Frank T. Dulong

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

Abstract 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.

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

Abstract 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.

Origin and significance of high nickel and chromium concentrations in Pliocene lignite of the Kosovo Basin, Serbia

Abstract Trace element data from 59 Pliocene lignite cores from the lignite field in the Kosovo Basin, southern Serbia, show localized enrichment of Ni and Cr (33–304 ppm and 8–176 ppm, respectively, whole-coal basis). Concentrations of both elements decrease from the western and southern boundaries of the lignite field. Low-temperature ash and polished coal pellets of selected bench and whole-coal samples were analyzed by X-ray diffraction and scanning electron microscopy with energy-dispersive X-ray analyses. These analyses show that most of the Ni and Cr are incorporated in detrital and, to a lesser degree, in authigenic minerals. The Ni- and Cr-bearing detrital minerals include oxides, chromites, serpentine-group minerals and rare mixed-layer clays. Possible authigenic minerals include Niue5f8Fe sulfates and sulfides. Analyses of three lignite samples by a supercritical fluid extraction technique indicate that some (1–11%) of the Ni is organically bound. Ni- and Cr-bearing oxides, mixed-layer clays, chromites and serpentine-group minerals were also identified in weathered and fresh samples of laterite developed on serpentinized Paleozoic peridotite at the nearby Glavica and Cikatovo Ni mines. These mines are located along the western and northwestern rim, respectively, of the Kosovo Basin, where Ni contents are highest. The detrital Ni- and Cr-bearing minerals identified in lignite samples from the western part of the Kosovo Basin may have been transported into the paleoswamp by rivers that drained the two Paleocene laterites. Some Ni may have been transported directly into the paleoswamp in solution or, alternatively, Ni may have been leached from detrital minerals by acidic peat water and adsorbed onto organic matter and included into authigenic mineral phases. No minable source of Ni and Cr is known in the southern part of the lignite field; however, the mineral and chemical data from the lignite and associated rocks suggest that such a source area may exist.

The 57Fe Mossbauer parameters of pyrite and marcasite with different provenances

Eighteen pyrite and twelve marcasite samples which have different provenances have been investigated to determine the systematics of the influence of mineralogical and geological factors on the 57Fe Mossbauer spectra at 298 K. The following results have been obtained: there is no ambiguity in distinguishing single phase pyrite from single phase marcasite by means of 57Fe Mossbauer spectroscopy at 298 K. At 298 K the average electric quadrupole splitting, 〈ΔEQ〉, and average isomer shift, 〈δ〉, with respect to Fe metal, are 0.6110 ± 0.0030 mm s−1 and 0.313 ± 0.008 mm s−1, respectively, for the 18 pyrites; 〈ΔEQ〉 = 0.5030 ± 0.0070 mm s−1 and 〈δ〉 = 0.2770 ± 0.0020 mm s−1 for the 12 marcasites. At 77 K, ΔEQ is 0.624 mm s−1 for pyrite and 0.508 mm s−1 for marcasite. In distinguishing pyrites from marcasites, spectra obtained at 77 K are not warranted. n nThe Mossbauer parameters of pyrite and marcasite exhibit appreciable variations, which bear no simple relationship to the geological environment in which they occur but appear to be selectively influenced by impurities, especially arsenic, in the pyrite lattice. Quantitative and qualitative determinations of pyrite/marcasite mechanical mixtures are straightforward at 298 K and 77 K but do require least-squares computer fittings and are limited to accuracies ranging from ±5 to ±15 per cent by uncertainties in the parameter values of the pure phases. The methodology and results of this investigation are directly applicable to coals for which the presence and relative amounts of pyrite and marcasite could be of considerable genetic significance.

Effects of detrital influx in the Pennsylvanian Upper Freeport peat swamp

Abstract 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.

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

Abstract 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.

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 mz 85 peak (C7H) 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 KCa

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

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 mz 64, 65, 66 signals (possibly S2+, HS2+, H2S2+, 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).

Semi-quantitative ion microprobe mass analyses of mineral-rich particles from the upper freeport coal

Abstract 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 34S-enriched.

Superparamagnetic Fe3O4 particles formed by oxidation of pyrite heated in an anoxic atmosphere

Abstract An ion microprobe mass analyzer (IMMA) has been used to analyze semi-quantitatively mineral-rich coal particles from two separate facies of the Upper Freeport coal bed. Accuracy is estimated to be ∓ 20% for those elements making up more than 0.1 wt.% of the particles and ∓ 50% for elements making up less than 0.1 wt.%. Using IMMA data, we found statistically significant differences between the two samples for five (Fe, Ca, Mn, Li, Ce) of the 25 elements detected. For Li and Mn the differences between the mineral-rich particles within samples were similar to differences found between samples on a whole-coal basis. For Ca and Fe, the differences are attributed to different modes of occurrence, and for Ce, the differences are probably due to an irregular distribution of an inorganic phase. We conclude that the IMMA can be used to obtain semi-quantitative data that may provide insight into the distribution and mode of occurrence of some of the elements in coal.