Geology topics

Maria Mastalerz

Publications and source records attributed to Maria Mastalerz.

At least 19 recordsLinked to original sources

USGS2025

Component identification of solid biomass fuels using reflected light microscopy: Interlaboratory study 2

As nations transition toward sustainable energy systems , biomass has become a vital component of global energy portfolios. Derived from organic materials such as wood, agricultural residues, forestry byproducts, and organic waste, biomass is a renewable energy source with significant environmental and economic benefits. Responsible biomass energy production can improve waste management, reduce emissions of greenhouse gases, and mitigate environmental pollution. However, as the diversity of biomass-derived fuels increases, robust quality assessment methods are essential to ensure their efficiency, safety, and minimal environmental impact. Reflected light microscopy (RLM) is one such technique with the potential to complement conventional physico-chemical analyses by enabling a rapid identification of material constituents and impurities. To refine this methodology and evaluate the reproducibility of solid biomass component identification using RLM, an interlaboratory study (ILS) was conducted. The study involved the recognition of 58 components across 45 photomicrographs, with the participation of 65 scientists and students from 25 countries. The participants faced high difficulty identifying some of the marked components, and as a result, the percentage of correct answers ranged from 19.0 % to 98.3 %, with an average correct identification rate of 62.7 %. The most challenging aspects of the identification process included distinguishing between woody and non-woody (agro) biomass, accurately identifying petroleum-derived materials, and differentiating agro biomass from inorganic matter. The results suggest that while RLM is an important tool for characterizing solid biomass, further development of methodology guidelines and training are necessary to enhance its effectiveness. Future research should prioritize preparing detailed, image-rich, microscopic morphological descriptions of biomass fuel components, which could improve the accuracy and reliability of using RLM in biomass fuel characterization.

International Journal of Coal Geology↗

USGS2024

Atlas of microscopic images of biochar using reflected light microscopy in biochar characterization

Derived through the thermochemical conversion of biomass, biochar is a carbon-rich substance recognized for its significance in environmental applications and sustainable agriculture. As interest in its utilization continues to rise, it becomes crucial to comprehend how the source material and pyrolysis parameters influence the properties of biochar and, consequently, to research the suitability of various analytical methods for characterizing it. Despite the current utilization of numerous physical and chemical methods, the untapped potential of reflected light microscopy warrants further exploration. While a few recent studies suggest a correlation between certain microscopic characteristics and selected physical and chemical properties of biochar, the data are limited and difficult to compare. This is primarily due to variations in the types of original biomass used and lack of information about pyrolysis conditions. Moreover, because only a limited number of photographs taken under a reflected light microscope are publicly available to-date, it is difficult to evaluate morphological differences between various biochars and other organic materials such as inertinites from coal, charcoal, etc. To address limited availability of publicly available data, this “Atlas of Microscopic Images of Biochar” presents a collection of more than 300 images contributed by researchers from Poland, the United States, Canada, Australia, Brazil, and Denmark. These photomicrographs capture optical characteristics of a diverse array of biochar, demonstrating its unique morphological and structural features. This visual documentation can serve as a valuable resource for researchers, industry professionals, educators, and enthusiasts interested in investigating the complexities of biochar forms.

Indiana Journal of Earth Sciences↗

USGS2024

Exploring the uncertainty of machine learning models and geostatistical mapping of rare earth element potential in Indiana coals, USA

Rare earth elements and yttrium (REEs) have a wide range of applications in high- and low-carbon technologies. The strategic significance of REEs has grown due to their expanding applications in manufacturing industries and the constrained availability of these essential resources. This research explores the applicability of machine learning models and their uncertainty for assessing the REE potential in coal beds using various coal parameters as inputs. The work focuses on developing a predictive model based on geological variables, excluding considerations related to potential shifts in the commodities market. The Indiana Coal Quality Database was used as the data source. The promising and unpromising indicators derived from the outlook coefficient of samples from the database were used as the REE potential indicator for machine learning classification models. The filter-based approach with bootstrap was used to evaluate the importance of the coal parameters and their prediction uncertainties. Four machine learning methods (linear discriminant analysis (LDA), random forest (RF), support vector machine (SVM), and artificial neural networks (ANN), a data balancing and augmentation approach (Synthetic Minority Over-sampling Technique), and bootstrap resampling techniques were used for building the models and evaluating their prediction capabilities under uncertainty. It was determined that the SVM bootstrap model with ten-times balanced and augmented data provided superior results compared with other models. Finally, stochastic spatial maps of the REE potential within the coal basin were generated using sequential indicator simulation. The spatial maps of the REE potential showed that a 29% area of the Indiana section of the Illinois coal basin has economic potential of REEs, with 90% confidence.

Indiana↗

USGS2023

Interlaboratory study: Testing reproducibility of solid biofuels component identification using reflected light microscopy

Considering global market trends and concerns about climate change and sustainability, increased biomass use for energy is expected to continue. As more diverse materials are being utilized to manufacture solid biomass fuels, it is critical to implement quality assessment methods to analyze these fuels thoroughly. One such method is reflected light microscopy (RLM), which has the potential to complement and enhance current standard testing, leading to improving fuel quality assessment and, ultimately, preventing avoidable air pollution. An interlaboratory study (ILS) was conducted to test the reproducibility of biomass fuels component identification using a reflected light microscopy technique. The exercise was conducted on thirty photomicrographs showing biomass and various undesired components (like plastics or mineral matter), which were purposely added (by the ILS organizers) to contaminate wood pellets and charcoal-based grilling fuels. Forty-six participants had various levels of difficulty identifying the marked components, and as a result, the percentage of correct answers ranged from 52.2 to 94.4%. Among the most difficult components to distinguish were petroleum products and inorganic matter. Various reasons led to the misidentification, including insufficient morphological descriptions of the components provided to participants, ambiguities of the nomenclature, limitations of the analytical and exercise method, and insufficient experience of the participants. Overall, the results indicate that RLM has the potential to enhance the quality assessment of biomass fuels. However, they also demonstrate that the petrographic classification used in this exercise requires further refinement before it can be standardized. While a new simplified classification of solid biomass fuels components was created as an outcome of this study, future research is necessary to refine the nomenclature, develop a microscopic morphological description of the components, and verify the accuracy of component identification with a follow-up ILS.

International Journal of Coal Geology↗

USGS2022

Machine learning and data augmentation approach for identification of rare earth element potential in Indiana Coals, USA

Rare earth elements and yttrium (REYs) are critical elements and valuable commodities due to their limited availability and high demand in a wide range of applications and especially in high-technology products. The increased demand and geopolitical pressures motivate the search for alternative sources of REYs, and coal, coal waste, and coal ash are considered as new sources for these critical elements. This research evaluates the REY potential of coals from Indiana (USA). However, although coal data revealed REY potential, it suffered from sparse samples with complete REY measurements. Therefore, we explore the applicability of machine learning (ML) models and data augmentation techniques to demonstrate their applicability to evaluate REY potential in Indiana, and other areas in coal basins, using selected coal parameters (Al2O3, Fe2O3, C, Ash, S, P, Mo, Zn, and As contents) as covariates (indicators). Due to the relatively small sample size with complete REY data in the Indiana Coal Database, two data augmentation techniques (Random Over-Sampling Examples and Synthetic Minority Over-Sampling Technique) were used. Four machine learning algorithms (linear discriminate analysis, support vector machine, random forest, and artificial neural networks) were applied for modeling REY potential as a classification problem. The results show that application of Synthetic Minority Over-Sampling Technique prior to development of the support vector machine (SVM) models generated the best REY classification with an accuracy of 95%. The encouraging results based on Indiana coal data may suggest that a similar approach can be used for other coal basins for screening the locations with REY potential. Those locations then can be targeted for more detailed geochemical surveys to identify most promising areas and evaluate overall REY resources.

Indiana↗

USGS2021

Geochemical data for Illinois Basin coal samples, 2015–2018

Researchers at the U.S. Geological Survey (USGS) and their collaborators conducted a study of the geochemical properties of coals currently produced for electric power generation in the Illinois Basin in Illinois and Indiana. The study follows from recommendations by an expert panel for the USGS to investigate the distribution and controls of trace constituents such as mercury (Hg) in Illinois Basin coals and the behavior of these constituents in coal preparation. A total of 72 new samples were collected by USGS collaborators between 2015 and 2017. These samples include raw coals, prepared coals, and waste coals from coal preparation. To understand the geochemistry and cleaning behavior of these coals, these samples were subjected to an integrated series of analyses described here, including microanalysis of coal constituents and bulk sample chemical analysis. Of the procedures used, whole-sample Hg analysis quantified overall mercury contents and its reduction by coal preparation. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) of pyrite in coal quantified Hg and other potentially harmful elements contained in pyrite, the most likely host of these constituents. Trace elements investigated include those whose emissions are regulated under the U.S. Environmental Protection Agency Mercury and Air Toxics Standards. This report and the corresponding data release, serve as an archive for geochemical data obtained in our study of the geochemistry of Illinois Basin coals. Material included in this report also define approaches used by the USGS over the period of study to characterize coal samples, requiring combined use of results from USGS and non-USGS laboratories.

Illinois↗

USGS2020

Testing reproducibility of vitrinite and solid bitumen reflectance measurements in North American unconventional source-rock reservoir petroleum systems

An interlaboratory study (ILS) was conducted to test reproducibility of vitrinite and solid bitumen reflectance measurements in six mudrock samples from United States unconventional source-rock reservoir petroleum systems. Samples selected from the Marcellus, Haynesville, Eagle Ford, Barnett, Bakken and Woodford are representative of resource plays currently under exploitation in North America. All samples are from marine depositional environments, are thermally mature (T max >445 °C) and have moderate to high organic matter content (2.9–11.6 wt% TOC). Their organic matter is dominated by solid bitumen, which contains intraparticle nano-porosity. Visual evaluation of organic nano-porosity (pore sizes < 100 nm) via SEM suggests that intraparticle organic nano-pores are most abundant in dry gas maturity samples and less abundant at lower wet gas/condensate and peak oil maturities. Samples were distributed to ILS participants in forty laboratories in the Americas, Europe, Africa and Australia; thirty-seven independent sets of results were received. Mean vitrinite reflectance (VR o ) values from all ILS participants range from 0.90 to 1.83% whereas mean solid bitumen reflectance (BR o ) values range from 0.85 to 2.04% (no outlying values excluded), confirming the thermally mature nature of all six samples. Using multiple statistical approaches to eliminate outlying values, we evaluated reproducibility limit R, the maximum difference between valid mean reflectance results obtained on the same sample by different operators in different laboratories using different instruments. Removal of outlying values where the individual signed multiple of standard deviation was >1.0 produced lowest R values, generally ≤0.5% (absolute reflectance), similar to a prior ILS for similar samples. Other traditional approaches to outlier removal (outside mean ± 1.5*interquartile range and outside F10 to F90 percentile range) also produced similar R values. Standard deviation values < 0.15*(VR o or BR o ) reduce R and should be a requirement of dispersed organic matter reflectance analysis. After outlier removal, R values were 0.1%–0.2% for peak oil thermal maturity, about 0.3% for wet gas/condensate maturity and 0.4%–0.5% for dry gas maturity. That is, these R values represent the uncertainty (in absolute reflectance) that users of vitrinite and solid bitumen reflectance data should assign to any one individual reported mean reflectance value from a similar thermal maturity mudrock sample. R values of this magnitude indicate a need for further standardization of reflectance measurement of dispersed organic matter. Furthermore, these R values quantify realistic interlaboratory measurement dispersion for a difficult but critically important analytical technique necessary for thermal maturity determination in the source-rock reservoirs of unconventional petroleum systems.

Marine and Petroleum Geology↗

USGS2017

Organic petrology and micro-spectroscopy of Tasmanites microfossils: Applications to kerogen transformations in the early oil window

The transformation of kerogen to hydrocarbons in the early stages of oil generation is critical for understanding the resource potential of liquid-rich shale plays. Organic petrology commonly is used for visual evaluation of type, quality, and thermal maturity of organic matter, but the relationship of visual petrographic changes to chemical transformations is not well characterized. To improve understanding of these processes, organic-walled microfossils of the unicellular green alga Tasmanites (composed of algaenan) in Upper Devonian Ohio Shale (Huron Member, Appalachian Basin) were analyzed by micro-spectroscopy techniques including micro-Fourier transform infrared (micro-FTIR), X-ray photoelectron (XPS), electron probe microanalysis (EPMA), and fluorescence. Immature to mid-oil window maturation sequences of core and outcrop samples with solid bitumen reflectance (BR) and vitrinite reflectance (VR) values ranging from 0.45 to 0.80 %Ro were used. Hydrous pyrolysis was applied to low-maturity (BR: 0.25–0.39 %Ro) Huron and time-correlative New Albany shale samples to create similar artificial maturation sequences for comparison. Micro-FTIR spectroscopy revealed a decrease in the CH 2 /CH 3 ratio with increasing maturity, indicating Tasmanites aliphatic chains become shorter and more branched. Oxygenated functional groups decreased relative to aliphatic stretching bands and increased aromaticity was noted at the highest maturities. In samples that were pyrolyzed for 72 h at temperatures of 300–320 °C (BR: 0.56–0.68 %Ro), Tasmanites showed similar trends, whereas at pyrolysis temperatures of 340 °C and higher (BR > 1.0 %Ro), Tasmanites was pseudomorphed by accumulations of solid bitumen, carbonate and sulfide. Replacement of Tasmanites by these phases in hydrous pyrolysis experiments ≥340 °C and its absence at higher maturities (peak oil, VR and BR ≥ 0.9 %Ro) in naturally matured samples, as documented in a previous study, implies that a large fraction of the algaenan component of original organic carbon is converted to petroleum during thermal maturation. XPS analysis indicated the molar proportion of aliphatic carbon increases with increasing thermal maturity, accompanied by decreases in oxygenated functional groups and olefinic carbon. EPMA of Tasmanites showed highest concentrations of S, with concentrations of redox-sensitive trace elements U, Mo, Ni and V generally at or below detection limits. Decrease in organic S with increasing thermal maturity may be related to cleavage of Tasmanites at C S linkages; however, this relationship was inconsistent and presence of adjacent or entrained nanoscale silicate or sulfide phases may impact measured trace element concentrations. Fluorescence microscopy and spectroscopy showed a red shift in spectral maxima and decreased emission intensities with increasing maturity, interpreted as due to non-radiative energy loss possibly because of increased aromaticity. Collectively, these results provide new insights into the in situ chemical transformations that accompany petrographic changes as oil-prone kerogen converts to petroleum with thermal advance from immature conditions into the mid-oil window.

Organic Geochemistry↗

USGS2015

Microscopical characterization of carbon materials derived from coal and petroleum and their interaction phenomena in making steel electrodes, anodes and cathode blocks for the Microscopy of Carbon Materials Working Group of the ICCP

This paper describes the evaluation of petrographic textures representing the structural organization of the organic matter derived from coal and petroleum and their interaction phenomena in the making of steel electrodes, anodes and cathode blocks. This work represents the results of the Microscopy of Carbon Materials Working Group in Commission III of the International Committee for Coal and Organic Petrology between the years 2009 and 2013. The round robin exercises were run on photomicrograph samples. For textural characterization of carbon materials the existing ASTM classification system for metallurgical coke was applied. These round robin exercises involved 15 active participants from 12 laboratories who were asked to assess the coal and petroleum based carbons and to identify the morphological differences, as optical texture (isotropic/anisotropic), optical type (punctiform, mosaic, fibre, ribbon, domain), and size. Four sets of digital black and white microphotographs comprising 151 photos containing 372 fields of different types of organic matter were examined. Based on the unique ability of carbon to form a wide range of textures, the results showed an increased number of carbon occurrences which have crucial role in the chosen industrial applications. The statistical method used to evaluate the results was based on the “raw agreement indices”. It gave a new and original view on the analysts' opinion by not only counting the correct answers, but also all of the knowledge and experience of the participants. Comparative analyses of the average values of the level of overall agreement performed by each analyst in the exercises during 2009–2013 showed a great homogeneity in the results, the mean value being 90.36%, with a minimum value of 83% and a maximum value of 95%.

International Journal of Coal Geology↗

USGS2015

Standardization of reflectance measurements in dispersed organic matter: results of an exercise to improve interlaboratory agreement

Vitrinite reflectance generally is considered the most robust thermal maturity parameter available for application to hydrocarbon exploration and petroleum system evaluation. However, until 2011 there was no standardized methodology available to provide guidelines for vitrinite reflectance measurements in shale. Efforts to correct this deficiency resulted in publication of ASTM D7708: Standard test method for microscopical determination of the reflectance of vitrinite dispersed in sedimentary rocks . In 2012-2013, an interlaboratory exercise was conducted to establish precision limits for the D7708 measurement technique. Six samples, representing a wide variety of shale, were tested in duplicate by 28 analysts in 22 laboratories from 14 countries. Samples ranged from immature to overmature (0.31-1.53% R o ), from organic-lean to organic-rich (1-22 wt.% total organic carbon), and contained Type I (lacustrine), Type II (marine), and Type III (terrestrial) kerogens. Repeatability limits (maximum difference between valid repetitive results from same operator, same conditions) ranged from 0.03-0.11% absolute reflectance, whereas reproducibility limits (maximum difference between valid results obtained on same test material by different operators, different laboratories) ranged from 0.12-0.54% absolute reflectance. Repeatability and reproducibility limits degraded consistently with increasing maturity and decreasing organic content. However, samples with terrestrial kerogens (Type III) fell off this trend, showing improved levels of reproducibility due to higher vitrinite content and improved ease of identification. Operators did not consistently meet the reporting requirements of the test method, indicating that a common reporting template is required to improve data quality. The most difficult problem encountered was the petrographic distinction of solid bitumens and low-reflecting inert macerals from vitrinite when vitrinite occurred with reflectance ranges overlapping the other components. Discussion among participants suggested this problem could not be easily corrected via kerogen concentration or solvent extraction and is related to operator training and background. No statistical difference in mean reflectance was identified between participants reporting bitumen reflectance vs. vitrinite reflectance vs. a mixture of bitumen and vitrinite reflectance values, suggesting empirical conversion schemes should be treated with caution. Analysis of reproducibility limits obtained during this exercise in comparison to reproducibility limits from historical interlaboratory exercises suggests use of a common methodology (D7708) improves interlaboratory precision. Future work will investigate opportunities to improve reproducibility in high maturity, organic-lean shale varieties.

Marine and Petroleum Geology↗

USGS2014

Petrographic maturity parameters of a Devonian shale maturation series, Appalachian Basin, USA. ICCP Thermal Indices Working Group interlaboratory exercise

This paper presents results of an interlaboratory exercise on organic matter optical maturity parameters using a natural maturation series comprised by three Devonian shale samples (Huron Member, Ohio Shale) from the Appalachian Basin, USA. This work was conducted by the Thermal Indices Working Group of the International Committee for Coal and Organic Petrology (ICCP) Commission II (Geological Applications of Organic Petrology). This study aimed to compare: 1. maturation predicted by different types of petrographic parameters (vitrinite reflectance and spectral fluorescence of telalginite), 2. reproducibility of the results for these maturation parameters obtained by different laboratories, and 3. improvements in the spectral fluorescence measurement obtained using modern detection systems in comparison with the results from historical round robin exercises. Mean random vitrinite reflectance measurements presented the highest level of reproducibility (group standard deviation 0.05) for low maturity and reproducibility diminished with increasing maturation (group standard deviation 0.12). Corrected fluorescence spectra, provided by 14 participants, showed a fair to good correspondence. Standard deviation of the mean values for spectral parameters was lowest for the low maturity sample but was also fairly low for higher maturity samples. A significant improvement in the reproducibility of corrected spectral fluorescence curves was obtained in the current exercise compared to a previous investigation of Toarcian organic matter spectra in a maturation series from the Paris Basin. This improvement is demonstrated by lower values of standard deviation and is interpreted to reflect better performance of newer photo-optical measuring systems. Fluorescence parameters measured here are in good agreement with vitrinite reflectance values for the least mature shale but indicate higher maturity than shown by vitrinite reflectance for the two more mature shales. This red shift in λ max beyond 0.65% vitrinite reflectance was also observed in studies of Devonian shale in other basins, suggesting that the accepted correlation for these two petrographic thermal maturity parameters needs to be re-evaluated. A good linear correlation between λ max and T max for this maturation series was observed and λ max 600 nm corresponds to T max of 440 °C. Nevertheless if a larger set of Devonian samples is included, the correlation is polynomial with a jump in λ max ranging from 540 to 570 nm. Up to 440 °C of T max , the λ max , mostly, reaches up to 500 nm; beyond a T max of 440 °C, λ max is in the range of 580–600 nm. This relationship places the “red shift” when the onset of the oil window is reached at T max of 440 °C. Moreover, the correlation between HI and λ max (r 2 = 0.70) shows a striking inflection and decrease in HI above a λ max of 600 nm, coincident with the approximate onset of hydrocarbon generation in these rocks.

International Journal of Coal Geology↗

USGS2012

Compression map, functional groups and fossilization: A chemometric approach (Pennsylvanian neuropteroid foliage, Canada)

Nearly all of the spectrochemical studies involving Carboniferous foliage of seed-ferns are based on a limited number of pinnules, mainly compressions. In contrast, in this paper we illustrate working with a larger pinnate segment, i.e., a 22-cm long neuropteroid specimen, compression-preserved with cuticle, the compression map. The objective is to study preservation variability on a larger scale, where observation of transparency/opacity of constituent pinnules is used as a first approximation for assessing the degree of pinnule coalification/fossilization. Spectrochemical methods by Fourier transform infrared spectrometry furnish semi-quantitative data for principal component analysis. The compression map shows a high degree of preservation variability, which ranges from comparatively more coalified pinnules to less coalified pinnules that resemble fossilized-cuticles, noting that the pinnule midveins are preserved more like fossilized-cuticles. A general overall trend of coalified pinnules towards fossilized-cuticles, i.e., variable chemistry, is inferred from the semi-quantitative FTIR data as higher contents of aromatic compounds occur in the visually more opaque upper location of the compression map. The latter also shows a higher condensation of the aromatic nuclei along with some variation in both ring size and degree of aromatic substitution. From principal component analysis we infer correspondence between transparency/opacity observation and chemical information which correlate with varying degree to fossilization/coalification among pinnules.

Nova Scotia↗

USGS2012

Organic geochemistry and petrology of subsurface Paleocene-Eocene Wilcox and Claiborne Group coal beds, Zavala County, Maverick Basin, Texas, USA

Coal samples from a coalbed methane exploration well in northern Zavala County, Maverick Basin, Texas, were characterized through an integrated analytical program. The well was drilled in February, 2006 and shut in after coal core desorption indicated negligible gas content. Cuttings samples from two levels in the Eocene Claiborne Group were evaluated by way of petrographic techniques and Rock–Eval pyrolysis. Core samples from the Paleocene–Eocene Indio Formation (Wilcox Group) were characterized via proximate–ultimate analysis in addition to petrography and pyrolysis. Two Indio Formation coal samples were selected for detailed evaluation via gas chromatography, and Fourier transform infrared (FTIR) and 13 C CPMAS NMR spectroscopy. Samples are subbituminous rank as determined from multiple thermal maturity parameters. Elevated rank (relative to similar age coal beds elsewhere in the Gulf Coast Basin) in the study area is interpreted to be a result of stratigraphic and/or structural thickening related to Laramide compression and construction of the Sierra Madre Oriental to the southwest. Vitrinite reflectance data, along with extant data, suggest the presence of an erosional unconformity or change in regional heat flow between the Cretaceous and Tertiary sections and erosion of up to >5 km over the Cretaceous. The presence of liptinite-rich coals in the Claiborne at the well site may indicate moderately persistent or recurring coal-forming paleoenvironments, interpreted as perennially submerged peat in shallow ephemeral lakes with herbaceous and/or flotant vegetation. However, significant continuity of individual Eocene coal beds in the subsurface is not suggested. Indio Formation coal samples contain abundant telovitrinite interpreted to be preserved from arborescent, above-ground woody vegetation that developed during the middle portion of mire development in forested swamps. Other petrographic criteria suggest enhanced biological, chemical and physical degradation at the beginning and end of Indio mire development. Fluorescence spectra of sporinite and resinite are consistent and distinctly different from each other, attributed to the presence of a greater proportion of complex asphaltene and polar molecules in resinite. Gas chromatography of resinite-rich coal shows sesquiterpenoid and diterpenoid peaks in the C 14–17 range, which are not present in resinite-poor coal. Quantities of extracts suggest bitumen concentration below the threshold for effective source rocks [30–50 mg hydrocarbon/g total organic carbon (HC/g TOC)]. Saturate/aromatic and pristane/phytane (Pr/Ph) ratios are different from values for nearby Tertiary-reservoired crude oil, suggesting that the Indio coals are too immature to source liquid hydrocarbons in the area. However, moderately high HI values (200–400 mg HC/g rock) may suggest some potential for naphthenic–paraffinic oil generation where buried more deeply down stratigraphic/structural dip. Extractable phenols and C 20+ alkanes are suggested as possible intermediates for acetate fermentation in microbial methanogenesis which may, however, be limited by poor nutrient supply related to low rainfall and meteoric recharge rate or high local sulfate concentration.

Texas↗

USGS2011

Mercury capture by selected Bulgarian fly ashes: Influence of coal rank and fly ash carbon pore structure on capture efficiency

Mercury capture by fly ash C was investigated at five lignite- and subbituminous-coal-burning Bulgarian power plants (Republika, Bobov Dol, Maritza East 2, Maritza East 3, and Sliven). Although the C content of the ashes is low, never exceeding 1.6%, the Hg capture on a unit C basis demonstrates that the low-rank-coal-derived fly ash carbons are more efficient in capturing Hg than fly ash carbons from bituminous-fired power plants. While some low-C and low-Hg fly ashes do not reveal any trends of Hg versus C, the 2nd and, in particular, the 3rd electrostatic precipitator (ESP) rows at the Republika power plant do have sufficient fly ash C range and experience flue gas sufficiently cool to capture measurable amounts of Hg. The Republika 3rd ESP row exhibits an increase in Hg with increasing C, as observed in other power plants, for example, in Kentucky power plants burning Appalachian-sourced bituminous coals. Mercury/C decreases with an increase in fly ash C, suggesting that some of the C is isolated from the flue gas stream and does not contribute to Hg capture. Mercury capture increases with an increase in Brunauer-Emmett-Teller (BET) surface area and micropore surface area. The differences in Hg capture between the Bulgarian plants burning low-rank coal and high volatile bituminous-fed Kentucky power plants suggests that the variations in C forms resulting from the combustion of the different ranks also influence the efficiency of Hg capture. ?? 2010 Elsevier Ltd.

Applied Geochemistry↗

USGS2011

Reply to Effect of concentration of organic matter on optical maturity parameters. Interlaboratory results of the organic matter concentration working group of the ICCP. Discussion by Vinay K. Sahay

This reply is motivated by Sahay's comments on the paper published by Mendonça Filho et al. (2010) dealing with the effect of concentration of an organic matter on optical maturity parameters. Four points were raised by Sahay: suggestion to use of chemical parameters to assess the effect of isolation, indication that suppression of vitrinite reflectance in liptinite-rich rocks was insufficiently addressed, discussion on the way to deal with the existence of multiple vitrinite populations in a dispersed organic matter, and contradictory explanation of results involving the influence of isolation procedure on fluorescence properties but no effect on vitrinite reflectance. The four points were separately addressed being the two first ones out of the scope of the paper. The existence of multiple vitrinite populations is a well-recognized problem whose importance in the results could be addressed because the participants provided individual records of vitrinite reflectance. These results indicated that election of different populations was not a major problem in the results. The influence of isolation procedure on the fluorescence spectra of alginite while the vitrinite reflectance remains unaltered is not considered contradictory because both parameters are measured on different components which may have a different response to the acid treatment.

International Journal of Coal Geology↗

USGS2011

Chemical structures of coal lithotypes before and after CO2 adsorption as investigated by advanced solid-state 13C 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 13 C 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 CO 2 adsorption isotherm analysis were also analyzed to determine possible changes in coal structure as a result of CO 2 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 CO 2 saturation. After exposure to high pressure CO 2 , 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-CO 2 adsorption samples compared to the original lithotypes. These observations suggested chemical CO 2 –coal interactions at high pressure and the selectivity of lithotypes in response to CO 2 adsorption.

International Journal of Coal Geology↗

USGS2011

Biogeochemistry of microbial coal-bed methane

Microbial methane accumulations have been discovered in multiple coal-bearing basins over the past two decades. Such discoveries were originally based on unique biogenic signatures in the stable isotopic composition of methane and carbon dioxide. Basins with microbial methane contain either low-maturity coals with predominantly microbial methane gas or uplifted coals containing older, thermogenic gas mixed with more recently produced microbial methane. Recent advances in genomics have allowed further evaluation of the source of microbial methane, through the use of high-throughput phylogenetic sequencing and fluorescent in situ hybridization, to describe the diversity and abundance of bacteria and methanogenic archaea in these subsurface formations. However, the anaerobic metabolism of the bacteria breaking coal down to methanogenic substrates, the likely rate-limiting step in biogenic gas production, is not fully understood. Coal molecules are more recalcitrant to biodegradation with increasing thermal maturity, and progress has been made in identifying some of the enzymes involved in the anaerobic degradation of these recalcitrant organic molecules using metagenomic studies and culture enrichments. In recent years, researchers have attempted lab and subsurface stimulation of the naturally slow process of methanogenic degradation of coal.

Annual Review of Earth and Planetary Sciences↗

USGS2011

Mercury in coals and fly ashes from Republika and Bobov dol thermoelectric power plants

Feed coal and y ash samples were collected at Republika and Bobov Dol thermoelectric power plants (TPPs). The y ashes (FAs) were collected fromthree rows of the hot-side electrostatic precipitators (ESPs) array. Each sam- ple was wet-screened at 100, 200, 325 and 500 mesh. The coals and y ashes were characterized with regard to their petrological and chemical composition (including mercury content) and to their surface area properties. The calculated enrichment factor (EF) shows that the Hg concentrations in the bulk coal samples from Republika and Bobov Dol TPPs are 2.19 and 1.41, respectively. In some coal size fractions the EF can be up to 4 times higher than the Clarke value. The calculated EF for fly ashes shows that the Hg concentrations in the bulk samples studied are lower (between 0.03 and 0.32) than the Clarke value. The most enriched in Hg are the fly ashes from the 3rd ESP row of Republika TPP. The Hg distribution in bulk FAs taken from dierent rows of the electrostatic precipitators of both TPPs studied shows well established tendency of gradual increase in the Hg content from the 1st to the 2nd and 3rd ESP rows. The correlation between Hg content and surface area, mesopore and micropore volume of y ashes was also done in the present investigation.

Comptes Rendus de L'Academie Bulgare des Sciences↗