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Effect of surface area and chemisorbed oxygen on the SO2 adsorption capacity of activated char
The objective of this study was to determine whether activated char produced from Illinois coal could be used effectively to remove sulfur dioxide from coal combustion flue gas. Chars were prepared from a high-volatile Illinois bituminous coal under a wide range of pyrolysis and activation conditions. A novel char preparation technique was developed to prepare chars with SO2 adsorption capacities significantly greater than that of a commercial activated carbon. In general, there was no correlation between SO2 adsorption capacity and surface area. Temperature-programmed desorption (TPD) was used to determine the nature and extent of carbon-oxygen (C-O) complexes formed on the char surface. TPD data revealed that SO2 adsorption was inversely proportional to the amount of C-O complex. The formation of a stable C-O complex during char preparation may have served only to occupy carbon sites that were otherwise reactive towards SO2 adsorption. A fleeting C(O) complex formed during SO2 adsorption is postulated to be the reaction intermediate necessary for conversion of SO2 to H2SO4. Copyright ?? 1996 Elsevier Science Ltd.
Modes of occurrence of potentially hazardous elements in coal: Levels of confidence
The modes of occurrence of the potentially hazardous elements in coal will be of significance in any attempt to reduce their mobilization due to coal combustion. Antimony and selenium may be present in solid solution in pyrite, as minute accessory sulfides dispersed throughout the organic matrix, or in organic association. Because of these modes of occurrence it is anticipated that less than 50% of these elements will be routinely removed by conventional coal cleaning procedures. Arsenic and mercury occur primarily in late-stage coarse-grained pyrite therefore physical coal cleaning procedures should be successful in removing substantial proportions of these elements. Cadmium occurs in sphalerite and lead in galena. Both of these minerals exhibit a wide range of particle sizes and textural relations. Depending on the particle size and textural relations, physical coal cleaning may remove as little as 25% of these elements or as much as 75%. Manganese in bituminous coal occurs in carbonates, especially siderite. Physical coal cleaning should remove a substantial proportion of this element. More information is needed to elucidate the modes of occurrence of beryllium, chromium, cobalt, and nickel.
Petrography and geochemistry of the Middle Devonian coal from Luquan, Yunnan Province, China
Coals from Luquan, Yunnan Province, China, have high contents of cutinite and microsporinite, with an average of 55 and 33.5 vol%, respectively, (on a mineral-free basis). The coals are classified as cutinitic liptobiolith, sporinite-rich durain, cutinite-rich durain, and sporinitic liptobiolith. These four liptinite-rich coals are often interlayered within the coal bed section and vary transversely within the coal bed. The vitrinite content varies from as low as 1.6-20.5% (mineral-free basis), and it is dominated by collodetrinite, collotelinite, and corpogelinite. The maceral composition may be attributed to the type of the peat-forming plant communities. Moreover, the Luquan coals are characterized by high contents of volatile matter, hydrogen, and oxygen, and the high values of the atomic hydrogen to carbon ratio as a result of the maceral composition. As compared with the common Chinese coals and the upper continental crust, the Luquan coals are enriched in Li, B, Cu, Ga, Se, Rb, Mo, Ba, Pb, Bi, and U, with averages of 99.9, 250, 111, 24.4, 4.55, 130, 58.8, 1276, 162, 3.85, and 34.1 ??g/g, respectively. The SEM-EDX results show that V, Cr, Ga, and Rb occur mainly in clay minerals, and Cu and Pb are associated with clay minerals and pyrite, and Mo and U are mainly in clay minerals and organic matter. Barite and clay minerals are the main carrier of barium. The high B and U contents are probably resulted from deep seawater influence during coal formation. ?? 2005 Elsevier Ltd. All rights reserved.
Concentration and distribution of sixty-one elements in coals from DPR Korea
Fifty coal samples (28 anthracite and 22 lignites) were collected from both main and small coal mines in DPR Korea prioritized by resource distribution and coal production. The concentrations of 61 elements in 50 coal samples were determined by several multielement and element-specific techniques, including inductively coupled plasma atomic emission spectrometry (ICP-AES), and inductively coupled plasma mass spectrometry (ICP-MS), ion chromatogram (IC), cold-vapor atomic absorption spectrometry (CV-AAS), and hydride generation atomic absorption spectrometry (HGAAS). The ranges, arithmetic means and geometric means of concentrations of these elements are presented. A comparison with crustal abundances (Clarke values) shows that some potentially hazardous elements in the coals of DPR Korea are highly enriched Li, B, S, Cl, Zn, As, Se, Cd, Sn, Sb, W, Te, Hg, Ag, Pb, and La, Ce, Dy, Tm, Ge, Mo, Cs, Tl, Bi, Th and U are moderately enriched. A comparison of ranges and means of elemental concentrations in DPR Korea, Chinese, and world coals shows the ranges of most elements in DPR Korea coals are very close to the ranges of world coals. Arithmetic means of most elements in DPR Korea coals are close to that of American coals. Most elements arithmetic means are higher in Jurassic and Paleogene coals than coals of other ages. In DPR Korea coals, only seven elements in early Permian coals are higher than other periods: Li, Zn, Se, Cd, Hg, Pb, and Bi. Only five elements B, As, Sr, Mo, W in Neogene coals have arithmetic means higher than others. SiO2 and Al2O 3 in ashes are more than 70% except six samples. The correlation between ash yields and major elements from high to low is in the order of Si>Al>Ti>K>Mg>Fe>Na>Ca>P>S. Most elements have high positive correlation with ash (r>0.5) and show high inorganic affinity. ?? 2005 Elsevier Ltd. All rights reserved.
Mode of occurrence of arsenic in feed coal and its derivative fly ash, Black Warrior Basin, Alabama
An arsenic-rich (As = 55 ppm) bituminous feed coal from the Black Warrior Basin, Alabama and its derivative fly ash (As = 230 ppm) were selected for detailed investigation of arsenic residence and chemical forms. Analytical techniques included microbeam analysis, selective extraction, and As K-edge X-ray absorption fine-structure (XAFS) spectroscopy. Most As in the coal is contained in a generation of As-bearing pyrite (FeS2) that formed in response to epigenetic introduction of hydrothermal fluids. XAFS results indicate that approximately 50% of the As in the coal sample occurs as the oxidized As(V) species, possibly the result of incipient oxidation of coal and pyrite prior to our analysis. Combustion of pyrite and host coal produced fly ash in which 95% of As is present as As(V). Selective extraction of the fly ash with a carbonate buffer solution (pH = 10) removed 49% of the As. A different extraction with an HCl-NH2OH mixture, which targets amorphous and poorly crystalline iron oxides, dissolved 79% of the As. XAFS spectroscopy of this highly acidic (pH = 3.0) fly ash indicated that As is associated with some combination of iron oxide, oxyhydroxide, or sulfate. In contrast, a highly alkaline (pH = 12.7) fly ash from Turkey shows most As associated with a phase similar to calcium orthoarsenate (Ca3(AsO4)2). The combined XAFS results indicate that fly ash acidity, which is determined by coal composition and combustion conditions, may serve to predict arsenic speciation in fly ash.
An analytical model of the mechanical properties of bulk coal under confined stress
This paper presents the development of an analytical model which can be used to relate the structural parameters of coal to its mechanical properties such as elastic modulus and Poisson's ratio under a confined stress condition. This model is developed primarily to support process modeling of coalbed methane (CBM) or CO2-enhanced CBM (ECBM) recovery from coal seam. It applied an innovative approach by which stresses acting on and strains occurring in coal are successively combined in rectangular coordinates, leading to the aggregated mechanical constants. These mechanical properties represent important information for improving CBM/ECBM simulations and incorporating within these considerations of directional permeability. The model, consisting of constitutive equations which implement a mechanically consistent stress-strains correlation, can be used as a generalized tool to study the mechanical and fluid behaviors of coal composites. An example using the model to predict the stress-strain correlation of coal under triaxial confined stress by accounting for the elastic and brittle (non-elastic) deformations is discussed. The result shows a good agreement between the prediction and the experimental measurement. ?? 2007 Elsevier Ltd. All rights reserved.
Thermal maturity of northern Appalachian Basin Devonian shales: Insights from sterane and terpane biomarkers
To better estimate thermal maturity of Devonian shales in the northern Appalachian Basin, eleven samples of Marcellus and Huron Shale were characterized via multiple analytical techniques. Vitrinite reflectance, Rock–Eval pyrolysis, gas chromatography (GC) of whole rock extracts, and GC–mass spectrometry (GCMS) of extract saturate fractions were evaluated on three transects that lie across previously documented regional thermal maturity isolines. Results from vitrinite reflectance suggest that most samples are immature with respect to hydrocarbon generation. However, bulk geochemical data and sterane and terpane biomarker ratios from GCMS suggest that almost all samples are in the oil window. This observation is consistent with the presence of thermogenic gas in the study area and higher vitrinite reflectance values recorded from overlying Pennsylvanian coals. These results suggest that vitrinite reflectance is a poor predictor of thermal maturity in early mature areas of Devonian shale, perhaps because reported measurements often include determinations of solid bitumen reflectance. Vitrinite reflectance interpretations in areas of early mature Devonian shale should be supplanted by evaluation of thermal maturity information from biomarker ratios and bulk geochemical data.
Molecular-level characterization of crude oil compounds combining reversed-phase high-performance liquid chromatography with off-line high-resolution mass spectrometry
A reversed-phase separation technique was developed in a previous study (Loegel et al., 2012) and successfully applied to the de-asphalted fraction of crude oil. However, to the best of our knowledge, the molecular-level characterization of oil fractions obtained by reversed-phase high-performance liquid chromatography (HPLC) coupled with high-resolution mass spectrometry (MS) has not yet been reported. A detailed characterization of the oil fractions prepared by reversed-phase HPLC was performed in this study. HPLC fractionation was carried out on conventional crude oil and an oil shale pyrolysate. The analyses of the fractions showed that the carbon number of alkyl chains and the double bond equivalent (DBE) value were the major factors determining elution order. The compounds with larger DBE (presumably more condensed aromatic structures) and smaller carbon number (presumably compounds with short side chains) were eluted earlier but those compounds with lower DBE values (presumably less aromatic structures) and higher carbon number (presumably compounds with longer alkyl chains) eluted later in the chromatograms. This separation behavior is in good agreement with that expected from the principles of reversed-phase separation. The data presented in this study show that reversed-phase chromatography is effective in separating crude oil compounds and can be combined with ultrahigh-resolution MS data to better understand natural oils and oil shale pyrolysates.
Thermal maturity of Tasmanites microfossils from confocal laser scanning fluorescence microscopy
We report here, for the first time, spectral properties of Tasmanites microfossils determined by confocal laser scanning fluorescence microscopy (CLSM, using Ar 458 nm excitation). The Tasmanites occur in a well-characterized natural maturation sequence ( R o 0.48–0.74%) of Devonian shale ( n = 3 samples) from the Appalachian Basin. Spectral property λ max shows excellent agreement ( r 2 = 0.99) with extant spectra from interlaboratory studies which used conventional fluorescence microscopy techniques. This result suggests spectral measurements from CLSM can be used to infer thermal maturity of fluorescent organic materials in geologic samples. Spectra of regions with high fluorescence intensity at fold apices and flanks in individual Tasmanites are blue-shifted relative to less-deformed areas in the same body that have lower fluorescence intensity. This is interpreted to result from decreased quenching moiety concentration at these locations, and indicates caution is needed in the selection of measurement regions in conventional fluorescence microscopy, where it is common practice to select high intensity regions for improved signal intensity and better signal to noise ratios. This study also documents application of CLSM to microstructural characterization of Tasmanites microfossils. Finally, based on an extant empirical relation between conventional λ max values and bitumen reflectance, λ max values from CLSM of Tasmanites microfossils can be used to calculate a bitumen reflectance equivalent value. The results presented herein can be used as a basis to broaden the future application of CLSM in the geological sciences into hydrocarbon prospecting and basin analysis.
Stochastic reservoir simulation for the modeling of uncertainty in coal seam degasification
Coal seam degasification improves coal mine safety by reducing the gas content of coal seams and also by generating added value as an energy source. Coal seam reservoir simulation is one of the most effective ways to help with these two main objectives. As in all modeling and simulation studies, how the reservoir is defined and whether observed productions can be predicted are important considerations. Using geostatistical realizations as spatial maps of different coal reservoir properties is a more realistic approach than assuming uniform properties across the field. In fact, this approach can help with simultaneous history matching of multiple wellbores to enhance the confidence in spatial models of different coal properties that are pertinent to degasification. The problem that still remains is the uncertainty in geostatistical simulations originating from the partial sampling of the seam that does not properly reflect the stochastic nature of coal property realizations. Stochastic simulations and using individual realizations, rather than E-type, make evaluation of uncertainty possible. This work is an advancement over Karacan et al. (2014) in the sense of assessing uncertainty that stems from geostatistical maps. In this work, we batched 100 individual realizations of 10 coal properties that were randomly generated to create 100 bundles and used them in 100 separate coal seam reservoir simulations for simultaneous history matching. We then evaluated the history matching errors for each bundle and defined the single set of realizations that would minimize the error for all wells. We further compared the errors with those of E-type and the average realization of the best matches. Unlike in Karacan et al. (2014), which used E-type maps and average of quantile maps, using these 100 bundles created 100 different history match results from separate simulations, and distributions of results for in-place gas quantity, for example, from which uncertainty in coal property realizations could be evaluated. The study helped to determine the realization bundle that consisted of the spatial maps of coal properties, which resulted in minimum error. In addition, it was shown that both E-type and the average of realizations that gave the best match for invidual approximated the same properties resonably. Moreover, the determined realization bundle showed that the study field initially had 151.5 million m 3 (cubic meter) of gas and 1.04 million m 3 water in the coal, corresponding to Q90 of the entire range of probability for gas and close to Q75 for water. In 2013, in-place fluid amounts decreased to 138.9 million m 3 and 0.997 million m 3 for gas and water, respectively.
Type and amount of organic amendments affect enhanced biogenic methane production from coal and microbial community structure
Slow rates of coal-to-methane conversion limit biogenic methane production from coalbeds. This study demonstrates that rates of coal-to-methane conversion can be increased by the addition of small amounts of organic amendments. Algae, cyanobacteria, yeast cells, and granulated yeast extract were tested at two concentrations (0.1 and 0.5 g/L), and similar increases in total methane produced and methane production rates were observed for all amendments at a given concentration. In 0.1 g/L amended systems, the amount of carbon converted to methane minus the amount produced in coal only systems exceeded the amount of carbon added in the form of amendment, suggesting enhanced coal-to-methane conversion through amendment addition. The amount of methane produced in the 0.5 g/L amended systems did not exceed the amount of carbon added. While the archaeal communities did not vary significantly, the bacterial populations appeared to be strongly influenced by the presence of coal when 0.1 g/L of amendment was added; at an amendment concentration of 0.5 g/L the bacterial community composition appeared to be affected most strongly by the amendment type. Overall, the results suggest that small amounts of amendment are not only sufficient but possibly advantageous if faster in situ coal-to-methane production is to be promoted.
Evolution of sulfur speciation in bitumen through hydrous pyrolysis induced thermal maturation of Jordanian Ghareb Formation oil shale
Previous studies on the distribution of bulk sulfur species in bitumen before and after artificial thermal maturation using various pyrolysis methods have indicated that the quantities of reactive (sulfide, sulfoxide) and thermally stable (thiophene) sulfur moieties change following consistent trends under increasing thermal stress. These trends show that sulfur distributions change during maturation in ways that are similar to those of carbon, most clearly illustrated by the increase in aromatic sulfur (thiophenic) as a function of thermal maturity. In this study, we have examined the sulfur moiety distributions of retained bitumen from a set of pre- and post-pyrolysis rock samples in an organic sulfur-rich, calcareous oil shale from the Upper Cretaceous Ghareb Formation. Samples collected from outcrop in Jordan were subjected to hydrous pyrolysis (HP). Sulfur speciation in extracted bitumens was examined using K-edge X-ray absorption near-edge structure (XANES) spectroscopy. The most substantial changes in sulfur distribution occurred at temperatures up to the point of maximum bitumen generation (∼300 °C) as determined from comparison of the total organic carbon content for samples before and after extraction. Organic sulfide in bitumen decreased with increasing temperature at relativ ely low thermal stress (200–300 °C) and was not detected in extracts from rocks subjected to HP at temperatures above around 300 °C. Sulfoxide content increased between 200 and 280 °C, but decreased at higher temperatures. The concentration of thiophenic sulfur increased up to 300 °C, and remained essentially stable under increasing thermal stress (mg-S/g-bitumen basis). The ratio of stable-to-reactive+stable sulfur moieties ([thiophene/(sulfide+sulfoxide+thiophene)], T/SST) followed a sigmoidal trend with HP temperature, increasing slightly up to 240 °C, followed by a substantial increase between 240 and 320 °C, and approaching a constant value (∼0.95) at temperatures above 320 °C. This sulfur moiety ratio appears to provide complementary thermal maturity information to geochemical parameters derived from other analyses of extracted source rocks.
Quantitative evaluation of vitrinite reflectance and atomic O/C in coal using Raman spectroscopy and multivariate analysis
Vitrinite reflectance (VRo) is a standard petrographic method for assessing thermal maturity (rank) of coal. The vitrinite reflectance technique, however, requires significant petrographic experience, can be time-consuming, and may be biased by analyst subjectivity. Correlations between coal rank and Raman spectral properties are a promising alternative that can supplant some of the limitations inherent in the VRo protocol. The traditional peak-fitting methodologies for quantifying metrics from Raman spectra, however, also suffer from analyst subjectivity that can affect correlations between analyte and spectral properties. This research combines high-throughput Raman spectroscopy with multivariate analysis (MVA) to create calibration models for the prediction of coal rank though VRo and atomic O/C ratio. MVA techniques eliminate the ambiguous subjectivity prevalent in peak-fitting methods by evaluating the full Raman spectrum, then identifying the integral vibrational modes for constructing accurate models. Partial least squares (PLS) regression models were developed using Raman spectra and VRo values (0.23–5.23%) for 68 geographically diverse coal samples. The calibration set was validated using one-half of the samples to rigorously assess the model’s predictive accuracy. The root mean standard error of prediction was 0.19 for the VRo model and 0.014 for the atomic O/C model. Both models exhibited linear correlations, with coefficients of determination ( R 2 ) for the validation set of 0.99 (VRo) and 0.93 (atomic O/C), despite the geographic and rank diversity of the samples. This study demonstrates the applicability and power of using PLS models for the prediction of both the VRo and atomic O/C ratio from Raman spectra. The quantitative MVA protocol contained herein provides a Raman alternative to the VRo industry benchmark for coal rank that is not subject to the limitations and subjectivity of peak-fitting methods.
Quantitative evaluation of vitrinite reflectance in shale using Raman spectroscopy and multivariate analysis
The current research builds upon a previously published study that demonstrated the combination of Raman spectroscopy coupled with multivariate analysis (MVA) for the prediction of thermal maturity in coal by evaluating the efficacy of this method for the prediction of thermal maturity in shale. MVA techniques eliminate analyst bias in peak-fitting methods by using the full Raman spectrum, and then extricating the important spectral regions for distinguishing samples and building accurate, robust models. Partial least squares (PLS) regression models were developed using Raman spectra and VRo values (0.58–4.59%) for 53 geographically diverse shale chip samples, and 43 shale powder samples. Separate PLS models were built using Raman spectra from shale chips or powders. The calibration sets were validated using approximately one-third of the samples to rigorously assess the predictive accuracy of the models. The root mean standard error of prediction was 0.24 for the shale chip model, and 0.28 for the shale powder model. The coefficients of determination ( R 2 ) for the cross-validated data sets were identical (0.90, chips; 0.90, powders), revealing a strong linearity despite the geographic and age diversity of the samples. This study demonstrates the validity of using PLS models for the prediction of shale VRo from Raman spectra. The MVA method described herein presents a Raman alternative to the VRo industry benchmark for assessing thermal maturity in shale that is not imperiled by the shortcomings and subjectivity of peak-fitting methods.
Biogenic coal-to-methane conversion can be enhanced with small additions of algal amendment in field-relevant upflow column reactors
ubsurface coal environments, where biogenic coal-to-methane conversion occurs, are difficult to access, resulting in inherent challenges and expenses for in situ experiments. Previous batch reactor studies provided insights into specific processes, pathways, kinetics, and engineering strategies, but field-relevance is restricted due to limited substrate availability or byproduct accumulation that may influence reactions or metabolisms. In this study, continuous-flow column reactors were used to overcome some batch limitations, improve the understanding of in situ conditions, and increase field-relevance for subsurface engineering technology development. The bench-scale reactor system was constructed to investigate the addition of algal amendment for enhancing microbial coal-to-methane conversion previously developed in batch systems. Four reactor columns were packed with coal and inoculated with a microbial consortium from the same Flowers-Goodale coal bed. Two reactors were amended with 13 C-labeled algal amendment on day 0, and two were unamended. On day 61, one previously amended and one previously unamended reactor were re-amended. Produced gases were captured in a gas trap, and CH 4 and CO 2 were quantified. The reactor amended twice produced 1712.6 µmol CH 4 (4.6% as 13 CH 4 ). The reactor amended only on day 0 produced 1485.5 µmol CH 4 (2.6% as 13 CH 4 ). The reactor amended only on day 61 produced 278.9 µmol CH 4 (3.9% as 13 CH 4 ). The reactor with no amendment produced no measurable gases for the duration of the 172-day experiment. Amendment increased the rate of coal-to-methane conversion and total gas production; most of the produced gases were due to coal conversion with only small contributions (<7%) from amendment conversion.
Petrology and geochemistry of migrated hydrocarbons associated with the Albert Formation oil shale in New Brunswick, Canada
Samples of the Carboniferous oil shale of the Albert Formation in New Brunswick, Canada, were examined using reflected white and fluorescence light microscopy, Rock-Eval pyrolysis, and ICP-MS (for elements). The presence of fractured filled solid bitumen in contact with, and within the Albert Formation oil shale, particularly in fractures at the right angle to the bedding of oil shale indicated that migrated oil had enough force to overcome the tensil strength of oil shale matrix, and penetrating the oil shale. Migrating fluid also caused thermal alteration of the oil shale matrix, as evident by the presence primary bitumen and oil droplets. The evidence of oil migration included the presence of solid bitumen and crystalline carbonates in contact with the immature oil shale. The low permeability oil shale acted as a seal/aquitard and created a diagenetic ‘front’ by reducing/slowing the advance of migrating oil, resulting in the formation of a reaction zone. Oil droplets were found in this reaction zone. Albertite was the only solid bitumen reported in the Albert Mine area previously. However, the present study found that migrated solid bitumen consisted of both soluble solid bitumen types such as gilsonite and glance-pitch, and non-soluble solid bitumen such as wurtzilite and albertite. The high hydrocarbon yield of oil shales in the Albert Mine area was due to the presence of various solid bitumen types associated with the oil shale and possibly slight thermal alteration that the oil shale experienced when it came in contact with migrating oil. The variation of Th/K ratio and TOC (wt%) indicates that most of oil shales from the Albert Mine area and within the vicinity of oil migration have higher content of TOC (17-25 wt%) as compared to the other Albert oil shales ( TOC=<10 %). The oil shales examined in this study were immature to marginally mature and had a wide range of hydrocarbon yield (2-213 L/Tonne). The highest hydrocarbon yield range (66-199 L/Tonne) was associated with oil shale outcrop samples collected in the Albert Mine itself, where the oil shale was heavily impregnated by migrated solid bitumen.
Investigating the effects of broad ion beam milling to sedimentary organic matter: Surface flattening or heat-induced aromatization and condensation?
Previous work has proposed transfer of kinetic heat energy from low-energy broad ion beam (BIB) milling causes thermal alteration of sedimentary organic matter, resulting in increases of organic matter reflectance. Whereas, other studies have suggested the organic matter reflectance increase from BIB milling is due to decreased surface roughness. To test if reflectance increases to sedimentary organic matter (vitrinite) caused by BIB milling were related to molecular aromatization and condensation, Raman and Fourier transform infrared (FTIR) spectroscopies were used to evaluate potential compositional changes in the same vitrinite locations pre- and post-BIB milling. The same locations also were examined by atomic force microscopy (AFM) to determine topographic changes caused by BIB milling (as quantified by the areal root-mean-square roughness parameter S q ). Samples consisted of four medium volatile bituminous coals. A non-aggressive BIB milling approach was used with conditions of 5 min, 4 keV, 15°incline, 360° rotation at 25 rpm and 100% focus (1.5 kV discharge; ∼100 μA). This gentle BIB milling caused vitrinite reflectance (VR o ) increases of 12 to 36% of the original values determined optically before milling (average 26% increase). When molecular proxies from FTIR (A- and C-factor, branching ratio) were plotted against each other for the same vitrinite locations pre- and post-milling, mean data points for each sample generally lie within error of a 1:1 line. Likewise, mean Raman thermal proxy [full-width half maximum of G-band (G-FWHM), Raman band separation (RBS) and D1/G band intensity ratio] values were similar for pre- and post-milled locations, also plotting within error of a 1:1 line. AFM confirms the majority (24 of 36) of pre- and post-ion milled surface pairs were smoother (lower S q values) after BIB milling. These results are interpreted to indicate VR o increase induced by the gentle BIB milling conditions used in this study is an effect of decreased diffuse reflectance due to flatter surfaces, causing more photons to reflect directly back to the detector. Little evidence was observed for molecular aromatization and condensation of vitrinite molecules following BIB milling (with the conditions used). The presence of milling-induced artifacts, including differential milling effects dependent on location and the development of self-organized patterned structures, indicate much work remains in standardization of BIB milling before its promulgation as a routine sample preparation technique for organic petrography. These results provide better understanding of anthropogenic-induced changes to geological samples caused by the now widespread adoption of BIB milling as a disruptive innovation in sample preparation.