire↗
USGS1990

Palynological assessment of organic tissues and metallic minerals in the Jerritt Canyon gold deposit, Nevada (U.S.A.)

Organic tissues and metallic minerals were studied in acid residues and thin section of the Jerritt Canyon (Bell Mine) gold deposit. The purpose was to compare gold-bearing and gold-free rocks, characterize their differences, and assess a possible relationship between the invisible gold and the organic tissues in these early Paleozoic, carbonaceous limestones, dolomites, and claystones. The most visually abundant acid-resistant component in the sooty, unoxidized, gold-bearing rocks is a black, rectangular, carbon-bearing mineraloid. In X-ray diffraction, it is poorly crystalline; in nuclear magnetic resonance, it is a highly aromatized structure. The increase in gold content that accompanies the increase in content of this protographite suggests that it may be the major gold-bearing compound. Less abundant among the acid-resistant residues are uncarbonized organic tissues that are typical of marine settings. The tissues not in the vicinity of silicified veins are medium to dark brown. The dominant tissues are the amorphous remains of algae and their zooplankton predators. These uncarbonized indigenous tissues indicate that temperatures were lower than those determined by geochemical and fluid inclusion methods. The presence of different kinds of carbon-bearing compounds could account for the discrepancy between the palynological and geochemical data. The uncarbonized organic tissues comprise such a small percentage of these rocks that they could be easily missed by bulk analytical methods. The presence of uncarbonized tissues helps to constrain the duration of the high heat flow that is shown by the fluid inclusion data. The presence of mixed signals suggests that the protographite may be the product of chemical rather than thermal reactions.

Nevada↗
USGS1989

Marine origin of pyritic sulfur in the Lower Bakerstown coal bed, Castleman coal field, Maryland (U.S.A.)

The amount, kind, distribution, and genesis of pyrite in the Lower Bakerstown coal bed in a 150 × 15 m area of the Bettinger mine, Castleman coal field, Maryland, were studied by various analytical techniques. The mined coal, which had a nonmarine roof rock, contained 1.4–2.8 wt.% total sulfur, generally much lower than the high-sulfur coal (> 3.0 wt.% total S) to the north, which is associated with marine roof rocks. Small-scale systematic and nonsystematic variations in total sulfur and pyrite distribution were found in the mined area. In the column sample, most of the pyrite was found in the upper 9 cm of the 69-cm-thick mined coal and occurred mainly as a pyrite lens containing cell fillings in seed-fern tissue (coal ball). As-bearing pyrite was detected by laser microprobe techniques in the cell walls of this tissue but not elsewhere in the column sample. This may indicate that the As was derived from decomposition of organic matter in the cell walls. The sulfur isotopic composition and distribution of pyrite in the coal are consistent with introduction of marine sulfate shortly after peat deposition, followed by bacterial reduction and pyrite precipitation. Epigenetic cleat pyrite in the coal is isotopically heavy, implying that later aqueous sulfate was 34 S-enriched.

International Journal of Coal Geology↗
USGS1989

Chemistry and origin of minor and trace elements in vitrinite concentrates from a rank series from the eastern United States, England, and Australia

A rank series consisting of twelve vitrinite concentrates and companion whole-coal samples from mined coal beds in the eastern United States, England, and Australia were analyzed for C, H, N, O, ash, and 47 trace and minor elements by standard elemental, instrumental neutron activation analysis (INAA), and direct-current-arc spectrographic (DCAS) techniques. The reflectance of vitrinite, atomic H:C and O:C, and ash-free carbon data were used to determine ranks that range from high-volatile C bituminous coal to meta-anthracite. A van Krevelen (atomic H:C vs. O:C) diagram of the vitrinite concentrates shows a smooth curve having its lowest point at H:C = 0.18 and O:C = 0.01. This improves the van Krevelen diagram by the addition of our vitrinite concentrate from meta-anthracite from the Narragansett basin of New England. Boron content (400–450 ppm) in two Illinois basin vitrinite concentrates was about an order of magnitude higher than B contents in other concentrates analyzed. We attribute this to marine origin or hydrothermal activity. The alkaline-earth elements Ca, Mg and Ba (DCAS) have higher concentrations in our vitrinite concentrates from bituminous coals of the Appalachian basin, than they do in vitrinite concentrates from the marine-roofed bituminous coals of the Illinois basin; therefore, a nonmarine origin for these alkaline-earth elements is postulated for the Appalachian basin coals. An ion-exchange mechanism due to high concentrations of these elements as ions in diagenetic water, but probably not recent ground water, may be responsible for the relatively high values of these elements in Appalachian concentrates. Higher concentrations of Ni and Cr in one of the English vitrinite concentrates and of Zr in the Australian concentrate probably indicate organic association and detrital influence, respectively.

International Journal of Coal Geology↗
USGS1987

Oxidation of pyrite in an anoxic atmosphere

Pyrite (FeS 2 ) inclusions in coal, when heated in an oxygen deficient atmosphere (approximately 1% oxygen), become coated with magnetic Fe 3 O 4 due to oxidation. Most of the FeS 2 can thus be removed from the coal by magnetic separation to reduce the sulphur concentration. The oxidation products have been studied in greater detail by measuring the SO 2 and O 2 in the effluent gas during the heating process and by performing further magnetic measurements. At 582 K, the pyrite surface was oxidized to FeSO 4 . Significant oxidation of FeSO 4 and FeS 2 to Fe 3 O 4 was observed starting at 677 K. At about 681 K, the Fe 3 O 4 is further oxidized to α-Fe 2 O 3 . At 681 K, under isothermal conditions, the oxidation is impeded by the α-Fe 2 O 3 formed on the surfaces of the grains. If the temperature is rapidly increased, the oxygen penetrates the α-Fe 2 O 3 veneer to the FeS 2 core of the pyrite grains and oxidizes essentially the whole pyrite mass to Fe 3 O 4 before α-Fe 2 O 3 can be formed.

Fuel↗
USGS1987

PROTON MICROPROBE ANALYSIS OF TRACE-ELEMENT VARIATIONS IN VITRINITES IN THE SAME AND DIFFERENT COAL BEDS.

The PIXE (proton-induced X-ray emission) microprobe can be used for nondestructive, in-situ analyses of areas as small as those analyzed by the electron microprobe, and has a sensitivity of detection as much as two orders of magnitude better than the electron microprobe. Preliminary studies demonstrated that PIXE provides a capability for quantitative determination of elemental concentrations in individual coal maceral grains with a detection limit of 1-10 ppm for most elements analyzed. Encouraged by the earlier results, we carried out the analyses reported below to examine trace element variations laterally (over a km range) as well as vertically (cm to m) in the I and J coal beds in the Upper Cretaceous Ferron Sandstone Member of the Mancos Shale in central Utah, and to compare the data with the data from two samples of eastern coals of Pennsylvanian age.

Scanning Micros↗
USGS1986

SULFUR CONTENT OF THE COAL RESOURCES OF THE UNITED STATES: CURRENT STATUS.

The sulfur content of United States coal can be assessed using a variety of approaches. The sulfur content may be expressed in terms of total sulfur in the coal, pounds of sulfur per million Btu, or sulfur remaining after reduction by coal preparation. In addition, sulfur content may be applied to the demonstrated reserve base or to coal resource estimates. Unfortunately, current data bases do not allow for an integrated assessment at the national level. Although classification of coal resources and reserves according to sulfur content is arbitrary, preferential production of low-sulfur reserves will positively skew the total sulfur of the remaining coal resource.

Conference Paper↗
USGS1985

Paleoclimate controls on late paleozoic sedimentation and peat formation in the central appalachian basin (U.S.A.)

In the central Appalachian basin, at least two major climate changes affected sedimentation during the late Paleozoic. Stratigraphically, these two changes are indicated by the distribution of coal beds, the variation in coal quality, and the variation in rock lithologies. In latest Mississippian or earliest Pennsylvanian time, the climate changed from dry-seasonal tropical to ever-wet (equable) tropical. The equable climate prevailed into the Middle Pennsylvanian, influencing the morphology and geochemistry in peat-forming environments. Many of the peat deposits, which formed under the equable climate, were probably domed (raised bogs); low concentrations of dissolved solids in peat formation water resulted in low buffering capacity. Organic acids caused acidic (pH < 4), antiseptic conditions that resulted in intense leaching of mineral matter, minimal degradation of organic matter, and low-ash and low-sulfur peat deposits; the resulting coal beds are also low in ash and sulfur. Associated rocks are noncalcareous and consist of sequences of interbedded shale, siltstone, and sandstone including quartz arenite. Another climate change occurred in late Middle Pennsylvanian time when evapopation periodically exceeded rainfall resulting in an increase of both dissolved solids and pH (4 to ∼ 7) in surface and near-surface water. Throughout the remainder of the Pennsylvanian, the surfaces of peat deposits were probably planar (not domed); water in peat-forming and other depositional environments became more nearly neutral. The coal beds derived from these peats are highly variable in both ash and sulfur contents. Drier or more seasonal climates are also indicated by sequences of (1) calcareous sandstone and shale, (2) nonmarine limestone that shows shallow-water and subaerial exposure features, and (3) calcareous paleosols that have caliche characteristics. Our data and observations indicate that physical depositional environment models for the origin of coal do not adequately explain variations in mineral matter content and composition in commercial quality coal beds in the central Appalachian basin. Stratigraphic variation in mineral matter in coal beds, and in syngenetic and early diagenetic minerals in rocks associated with the coal beds, appears to be better explained by changes in geochemical conditions of nonmarine sedimentation. Paleoclimate was a principle control on these geochemical conditions.

International Journal of Coal Geology↗
USGS1985

GEOLOGIC PROCESSES AFFECTING THE QUALITY OF THE UPPER FREEPORT COAL BED, WEST-CENTRAL PENNSYLVANIA.

The number or types of origins of the components of a coal bed cannot be determined from its bulk composition. Minerals such as quartz, calcite, and pyrite as well as macerals such as vitrinite can originate from a variety of processes that result from different depositional conditions. The Upper Freeport coal bed was studied and characterized by sampling and analyzing its mappable subunits (facies) over a 120-sq mi area in west-central Pennsylvania. The study was based on field description of mine faces and description of X-ray radiographs of core. A geochemical model proposed for the origin of facies of the Upper Freeport coal bed is consistent with interpretations of modern peat formation resulting from the interaction of climate, plant types, rainfall, ground water geochemistry, nutrient supply, and sedimentation. This model provides a means to evaluate and predict more precisely the variability of a coal resource's quality.

Conference Paper↗