Mineral matter and the nature of pyrite in some high-sulfur tertiary coals of Meghalaya, northeast India

Coal samples collected from four different sources in the Jaintia Hills of Meghalaya, northeast India, have been investigated for their sulfur content, mineral matter, and to assess their potential behavior upon beneficiation. These coals contain high sulfur which occurs both in organic and inorganic forms. The organic sulfur content is much higher than the inorganic sulfur. Studies on different size and gravity fractions indicated that the mineral phases are concentrated in higher density fractions (d > 1.8) and in general are fine grained (<50 μm). Data of reflected-light optical microscope and electron probe micro-analysis (EPMA) revealed that minerals in these coals are sulfides-pyrite, marcasite, sphalerite, pentlandite; sulfates-barite, jarosite; oxides-hematite, rutile; hydroxides-gibbsite, goethite; phosphate-monazite; carbonate-calcite, siderite and silicates-quartz, mica, chlorite, and kaolinitic clay. The disulfides of iron occur in two modes — mainly pyrite and occasionally marcasite with wide size ranges and in various forms, such as: framboid, colloidal precipitate, colloform-banded, fine disseminations, discrete grains, dendritic (feathery), recrystallized, nuggets, discoidal, massive, cavity-fracture- and cleat-fillings. Framboidal pyrite has formed primarily due to biological activities of sulfur reducing bacteria in the early stages of coalification. Massive and other varieties have formed at later stages due to coalescence and recrystallization of the earlier formed pyrites. Sulfur isotopic values indicate a biogenic origin for the pyrites. Association of trace metals, such as Ni, and Zn has been recorded in these pyrites. Given the large fractions of organic sulfur present, these coals can be upgraded only partially to reduce the sulfur content by beneficiation.     

Mineralogy and geochemistry of feed coals and their combustion residues from the Cayirhan power plant,Ankara, Turkey

A total of 48 samples, feed (run-of-mine) coals and their combustion residues (fly ash and bottom ash) were systematically collected twice a week over a 4 week period (June 1998) from two boiler units (I and II) of the Cayirhan power plant (630 MW) that burns zeolite-bearing coals of late Miocene age. The feed coals are high in moisture (22.8% as-received) content and ash (44.9%) yield and total S content (5.1%), and low in calorific value (2995 kcal/kg). The mineralogy of the feed coals contains unusually high contents of the zeolites (clinoptilolite/heulandite and analcime), which are distributed within the organic matter of coal. Other minerals determined are gypsum, quartz, feldspar, pyrite, dolomite, calcite, cristobalite and clays. Common minerals in the crystalline phase of the combustion residues are anhydrite, feldspar, quartz, hematite, lime and Ca–Mg silicate. Minor and trace amounts of magnetite, cristobalite, maghemite, gehlenite, calcite and clinoptilolite/heulandite are also present in the combustion residues. Trace element contents of the feed coals, except for W, fall within the estimated range of values for most world coals; however, the mean values of Mn, Ta, Th, U and Zr are near maximum values of most world coals. Elements such as As, Bi, Ge, Mo, Pb, Tl, W and Zn are enriched more in the fly ash compared to the bottom ash.     

Isotopic evidence for the origin of sulfur in the Herrin (no. 6) coal member of Illinois

The sulfur isotopic composition of the Herrin (No. 6) Coal from several localities in the Illinois Basin was measured. The sediments immediately overlying these coal beds range from marine shales and limestones to non-marine shales. Organic sulfur, disseminated pyrite, and massive pyrite were extracted from hand samples taken in vertical sections.The $\text{δ}{}^{34}\text{S}$ values from low-sulfur coals (< 0.8% organic sulfur) underlying nonmarine shale were +3.4 to +7.3%₀ for organic sulfur, +1.8 to +16.8%₀ for massive pyrite, and +3.9 to +23.8%₀ for disseminated pyrite. In contrast, the $\text{δ}{}^{34}\text{S}\text{values from high-sulfur coals}$ (> 0.8% organic sulfur) underlying marine sediments were more variable: organic sulfur, ?7.7 to +0.5%₀, pyrites, ?17.8 to +28.5%₀. In both types of coal, organic sulfur is typically enriched in ³⁴S relative to pyritic sulfur.In general, δ ³⁴S values increased from the top to the base of the bed. Vertical and lateral variations in δ ³⁴S are small for organic sulfur but are large for pyritic sulfur. The sulfur content is relatively constant throughout the bed, with organic sulfur content greater than disseminated pyrite content. The results indicate that most of the organic sulfur in high-sulfur coals is derived from post-depositional reactions with a ³⁴S-depleted source. This source is probably related to bacterial reduction of dissolved sulfate in Carboniferous seawater during a marine transgression after peat deposition. The data suggest that sulfate reduction occurred in an open system initially, and then continued in a closed system as sea water penetrated the bed.Organic sulfur in the low-sulfur coals appears to reflect the original plant sulfur, although diagenetic changes in content and isotopic composition of this fraction cannot be ruled out. The wide variability of the δ ³⁴S in pyrite fractions suggests a complex origin involving varying extents of microbial H₂S production from sulfate reservoirs of different isotopic compositions. The precipitation of pyrite may have begun soon after deposition and continued throughout the coalification process.     

Observations on low-temperature oxidation of minerals in bituminous coals

Mineral matter in three naturally weathered coals from Pennsylvania strip mines and in two laboratory-oxidized coals has been characterized by ⁵⁷Fe Mössbauer spectroscopy, scanning electron microscopy and other techniques to determine mineralogical trasnformations that occur in coals during weathering. Pyrite was found to be the most readily oxidized mineral, forming a variety of iron sulfates initially and geethite eventually. The iron sulfates formed were different in the two laboratory-oxidized coals, despite identical oxidation treatments. Calcite disappeared from one calcite-rich coal with increasing oxidation, but was not replaced by an equivalent amount of gypsum. A severely weathered strip-mine coal was enriched in calcium, which was dispersed through the oxidized macerals. Extended X-ray absorption fine-structure spectroscopy indicated that this dispersed calcium was most likely present as salts of carboxylic acids. Siderite was suprisingly resistant to oxidation at room temperature. Less direct evidence indicates that clay minerals also take part in the alteration to some extent.The coals oxidized in the laboratory showed alteration behavior that differed in a number of respects from that of the strip-mine coals. For example, iron sulfates were much less common in the latter coals; also, the formation of geothite appeared to be controlled to a large extent by the pyrite particle size in the strip-mine coals, but not in the laboratory-oxidized coals.The oxidation of an individual pyrite grain is not only a function of general conditions (temperature, humidity, oxygen partial pressure), but also the immediate local (< 1 mm) chemistry, as a variety of iron sulfates were observed in the coals, often in close proximity. Also, assemblages of gypsum and goethite were observed in otherwise slightly oxidized coal, which indicates that the alteration of pyrite and calcite, when in close contact, proceeds most rapidly.     

Sulfur geochemistry of Jurassic high-sulfur coals from Egypt

Jurassic high-sulfur coals from the Maghara area in Egypt were analyzed for the abundance and isotopic composition of different forms of sulfur. Analyses indicated that the sulfur occurs in the form of organic, pyrite, and sulfate forms. Pyrite sulfur represents the major fraction, while sulfate sulfur is minor and could be formed during sample preparation for the analyses.The δ³⁴S CDT values of the organic sulfur are positive ranging between 1.0‰ and 13.5‰ with an average of 9.1‰. Pyrite δ³⁴S values are also positive ranging between 1.5‰ and 15.4‰ with an average of 6.6‰. The high δ³⁴S values of the organic sulfur in the Maghara coals suggest a freshwater origin of the organic components of these coals. The lack of correlation between pyrite and organic sulfur isotopes implies different incorporation mechanisms of sulfur. The high-sulfur contents along with the positive and high δ³⁴S values suggest a marine origin of pyrite sulfur and support the geological interpretation of marine invasion after the peat formation that was responsible for the incorporation of the pyrite sulfur.The occurrence of pyrite as euhedral crystals as well as the high and positive δ³⁴S values of the pyrite sulfur indicates the formation of pyrite during diagenesis as a result of marine water invasion of the preexisting peat in a brackish coastal plain environment.     

Processes controlling the composition of acid sulfate solutions evolved from coal

Leaching of a series of Appalachian coals by distilled water has been studied in laboratory reactors. From columns open to air at 25°C, leachates were produced containing typically about 0.2 M SO₄²⁻, 0.1 M total Fe and having pH < 2. Leachates contained high concentrations of toxic trace metals, including Be, Al, Cu and Cd. Concentrations of sulfate and Fe in leachates from different coals were similar and were not related to concentrations of total S in the coals. Saturation with respect to melanterite (FeSO₄·7H₂O) and a ferric oxyhydroxide phase was observed in most solutions. Leachates were undersaturated with respect to anhydrous ferric sulfate and Na-jarosite, but supersaturated with respect to K-jarosite, suggesting that none of these phases controlled solution composition. The ratio of total ferric Fe to total ferrous Fe normally exceeded unity. Accumulation of ferric Fe indicates either that its reaction with pyrite is inhibited in weathered coals, or that the coals contain pockets of oxidized pore fluid that are out of contact with pyrite. Release of Be correlated with release of Al, and release of Cu correlated with release of Fe. Reducing the temperature, lowering the partial pressure of oxygen or adding limestone retarded the release of pyrite oxidation products from the coals. Addition of limestone should be considered if it is necessary to control release of acid leachates from coal piles.     

Mineralogy and geochemistry of different morphological pyrite in Late Permian coals,South China

The mineralogical and morphological characteristics, concentration of major and trace elements, and sulfur isotopic composition of three pyrite and two coal samples in the Upper Permian high-sulfur coals from Xingren, Zhijin, and Hefeng mining area, South China, were investigated, by using optical microscopy, field emission-scanning electron microscopy in conjunction with an energy-dispersive X-ray spectrometer (FE SEM-EDS), X-ray powder diffraction (XRD), X-ray fluorescence (XRF), inductively coupled plasma mass spectrometry (ICP-MS), cold vapor atomic absorption spectrometry (CVAAS), and isotopic ratio mass spectrometer. The pyrite in Xingren and Zhijin coals mainly occurs as nodular, lens-shaped, thin-layer, and massive forms, and it occurs mainly as fine vein fillings in the Hefeng coals. Microscopically, pyrite in the coals from Xingren, Zhijin, and Hefeng mainly occurs as framboidal, cell-filling, and vein-filling forms, respectively. There is a distinct difference in X-ray powder diffractogram and diffraction data of the three pyrite samples. There is a maximum diffraction peak (2.709 Å) in pyrite in the coals from Xingren and (2.707 Å) in pyrite in the coals from Zhijin; however, the maximum diffraction peak is 3.343 Å in pyrite in the coals from Hefeng. The average unit cell length (a ₀) is 5.4169 Å for the Xingren pyrite, 5.4159 Å for the Zhijin pyrite, and 5.4170 Å for the Hefeng pyrite. The ratio of S/Fe is 2.16 for the Xingren pyrite, 2.09 for the Zhijin pyrite, and 2.01 for the Hefeng pyrite. Copper (701 μg/g), Ni (369 μg/g), and Co (29.6 μg/g) concentrated in the Hefeng pyrite. The concentration of As is 126, 19.6, and 19.1 μg/g in the Hefeng, Zhijin, and Xingren pyrite, respectively. Mercury is 11.7 μg/g in the Xingren pyrite, 2.79 μg/g in the Zhijin pyrite, and 0.512 μg/g in the Hefeng pyrite. There is a clear tendency that elements Cu, Ni, Co, Cr, Se, Mo, and As are significantly enriched in the Hefeng pyrite. Mercury is greatly enriched in the Xingren pyrite, and Zn is enriched in Zhijin pyrite. Rare earth elements and yttrium (REY) are not abundant (8.276 μg/g) in the Hefeng pyrite and are characterized by maximum positive anomaly of Eu (Eu/Eu* = 6.54). The δ³⁴S value is ?26.9 ‰ in the Xingren pyrite, +3.8 ‰ in the Zhijin pyrite, and +3.7 ‰ in the Hefeng pyrite. The trace elements in the Hefeng pyrite and coal are As (126 and 6.1 μg/g), Hg (0.512 and 0.158 μg/g), Zn (276 and 56.7 μg/g), Se (16.5 and 1.07 μg/g), Mo (45.5 and 9.93 μg/g), Cu (701 and 37.8 μg/g), Ni (369 and 16.9 μg/g), Co (29.6 and 8.63 μg/g), Sb (2.64 and 0.742 μg/g), Cd (3.49 and 0.366 μg/g), and Pb (62.8 and 33.5 μg/g), demonstrating that these potentially toxic trace elements were mainly concentrated in pyrites. The strongly positive Eu anomaly (Eu/Eu* = 6.54) in the netted pyrite vein filled in the cleats of the Hefeng coal may be the product of epigenetic hydrothermal fluid.     

Lead isotope ratios in Spanish coals of different characteristics and origin

Lead isotope ratios in coals of different rank from several Spanish basins were estimated and related with their characteristics. The isotope ²⁰⁶Pb/²⁰⁷Pb ratio values of the coals studied range between 1.13 and 1.21, with the exception of some coal samples from the Cretaceous which are more radiogenic. Coals were classified into groups according to their lead isotope ratios. These in turn were related to the isotope ratios of the minerals galena, pyrite, chalcopyrite, and carbonates. Some of the low-rank coals, in which lead might be expected to be associated with the organic matter, were not found to be related with the isotope ratios of minerals. The isotope ratios of the individual densimetric fractions separated from a bituminous coal are different to those of the raw coal. The differences between these isotope ratios may not only be due to the diverse origin of lead in different coals, but also with the possible presence of several lead species incorporated from various sources in a particular coal. The results of this work represent an important contribution to the lead isotope ratio database essential for the accurate interpretation of data regarding pollution sources.     

Determination of elemental affinities by density fractionation of bulk coal samples from the Chongqing coal district, Southwestern China

The occurrence and distribution of major and trace elements have been investigated in two coal-bearing units in the Chonqing mining district (South China): the Late Permian and Late Triassic coals.The Late Permian coals have higher S contents than the Late Triassic coals due to the fixation of pyrite in marine-influenced coal-forming environments. The occurrence of pyrite accounts for the association of a large number of elements (Fe, S, As, Cd, Co, Cu, Mn, Mo, Ni, Pb, Sb, Se, and Zn) with sulphides, as deduced from the analysis of the density fractions. The marine influence is probably also responsible for the organic association of B. The REEs, Zr, Nb, and Hf, are enriched by a factor of 2–3 with respect to the highest levels fixed for the usual worldwide concentration ranges in coal for these elements. The content of these elements in the Late Permian coal is higher by a factor of 5–10 with respect to the Late Triassic coal. Furthermore, other elements, such as Cu, P, Th, U, V, and Y, are relatively enriched with respect to the common range values, with maximum values higher than the usual range or close to the maximum levels in coal. The content of these elements in the Late Permian coal is higher than the Late Triassic coal. These geochemical enrichments are the consequence of the occurrence, in relatively high levels, of phosphate minerals, such as apatite, xenotime, and monazite, as deduced from the study of the density fractions obtained from the bulk coal.The Late Triassic coal has a low sulphur content with a major organic affinity. The trace element contents are low when compared with worldwide ranges for coal. In this coal, the trace element distribution is governed by clay minerals, carbonate minerals, and to a lesser extent, by organic matter and sulphide minerals.Major differences found between late Permian and Triassic coals are probably related to the source rocks, given that the main source rock of the late Permian epicontinental marine basin is the Emeishan basalt formation, characterised by a high phosphate content.     

Flotation of calcareous Mussorie phosphate ore

Separation of Mussorie rock phosphate (P₂O₅ = 20%) from Uttar Pradesh, India, containing pyrite, calcite and other carbonaceous impurities by flotation has been successfully attempted to upgrade the phosphate values. Based on Hallimond cell flotation results of single and synthetic mineral mixtures of calcite and apatite using oleic acid and potassium phosphate, conditions were obtained for the separation of calcite from apatite which is considered to be the most difficult step in the beneficiation of calcareous phosphates. Further studies using 250 g of the mineral (?60 +150 and ?150 mesh fractions, deslimed) in laboratory size Fagergren subaeration machine employed a stagewise flotation viz. carbonaceous materials using terpineol, pyrite using potassium-ethyl xanthate and calcite using oleic acid respectively. Separation was, however, found to be unsatisfactory in the absence of a depressant.Among starch, hydrofluosilicic acid and dipotassium hydrogen phosphate, which were tried as depressants for apatite in the final flotation stage, dipotassium hydrogen phosphate proved to be superior to others. However, the tests with the above fractions did not yield the required grade. This was possibly due to insufficient liberation of the phosphate mineral from the ore body and different experimental conditions due to scale up operations. Experiments conducted using ?200 mesh deslimed fractions has yielded an acceptable grade of 27.6% P₂O₅ with a recovery of about 60%. The results have been explained in terms of the specific adsorption characteristics of phosphate ions on apatite and the liberation size of the mineral.     

Variation in pyrite size, form, and microlithotype association in the springfield (no. 9) and herrin (no. 11) coals, Western Kentucky

Channel samples of the Springfield (No. 9) and Herrin (No. 11) (Pennsylvanian, Desmoinesian/Westphalian D) coals were acquired in three mines each in the Western Kentucky coal field. Pyrite was characterized petrographically in terms of its size, form, and microlithotype association. Within each coal seam significant variations in the amount of pyrite of certain forms occurred between the sites. Pyritic sulfur as determined chemically did not exhibit significant variation between the seams or between the sites. The variation in dendritic pyrite in vitrite plus clarite between seams and between sites was highly significant and the variation in framboidal pyrite in vitrite plus clarite between sites was also highly significant.     

Methane and carbon dioxide adsorption–diffusion experiments on coal: upscaling and modeling

Numerical modelling of the processes of CO₂ storage in coal and enhanced coalbed methane (ECBM) production requires information on the kinetics of adsorption and desorption processes. In order to address this issue, the sorption kinetics of CO₂ and CH₄ were studied on a high volatile bituminous Pennsylvanian (Upper Carboniferous) coal (VR_r=0.68%) from the Upper Silesian Basin of Poland in the dry and moisture-equilibrated states. The experiments were conducted on six different grain size fractions, ranging from <0.063 to 3 mm at temperatures of 45 and 32 °C, using a volumetric experimental setup. CO₂ sorption was consistently faster than CH₄ sorption under all experimental conditions. For moist coals, sorption rates of both gases were reduced by a factor of more than 2 with respect to dry coals and the sorption rate was found to be positively correlated with temperature. Generally, adsorption rates decreased with increasing grain size for all experimental conditions.Based on the experimental results, simple bidisperse modelling approaches are proposed for the sorption kinetics of CO₂ and CH₄ that may be readily implemented into reservoir simulators. These approaches consider the combination of two first-order reactions and provide, in contrast to the unipore model, a perfect fit of the experimental pressure decay curves. The results of this modeling approach show that the experimental data can be interpreted in terms of a fast and a slow sorption process. Half-life sorption times as well as the percentage of sorption capacity attributed to each of the two individual steps have been calculated.Further, it was shown that an upscaling of the experimental and modelling results for CO₂ and CH₄ can be achieved by performing experiments on different grain size fractions under the same experimental conditions.In addition to the sorption kinetics, sorption isotherms of the samples with different grain size fractions have been related to the variations in ash and maceral composition of the different grain size fractions.     

煤中黄铁矿的铼-锇同位素含量及其地质意义

采用Carius管溶样方法,通过热电离质谱对淮北煤田煤中黄铁矿样品的Re、Os含量及其同位素进行了测定,得出黄铁矿样品中Re和Os含量分别为1·22~1·29ng/g和0·0046~0·0054ng/g。对两个样品同位素定年测定得出,其年龄值分别为(73·9±3·2)Ma和(33±9)Ma,两个样品的年龄相差约258~286Ma。含量和同位素年龄差值表明两个样品是不同时代形成的黄铁矿。Re-Os同位素体系比值揭示黄铁矿所赋存的地质体受到来自地壳物质的显著混染。另外,γOTs参数也证实了这一点。该参数分别为+17和+18,表明了有富含Re母体的地壳物质的加入,这为煤中Re-Os含量及地质理论研究提供了参考资料。     

Organic geochemical characteristics and depositional environments of the Jurassic coals in the eastern Taurus of Southern Turkey

In this study, organic matter content, type and maturity as well as some petrographic and physical characteristics of the Jurassic coals exposed in the eastern Taurus were investigated and their depositional environments were interpreted.The total organic carbon (TOC) contents of coals in the Feke–Akkaya, Kozan–Gedikli and Kozan–Kizilinc areas are 24.54, 66.78 and 49.15%, respectively. The Feke–Akkaya and Kozan–Kizilinc coals have low Hydrogen Index (HI) values while the Kozan–Gedikli coals show moderate HI values. All coal samples display very low Oxygen Index (OI) values. The Kozan–Gedikli coals contain Type II organic matter (OM), the Feke–Akkaya coals contain a mixture of type II and type III OM; and the Kozan–Kizilinc coals are composed of Type III OM. Sterane distribution was calculated as C₂₇ > C₂₉ > C₂₈ from the m/z 217 mass chromatogram for all coal samples.T_max values for the Feke–Akkaya, Kozan–Gedikli and Kozan–Kizilinc coals are 439, 412 and 427 °C. Vitrinite reflectance values (%R_o) for the Feke–Akkaya and Kozan–Kizilinc coal samples were measured as 0.65 and 0.51 and these values reveal that the Feke–Akkaya and Kozan–Kizilinc coals are at subbituminous A or high volatile C bituminous coal stage. On the basis of biomarker maturity parameters, these coals have a low maturity.The pristane/phytane (Pr/Ph) ratios for the Feke–Akkaya, Kozan–Gedikli and Kozan–Kizilinc coals are 1.53, 1.13 and 1.25, respectively. In addition, all coals show a homohopane distribution which is dominated by low carbon numbers, and C₃₅ homohopane index is very low for all coal samples. All these features may indicate that these coals were deposited in a suboxic environment.The high sterane/hopane ratios with high concentrations of steranes, low Pr/Ph ratios and C₂₅/C₂₆ tricyclic ratios > 1 may indicate that these coals formed in a swamp environment were temporarily influenced by marine conditions.     

Liquid hydrocarbon generation potential from Tertiary Nyalau Formation coals in the onshore Sarawak, Eastern Malaysia

Tertiary coals exposed in the north-central part of onshore Sarawak are evaluated, and their depositional environments are interpreted. Total organic carbon contents (TOC) of the coals range from 58.1 to 80.9 wt. % and yield hydrogen index values ranging from 282 to 510 mg HC/g TOC with low oxygen index values, consistent with Type II and mixed Type II–III kerogens. The coal samples have vitrinite reflectance values in the range of 0.47–0.67 Ro %, indicating immature to early mature (initial oil window). T _max values range from 428 to 436 °C, which are good in agreement with vitrinite reflectance data. The Tertiary coals are humic and generally dominated by vitrinite, with significant amounts of liptinite and low amounts of inertinite macerals. Good liquid hydrocarbons generation potential can be expected from the coals with rich liptinitic content (>35 %). This is supported by their high hydrogen index of up to 300 mg HC/g TOC and Py-GC (S ₂) pyrograms with n-alkane/alkene doublets extending beyond C₃₀. The Tertiary coals are characterised by dominant odd carbon numbered n-alkanes (n-C₂₃ to n-C₃₃), high Pr/Ph ratio (6–8), high T _m /T _s ratio (8–16), and predominant regular sterane C₂₉. All biomarkers parameters clearly indicate that the organic matter was derived from terrestrial inputs and the deposited under oxic condition.     

Studies of the relationship between coal petrology and grinding properties

The maceral and microlithotype composition of selected coals has been investigated with respect to the grinding properties, specifically Hardgrove grindability index (HGI), of the coals. The study expands upon previous investigations of HGI and coal petrology by adding the dimension of the amount and composition of the microlithotypes. Coal samples, both lithotypes and whole channels, were selected from restricted rank ranges based on vitrinite maximum reflectance: 0.75–0.80% R_max, 0.85–0.90% R_max and 0.95–1.00% R_max. In this manner, the influence of petrographic composition can be isolated from the influence of rank. Previous investigations of high volatile bituminous coals demonstrated that, while rank is an important factor in coal grindability, the amount of liptinite and liptinite-rich microlithotypes is a more influential factor. In this study, we provide further quantitative evidence for the influence of microlithotypes on HGI and, ultimately, on pulverizer performance.     

Modes of occurrence of minerals in the Carboniferous coals from the Wuda Coalfield,northern China: with an emphasis on apatite formation

The mineralogical compositions of the Nos. 9 and 13 coals, which are medium-volatile bituminous coals in rank, from the Wuda Coalfield at the northwestern margin of the Ordos Basin in northern China, were investigated by optical microscopy, field emission-scanning electron microscopy in conjunction with energy-dispersive X-ray spectrometry (SEM-EDX), and X-ray powder diffraction techniques. The minerals in the Wuda coals are mainly represented by quartz, kaolinite, illite, pyrite, marcasite, apatite, dolomite, and ankerite, with trace amounts of anatase, calcite, boehmite, jarosite, gibbsite, anhydrite, and bassanite in some samples. The rod-like pyritized bacteria have been identified with SEM-EDX in Wuda coals. Moreover, the slightly reducing and alkaline environment in the original peat swamp favored bacterial action and propagation. The average concentrations of P₂O₅ in the Nos. 9 and 13 coals are 0.47 and 0.18 %, respectively. Phosphorus is not uniformly distributed within the Wuda coal seam. The maximum content of apatite in Wuda coals in certain horizon can reach up to 91.4 % (on an organic matter-free basis), corresponding to the fluorine and P₂O₅ concentrations of 2803 μg/g and 5.96 %. The high proportion of fluorine and P₂O₅ in the Wuda coals is mainly due to the authigenic apatite. The phosphorus in Wuda coals was probably derived mainly from phospho-proteins in the organic matter of the original peat deposits.     

Mossbauer detection of goethite (α-FeOOH) in coal and its potential as an indicator of coal oxidation

Mössbauer spectroscopy of three suites of oxidized coals shows that the transformation of pyrite to FeOOH correlates with other parameters of oxidation. As pyrite is very common in coals and the transformation to FeOOH is sensitive to small degrees of oxidation, the Mössbauer technique shows considerable promise as a means for the detection of coal oxidation.     

The 57Fe Mössbauer 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 Mössbauer 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 Mössbauer spectroscopy at 298 K. At 298 K the average electric quadrupole splitting, 〈ΔE_Q〉, 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; 〈ΔE_Q〉 = 0.5030 ± 0.0070 mm s^?1 and 〈δ〉 = 0.2770 ± 0.0020 mm s^?1 for the 12 marcasites. At 77 K, ΔE_Q 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.The Mössbauer 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.