From in-situ coal to fly ash: a study of coal mines and power plants from Indiana

This paper presents data on the properties of coal and fly ash from two coal mines and two power plants that burn single-source coal from two mines in Indiana. One mine is in the low-sulfur (<1%) Danville Coal Member of the Dugger Formation (Pennsylvanian) and the other mines the high-sulfur (>5%) Springfield Coal Member of the Petersburg Formation (Pennsylvanian). Both seams have comparable ash contents (11%). Coals sampled at the mines (both raw and washed fractions) were analyzed for proximate/ultimate/sulfur forms/heating value, major oxides, trace elements and petrographic composition. The properties of fly ash from these coals reflect the properties of the feed coal, as well as local combustion and post-combustion conditions. Sulfur and spinel content, and As, Pb and Zn concentrations of the fly ash are the parameters that most closely reflect the properties of the source coal.     

Optical properties of pseudovitrinite; implications for its origin

A set of Pennsylvanian coals from the North American coal basins, ranging in vitrinite reflectance from 0.65% to 1.75%, was examined, with special emphasis on the optical properties of pseudovitrinite. The results suggest that pseudovitrinite originates from the same material as telocollinite. Slits in the pseudovitrinite seem to have originated in situ due to low-temperature oxidation of woody material; their opening might have been facilitated by devolatilization during coalification. The dominant orientation of the slits is perpendicular to bedding. The intensity and orientation of the slits in pseudovitrinite could be important factors in predicting coalbed gas extraction from coal.     

Anthropogenic organic matter in the Great Marsh of the Indiana Dunes National Lakeshore and its implications

Cores from the Great Marsh area of the Indiana Dunes National Lakeshore were examined in order to document variations in concentration, type and size of anthropogenic organic matter (A_nOM—coal, coke, etc.) and discuss their relationship to the concentration of such trace elements as Pb, Zn, and Mn in the near-surface sediment section. The results indicate that the first appearance of A_nOM corresponds to the onset of industrialization in the area. There is also a general relationship between the occurrence of A_nOM and Zn, Pb, and Mn. Trace metals were likely transported from the industrial sites to the area of their deposition as sulfur-bearing coatings on small anthropogenic particles. After deposition, these sulfur-bearing compounds reacted with organic matter within the marsh. As a result of bacterial reduction, the pyrite was produced, as suggested by a close relationship between the pyrite and A_nOM. Distance from the industrial complex upwind as well as local hydrologic conditions are among the major factors controlling distribution of A_nOM and trace elements. At the same distance from the source, types and sizes of A_nOM are influenced by the duration and frequency of flooding.     

Cleats and their relation to geologic lineaments and coalbed methane potential in Pennsylvanian coals in Indiana

Cleats and fractures in Pennsylvanian coals in southwestern Indiana were described, statistically analyzed, and subsequently interpreted in terms of their origin, relation to geologic lineaments, and significance for coal permeability and coalbed gas generation and storage. These cleats can be interpreted as the result of superimposed endogenic and exogenic processes. Endogenic processes are associated with coalification (i.e., matrix dehydration and shrinkage), while exogenic processes are mainly associated with larger-scale phenomena, such as tectonic stress.At least two distinct generations of cleats were identified on the basis of field reconnaissance and microscopic study: a first generation of cleats that developed early on during coalification and a second generation that cuts through the previous one at an angle that mimics the orientation of the present-day stress field. The observed parallelism between early-formed cleats and mapped lineaments suggests a well-established tectonic control during early cleat formation. Authigenic minerals filling early cleats represent the vestiges of once open hydrologic regimes. The second generation of cleats is characterized by less prominent features (i.e., smaller apertures) with a much less pronounced occurrence of authigenic mineralization. Our findings suggest a multistage development of cleats that resulted from tectonic stress regimes that changed orientation during coalification and basin evolution.The coals studied are characterized by a macrocleat distribution similar to that of well-developed coalbed methane basins (e.g., Black Warrior Basin, Alabama). Scatter plots and regression analyses of meso- and microcleats reveal a power-law distribution between spacing and cleat aperture. The same distribution was observed for fractures at microscopic scale. Our observations suggest that microcleats enhance permeability by providing additional paths for migration of gas out of the coal matrix, in addition to providing access for methanogenic bacteria.The abundance, distribution, and orientation of cleats control coal fabric and are crucial features in all stages of coalbed gas operations (i.e., exploration and production). Understanding coal fabric is important for coal gas exploration as it may be related to groundwater migration and the occurrence of methanogenic bacteria, prerequisite to biogenic gas accumulations. Likewise, the distribution of cleats in coal also determines pathways for migration and accumulation of thermogenic gas generated during coalification.     

Organic nitrogen chemistry during low-grade metamorphism

Most of the organic nitrogen (N_org) on Earth is disseminated in crustal sediments and rocks in the form of fossil nitrogen-containing organic matter. The chemical speciation of fossil N_org within the overall molecular structure of organic matter changes with time and heating during burial. Progressive thermal evolution of organic matter involves phases of enhanced elimination of N_org and ultimately produces graphite containing only traces of nitrogen. Long-term chemical and thermal instability makes the chemical speciation of N_org a valuable tracer to constrain the history of sub-surface metamorphism and to shed light on the subsurface biogeochemical nitrogen cycle and its participating organic and inorganic nitrogen pools. This study documents the evolutionary path of N_org speciation, transformation and elimination before and during metamorphism and advocates the use of X-ray photoelectron spectroscopy (XPS) to monitor changes in N_org speciation as a diagnostic tool for organic metamorphism. Our multidisciplinary evidence from XPS, stable isotopes, traditional quantitative coal analyses, and other analytical approaches shows that at the metamorphic onset N_org is dominantly present as pyrrolic and pyridinic nitrogen. The relative abundance of nitrogen substituting for carbon in condensed, partially aromatic systems (where N is covalently bonded to three C atoms) increases exponentially with increasing metamorphic grade, at the expense of pyridinic and pyrrolic nitrogen. At the same time, much N_org is eliminated without significant nitrogen isotope fractionation. The apparent absence of Rayleigh-type nitrogen isotopic fractionation suggests that direct thermal loss of nitrogen from an organic matrix does not serve as a major pathway for N_org elimination. Instead, we propose that hot H, O-containing fluids or some of their components gradually penetrate into the carbonaceous matrix and eliminate N_org along a progressing reaction front, without causing nitrogen isotope fractionation in the residual N_org in the unreacted core of the carbonaceous matrix. Before the reaction front can reach the core, an increasing part of core N_org chemically stabilizes in the form of nitrogen atoms substituting for carbon in condensed, partially aromatic systems forming graphite-like structural domains with delocalized π-electron systems (nitrogen atoms substituting for “graphitic” carbon in natural metamorphic organic matter). Thus, this nitrogen species with a conservative isotopic composition is the dominant form of residual nitrogen at higher metamorphic grade.     

Progression in sulfur isotopic compositions from coal to fly ash: Examples from single-source combustion in Indiana

Sulfur occurs in multiple mineral forms in coals, and its fate in coal combustion is still not well understood. The sulfur isotopic composition of coal from two coal mines in Indiana and fly ash from two power plants that use these coals were studied using geological and geochemical methods. The two coal beds are Middle Pennsylvanian in age; one seam is the low-sulfur (< 1%) Danville Coal Member of the Dugger Formation and the other is the high-sulfur (> 5%) Springfield Coal Member of the Petersburg Formation. Both seams have ash contents of approximately 11%. Fly-ash samples were collected at various points in the ash-collection system in the two plants. The results show notable difference in δ³⁴S for sulfur species within and between the low-sulfur and high-sulfur coal. The δ³⁴S values for all sulfur species are exclusively positive in the low-sulfur Danville coal, whereas the δ³⁴S values for sulfate, pyritic, and organic sulfur are both positive and negative in the high-sulfur Springfield coal. Each coal exhibits a distinct pattern of stratigraphic variation in sulfur isotopic composition. Overall, the δ³⁴S for sulfur species values increase up the section in the low-sulfur Danville coal, whereas they show a decrease up the vertical section in the high-sulfur Springfield coal. Based on the evolution of δ³⁴S for sulfur species, it is suggested that there was influence of seawater on peat swamp, with two marine incursions occurring during peat accumulation of the high-sulfur Springfield coal. Therefore, bacterial sulfate reduction played a key role in converting sulfate into hydrogen sulfide, sulfide minerals, and elemental sulfur. The differences in δ³⁴S between sulfate sulfur and pyritic sulfur is very small between individual benches of both coals, implying that some oxidation occurred during deposition or postdeposition.The δ³⁴S values for fly ash from the high-sulfur Springfield coal (averaging 9.7‰) are greatly enriched in ³⁴S relative to those in the parent coal (averaging 2.2‰). This indicates a fractionation of sulfur isotopes during high-sulfur coal combustion. By contrast, the δ³⁴S values for fly-ash samples from the low-sulfur Danville coal average 10.2‰, only slightly enriched in ³⁴S relative to those from the parent coal (average 7.5‰). The δ³⁴S values for bulk S determined directly from the fly-ash samples show close correspondence with the δ³⁴S values for SO₄^− 2 leached from the fly ash in the low-sulfur coal, suggesting that the transition from pyrite to sulfate occurred via high-temperature oxidation during coal combustion.     

C NMR, micro-FTIR and fluorescence spectra, and pyrolysis-gas chromatograms of coalified foliage of late Carboniferous medullosan seed ferns, Nova Scotia, Canada: Implications for coalification and chemotaxonomy

The cuticles and cuticle-free compressions of three Carboniferous medullosan seed-fern leaf species (Macroneuropteris scheuchzeri, Neuropteris ovata var. simonii and Alethopteris lesquereuxii) were analyzed by elemental, ¹³C nuclear magnetic resonance (NMR), micro-FTIR (Fourier transform infrared) and coal petrographic techniques. The 13C NMR spectra of the cuticle-free compressions and the associated whole coal (high volatile A/B bituminous coal rank) are generally similar and consist of a large aromatic carbon peak, a smaller aliphatic carbon peak and a shoulder on the aromatic peak, representing phenolic carbons. In contrast, the ¹³C NMR spectra of the cuticles from the same leaves have a predominant peak for aliphatic carbons and a much smaller aromatic carbon peak. This difference in aromaticity between the cuticles and the cuticle-free compressions is also reflected in the higher atomic H/C ratios of the cuticles. Micro-FTIR spectra of the cuticles show oxygenated functional groups (carboxyl and ketone) similar to those in modern cuticles but their most characteristic feature is very strong bands in the aliphatic stretching region. The cuticle-free compressions (mainly vitrinite), in turn, show the absence or significant reduction in oxygenated functional groups, reduction in aliphatic stretching bands and, usually, increased absorbance of aromatic out-of-plane deformation in the 700–900 cm⁻¹ region. Fluorescence spectra for the cuticles from all three species show a great similarity with a λ_max at 580–590 nm, probably reflecting a similardegree of coalification, which is consistent with the similar vitrinite reflectance (R_r) and H/C and O/C ratios of the cuticlefree compressions.These results indicate that leaf cuticle-free compressions, which were initially cellulose rich ( 90% cellulose and hemicellulose, < 10% lignin), can alter, during peatification and coalification, to a macromolecular structure similar to that of coalified wood (initially 50% cellulose and hemicellulose, 30%–50% lignin). Thus, a lignin-enriched structure is not a prerequisite for the formation of the macromolecular structure of vitrinite. In addition, the micro-FTIR spectra reveal the complexity of the molecular structure in coalified seed-fern leaves. The micro-FFIR data reveal some significant differences among the cuticles that may be of chemotaxonomic value. Clearly, a combination of macro- and micro-techniques offers a better basis for the interpretation of the molecular structure of pre-macerals and their alteration during peatification and coalification. Also, the data presented in this paper provide important new information that extends the data from morphological and cuticular taxonomic studies of some seed ferns. The data are encouraging preliminary advances in the chemotaxonomy of medullosan seed fern species.Pyrolysis-gas chromatography (PY-GC) data for the cuticles of three seed-fern leaves indicate distinct chemical signatures for the two neuropterid leaves as compared to the Alethopteris leaf. This perhaps indicates a chemotaxomic factor, or it could be related to the greater thickness of the cuticle of Alethopteris. Mass spectrometric data are needed to identify individual components in the PY-GC chromatograms.     

Chemical structures of coal lithotypes before and after CO2 adsorption as investigated by advanced solid-state C nuclear magnetic resonance spectroscopy

Four lithotypes (vitrain, bright clarain, clarain, and fusain) of a high volatile bituminous Springfield Coal from the Illinois Basin were characterized using advanced solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy. The NMR techniques included quantitative direct polarization/magic angle spinning (DP/MAS), cross polarization/total sideband suppression (CP/TOSS), dipolar dephasing, CH_n selection, and recoupled C-H long-range dipolar dephasing techniques. The lithotypes that experienced high-pressure CO₂ adsorption isotherm analysis were also analyzed to determine possible changes in coal structure as a result of CO₂ saturation at high pressure and subsequent evacuation. The main carbon functionalities present in original vitrain, bright clarain, clarain and fusain were aromatic carbons (65.9%-86.1%), nonpolar alkyl groups (9.0%-28.9%), and aromatic C-O carbons (4.1%-9.5%). Among these lithotypes, aromaticity increased in the order of clarain, bright clarain, vitrain, and fusain, whereas the fraction of alkyl carbons decreased in the same order. Fusain was distinct from other three lithotypes in respect to its highest aromatic composition (86.1%) and remarkably small fraction of alkyl carbons (11.0%). The aromatic cluster size in fusain was larger than that in bright clarain. The lithotypes studied responded differently to high pressure CO₂ saturation. After exposure to high pressure CO₂, vitrain and fusain showed a decrease in aromaticity but an increase in the fraction of alkyl carbons, whereas bright clarain and clarain displayed an increase in aromaticity but a decrease in the fraction of alkyl carbons. Aromatic fused-rings were larger for bright clarain but smaller for fusain in the post-CO₂ adsorption samples compared to the original lithotypes. These observations suggested chemical CO₂-coal interactions at high pressure and the selectivity of lithotypes in response to CO₂ adsorption.     

Changes in optical properties, chemistry, and micropore and mesopore characteristics of bituminous coal at the contact with dikes in the Illinois Basin

Changes in high-volatile bituminous coal (Pennsylvanian) near contacts with two volcanic intrusions in Illinois were investigated with respect to optical properties, coal chemistry, and coal pore structure. Vitrinite reflectance (R_o) increases from 0.62% to 5.03% within a distance of 5.5 m from the larger dike, and from 0.63% to 3.71% within 3.3 m from the small dike. Elemental chemistry of the coal shows distinct reductions in hydrogen and nitrogen content close to the intrusions. No trend was observed for total sulfur content, but decreases in sulfate content towards the dikes indicate thermochemical sulfate reduction (TSR). Contact-metamorphism has a dramatic effect on coal porosity, and microporosity in particular. Around the large dike, the micropore volume, after a slight initial increase, progressively decreases from 0.0417 cm³/g in coal situated 4.7 m from the intrusive contact to 0.0126 cm³/g at the contact. Strongly decreasing mesopore and micropore volumes in the altered zone, together with frequent cleat and fracture filling by calcite, indicate deteriorating conditions for both coalbed gas sorption and gas transmissibility.