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In situ sulfur isotope analysis of sulfide minerals by SIMS: Precision and accuracy, with application to thermometry of ~3.5Ga Pilbara cherts

Secondary ion mass spectrometry (SIMS) measurement of sulfur isotope ratios is a potentially powerful technique for in situ studies in many areas of Earth and planetary science. Tests were performed to evaluate the accuracy and precision of sulfur isotope analysis by SIMS in a set of seven well-characterized, isotopically homogeneous natural sulfide standards. The spot-to-spot and grain-to-grain precision for δ34S is ± 0.3‰ for chalcopyrite and pyrrhotite, and ± 0.2‰ for pyrite (2SD) using a 1.6 nA primary beam that was focused to 10 µm diameter with a Gaussian-beam density distribution. Likewise, multiple δ34S measurements within single grains of sphalerite are within ± 0.3‰. However, between individual sphalerite grains, δ34S varies by up to 3.4‰ and the grain-to-grain precision is poor (± 1.7‰, n = 20). Measured values of δ34S correspond with analysis pit microstructures, ranging from smooth surfaces for grains with high δ34S values, to pronounced ripples and terraces in analysis pits from grains featuring low δ34S values. Electron backscatter diffraction (EBSD) shows that individual sphalerite grains are single crystals, whereas crystal orientation varies from grain-to-grain. The 3.4‰ variation in measured δ34S between individual grains of sphalerite is attributed to changes in instrumental bias caused by different crystal orientations with respect to the incident primary Cs+ beam. High δ34S values in sphalerite correlate to when the Cs+ beam is parallel to the set of directions < uuw>, from [111] to [110], which are preferred directions for channeling and focusing in diamond-centered cubic crystals. Crystal orientation effects on instrumental bias were further detected in galena. However, as a result of the perfect cleavage along {100} crushed chips of galena are typically cube-shaped and likely to be preferentially oriented, thus crystal orientation effects on instrumental bias may be obscured. Test were made to improve the analytical precision of δ34S in sphalerite, and the best results were achieved by either reducing the depth of the analysis pits using a Köhler illuminated primary beam, or by lowering the total impact energy from 20 keV to 13 keV. The resulting grain-to-grain precision in δ34S improves from ± 1.7‰ to better than 0.6‰ (2SD) in both procedures. With careful use of appropriate analytical conditions, the accuracy of SIMS analysis for δ34S approaches ± 0.3‰ (2SD) for chalcopyrite, pyrite and pyrrhotite and ± 0.6‰ for sphalerite. Measurements of δ34S in sub-20 µm grains of pyrite and sphalerite in ∼ 3.5 Ga cherts from the Pilbara craton, Western Australia show that this analytical technique is suitable for in situ sulfur isotope thermometry with ± 50 °C accuracy in appropriate samples, however, sulfides are not isotopically equilibrated in analyzed samples.

Chemical Geology↗

Mercury speciation in the Mt. Amiata mining district (Italy): interplay between urban activities and mercury contamination

A fundamental step to evaluate the biogeochemical and eco-toxicological significance of Hg dispersion in the environment is to determine speciation of Hg in solid matrices. In this study, several analytical techniques such as scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), sequential chemical extractions (SCEs), and X-ray absorption spectroscopy (XANES) were used to identify Hg compounds and Hg speciation in samples collected from the Mt. Amiata Hg mining district, southern Tuscany, Italy. Different geological materials, such as mine waste calcine (retorted ore), soil, stream sediment, and stream water suspended particulate matter were analyzed. Results show that the samples were generally composed of highly insoluble Hg compounds such as sulphides (HgS, cinnabar and metacinnabar), and more soluble Hg halides such as those associated with the mosesite group. Other moderately soluble Hg compounds, HgCl 2 , HgO and Hg 0 , were also identified in stream sediments draining the mining area. The presence of these minerals suggests active and continuous runoff of soluble Hg compounds from calcines, where such Hg compounds form during retorting, or later in secondary processes. Specifically, we suggest that, due to the proximity of Hg mines to the urban center of Abbadia San Salvatore, the influence of other anthropogenic activities was a key factor for Hg speciation, resulting in the formation of unusual Hg-minerals such as mosesite.

Tuscany↗

Reactivity of As and U co-occurring in mine wastes in northeastern Arizona

The reactivity of co-occurring arsenic (As) and uranium (U) in mine wastes was investigated using batch reactors, microscopy, spectroscopy, and aqueous chemistry. Analyses of field samples collected in proximity to mine wastes in northeastern Arizona confirm the presence of As and U in soils and surrounding waters, as reported in a previous study from our research group. In this study, we measured As (<0.500 to 7.77 μg/L) and U (0.950 to 165 μg/L) in waters, as well as mine wastes (<20.0 to 40.0 mg/kg As and <60.0 to 110 mg/kg U) and background solids (<20.0 mg/kg As and <60.0 mg/kg U). Analysis with X-ray fluorescence (XRF) and electron microprobe show the co-occurrence of As and U with iron (Fe) and vanadium (V). These field conditions served as a foundation for additional laboratory experiments to assess the reactivity of metals in these mine wastes. Results from laboratory experiments indicate that labile and exchangeable As(V) was released to solution when solids were sequentially reacted with water and magnesium chloride (MgCl 2 ), while limited U was released to solution with the same reactants. The predominance of As(V) in mine waste solids was confirmed by X-ray absorption near edge (XANES) analysis. Both As and U were released to solution after reaction of solids in batch experiments with HCO 3 − . Both X-ray photoelectron spectroscopy (XPS) and XANES analysis determined the predominance of Fe(III) in the solids. Mössbauer spectroscopy detected the presence of nano-crystalline goethite, Fe(II) and Fe(III) in (phyllo)silicates, and an unidentified mineral with parameters consistent with arsenopyrite or jarosite in the mine waste solids. Our results suggest that As and U can be released under environmentally relevant conditions in mine waste, which is applicable to risk and exposure assessment.

Arizona↗

Purification of triolein for use in semipermeable membrane devices (SPMDs)

Analyses of triolein-containing semipermeable membrane devices (SPMDs) have sometimes been impeded by interferences caused by impurities endemic to triolein that codialyze with the analytes. Oleic acid and methyl oleate have been the most troublesome of these impurities because of their relatively high concentrations in triolein and because significant residues of both can persist even after size exclusion chromatographic (SEC) fractionation. These residues have also been blamed for false-positive signals during bioindicator testing of SPMD dialysates. To prevent these problems, a simple, cost-effective procedure was developed for purifying triolein destined for use in SPMDs: the bulk triolein is repeatedly (6×) partitioned against methanol. Tests of the procedure show that 14 C-oleic acid is completely removed from the triolein. After SEC fractionation, dialysates of standard-size SPMDs made with the purified triolein contain less than 5 μg of methyl oleate as compared to sometimes more than 500 μg for dialysates (also after SEC) of SPMDs made with unpurified triolein. Gas chromatographic analyses with flame ionization and electron capture detection show that the purification treatment also greatly reduces the number and size of peaks caused by unidentified contaminants in the triolein. Microtox basic assay of dialysates of SPMDs shows that those made with the purified triolein have lower acute toxicities than dialysates of SPMDs made with unpurified triolein. Yeast estrogen screen (YES) testing of SPMDs fabricated with unpurified and purified triolein demonstrates that the purification process removes all background estrogenic activity.

Chemosphere↗

Assessment of pesticide residues in army cutworm moths (Euxoa auxiliaris) from the Greater Yellowstone Ecosystem and their potential consequences to foraging grizzly bears (Ursus arctos horribilis)

During summer, a grizzly bear ( Ursus arctos horribilis ) in the Greater Yellowstone Ecosystem (GYE) (USA) can excavate and consume millions of army cutworm moths ( Euxoa auxiliaris ) (ACMs) that aggregate in high elevation talus. Grizzly bears in the GYE were listed as threatened by the US Fish and Wildlife Service in 1975 and were proposed for delisting in 2005. However, questions remain about key bear foods. For example, ACMs are agricultural pests and concern exists about whether they contain pesticides that could be toxic to bears. Consequently, we investigated whether ACMs contain and transport pesticides to bear foraging sites and, if so, whether these levels could be toxic to bears. In 1999 we collected and analyzed ACMs from six bear foraging sites. ACMs were screened for 32 pesticides with gas chromatography with electron capture detection (GC–ECD). Because gas chromatography with tandem mass spectrometry (GC–MS/MS) can be more sensitive than GC–ECD for certain pesticides, we revisited one site in 2001 and analyzed these ACMs with GC–MS/MS. ACMs contained trace or undetectable levels of pesticides in 1999 and 2001, respectively. Based on chemical levels in ACMs and numbers of ACMs a bear can consume, we calculated the potential of chemicals to reach physiological toxicity. These calculations indicate bears do not consume physiologically toxic levels of pesticides and allay concerns they are at risk from pesticides transported by ACMs. If chemical control of ACMs changes in the future, screening new ACM samples taken from bear foraging sites may be warranted.

Wyoming↗

In vivo retention of ingested Au NPs by Daphnia magna: No evidence for trans-epithelial alimentary uptake

In vivo studies with Daphnia magna remain inconclusive as to whether engineered nanoparticles (NPs) are internalized into tissues after ingestion. Here we used a three-pronged approach to study the in vivo retention and efflux kinetics of 20 nm citrate stabilized Au NPs ingested by this key aquatic species. Daphnids were exposed to suspended particles (600 μg L −1 ) for 5 h after which they were depurated for 24 h in clean water containing algae. Light microscopy was used to follow the passage of Au NPs through the gastrointestinal tract, Au body burdens were determined by ICP-MS (inductively coupled plasma mass spectrometry), and transmission electron microscopy (TEM) was used to examine the presence and distribution of Au NPs in tissues. Results revealed that the elimination of Au NPs was bi-phasic. The fast elimination phase lasted <1 h and the rate constant at which Au (of Au NPs) was eliminated was 1.12 ± 0.34 h −1 (±SE) which accounted for ∼75% of the ingested Au. The remaining ∼25% of the ingested Au NPs was eliminated at a 100-fold slower rate. TEM analysis revealed that Au NPs in the midgut were in close proximity to the peritrophic membrane after 1 and 24 h of depuration. There were no observations of Au NP uptake at the microvilli. Thus, although Au NPs were retained in the gut lumen, there was no observable internalization into the gut epithelial cells. Similar to carbon nanotubes and CuO NPs, our findings indicate that in daphnids the in vivo retention of Au NPs does not necessarily result in their internalization.

Chemosphere↗

The effects of co-contaminants and native wetland sediments on the activity and dominant transformation mechanisms of a 1,1,2,2-tetrachloroethane (TeCA)-degrading enrichment culture

Bioremediation strategies, including bioaugmentation with chlorinated ethene-degrading enrichment cultures, have been successfully applied in the cleanup of subsurface environments contaminated with tetrachloroethene (PCE) and/or trichloroethene (TCE). However, these compounds are frequently found in the environment as components of mixtures that may also contain chlorinated ethanes and methanes. Under these conditions, the implementation of bioremediation may be complicated by inhibition effects, particularly when multiple dehalorespirers are present. We investigated the ability of the 1,1,2,2-tetrachloroethane (TeCA)-dechlorinating culture WBC-2 to biotransform TeCA alone, or a mixture of TeCA plus PCE and carbon tetrachloride (CT), in microcosms. The microcosms contained electron donors provided to biostimulate the added culture and sediment collected from a wetland where numerous &ldquo;hotspots&rdquo; of contamination with chlorinated solvent mixtures exist. The dominant TeCA biodegradation mechanism mediated by the WBC-2 culture in the microcosms was different in the presence of these wetland sediments than in the sediment-free enrichment culture or in previous WBC-2 bioaugmented microcosms and column tests conducted with wetland sediment collected at nearby sites. The co-contaminants and their daughter products also inhibited TeCA biodegradation by WBC-2. These results highlight the need to conduct biodegradability assays at new sites, particularly when multiple contaminants and dehalorespiring populations are present.

Chemosphere↗

Multi-residue method for the analysis of 85 current-use and legacy pesticides in bed and suspended sediments

A multi-residue method was developed for the simultaneous determination of 85 current-use and legacy organochlorine pesticides in a single sediment sample. After microwave-assisted extraction, clean-up of samples was optimized using gel permeation chromatography and either stacked carbon and alumina solid-phase extraction cartridges or a deactivated Florisil column. Analytes were determined by gas chromatography with ion-trap mass spectrometry and electron capture detection. Method detection limits ranged from 0.6 to 8.9 ??g/kg dry weight. Bed and suspended sediments from a variety of locations were analyzed to validate the method and 29 pesticides, including at least 1 from every class, were detected.

Journal of Chromatography A↗

Surface complexation model of uranyl sorption on Georgia kaolinite

The adsorption of uranyl on standard Georgia kaolinites (KGa-1 and KGa-1B) was studied as a function of pH (3–10), total U (1 and 10 μmol/l), and mass loading of clay (4 and 40 g/l). The uptake of uranyl in air-equilibrated systems increased with pH and reached a maximum in the near-neutral pH range. At higher pH values, the sorption decreased due to the presence of aqueous uranyl carbonate complexes. One kaolinite sample was examined after the uranyl uptake experiments by transmission electron microscopy (TEM), using energy dispersive X-ray spectroscopy (EDS) to determine the U content. It was found that uraniumwas preferentially adsorbed by Ti-rich impurity phases (predominantly anatase), which are present in the kaolinite samples. Uranyl sorption on the Georgia kaolinites was simulated with U sorption reactions on both titanol and aluminol sites, using a simple non-electrostatic surface complexation model (SCM). The relative amounts of U-binding >TiOH and >AlOH sites were estimated from the TEM/EDS results. A ternary uranyl carbonate complex on the titanol site improved the fit to the experimental data in the higher pH range. The final model contained only three optimised log K values, and was able to simulate adsorption data across a wide range of experimental conditions. The >TiOH (anatase) sites appear to play an important role in retaining U at low uranyl concentrations. As kaolinite often contains trace TiO 2 , its presence may need to be taken into account when modelling the results of sorption experiments with radionuclides or trace metals on kaolinite.

Applied Clay Science↗

Mineralogy and geochemistry of a Late Permian coal in the Dafang Coalfield, Guizhou, China: Influence from siliceous and iron-rich calcic hydrothermal fluids

This paper describes the influence of siliceous and iron-rich calcic low-temperature hydrothermal fluids (LTHF) on the mineralogy and geochemistry of the Late Permian No. 11 Coal (anthracitic, Rr =2.85%) in the Dafang Coalfield in northwestern Guizhou Province, China. The No. 11 Coal has high contents of vein ankerite (10.2 vol.%) and vein quartz (11.4 vol.%), with formation temperatures of 85 and 180 ??C, respectively, indicating that vein ankerite and vein quartz were derived from low-temperature calcic and siliceous hydrothermal fluids in two epigenetic episodes. The vein quartz appears to have formed earlier than vein ankerite did, and at least three distinct stages of ankerite formation with different Ca/Sr and Fe/Mn ratios were observed. The two types of mineral veins are sources of different suites of major and trace metals. Scanning electron microscope and sequential extraction studies show that, in addition to Fe, Mg, and Ca, vein ankerite is the dominant source of Mn, Cu, Ni, Pb, and Zn in the coal, and the contents of these five elements are as high as 0.09% and 74.0, 33.6, 185, and 289 ??g/g, respectively. In contrast, vein quartz is the main carrier mineral for platinum-group elements (PGEs) Pd, Pt, and Ir in the coal, and the contents of Pd, Pt, and Ir are 1.57, 0.15, and 0.007 ??g/g, respectively. Sequential extraction showed a high PGE content in the silicate fraction, up to 10.4 ??g/g Pd, 1.23 ??g/g Pt, and 0.05 ??g/g Ir, respectively. It is concluded that the formation of ankerite and quartz and the anomalous enrichment of trace elements in the No. 11 Coal in the Dafang Coalfield, Guizhou, result from the influx of calcic and siliceous low-temperature hydrothermal fluids. ?? 2004 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

Chemical evolution of Miocene wood: Example from the Belchatow brown coal deposit, central Poland

Miocene conifer wood samples from the Belchatow brown coal deposit in Poland were studied in order to discuss a range of chemical variations that occur as a result of biochemical coalification. Petrographic analysis, ultimate analysis, electron microprobe technique, and FTIR spectroscopy were used in this study. Our data show several progressive trends in functional groups distribution that take place during the wood transformation from group 1 to group 4, such as an overall increase in aromaticity, an increase in lignin/cellulose ratio, and an increase in oxygen functionalities. Other observations include an increase in aliphatic stretching and bending functionalities from groups 1 to 3; followed by a decrease in the wood of group 4; appearance of aliphatic out-of-plane bands in group 3 and increase in group 4; an increase in CH2/CH3 in group 4 compared to the other groups; and decrease in O-H groups in group 4 compared to other groups. These observations, together with other chemical and petrological observations, indicate that the progressive elimination of cellulose and modification of lignin are dominant processes of the wood transformation. ?? 2005 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

Petrology and chemistry of Permian coals from the Paraná Basin: 1. Santa Terezinha, Leão-Butiá and Candiota Coalfields, Rio Grande do Sul, Brazil

The current paper presents results on petrological and geochemical coal seam characterization in Permian coal-bearing strata from the Paran&aacute; Basin, southern Brazil. Sequence stratigraphic analysis shows that peat accumulation in Permian time was closely linked to transgressive/regressive cycles, with peat accumulation occurring in a predominantly back barrier/lagoonal setting. Coal petrographic analysis indicates subbituminous coals at Candiota and Le&atilde;o-Buti&aacute; and high volatile bituminous coals at Santa Terezinha, where locally the coal seams are thermally altered by volcanic intrusions. Petrographic composition is highly variable, with seams at Candiota and Santa Terezinha frequently enriched in inertinite. Chemical analyses indicate that all coals are mineral matter-rich (mean 49.09 wt.%), with SiO 2 and Al 2 O 3 dominating as determined by ICP-AES. Quartz is also the predominant mineral detected by X-ray diffraction, where it is associated with feldspar, kaolinite and hematite and iron-rich carbonates. The results from Scanning Electron Microscopy are broadly consistent with the bulk chemical and mineralogical analysis. Quartz and clays are common in all samples analyzed. Other minerals observed were, amongst others, carbonates (calcite, siderite, ankerite), pyrite, monazite, kaolinite, barite, sphalerite, rutile and quartz of volcanic origin. The distribution of trace elements is well within the range typical for coal basins of other areas despite the fact that the Paran&aacute; Basin coals are very high in ash yields. The average concentrations for elements of environmental concern (As, B, Be, Cd, Co, Cr, Cu, Hg, Li, Mn, Mo, Ni, Pb, Sb, Se, Tl, U, V, Zn) are similar to or less than the mean values for U.S. coal. However, considered on an equal energy basis, Paran&aacute; Basin coals will produce in combustion 5 to 10 times the amount of most elements compared to an equal weight US coal. Concentrations of major and trace elements, such as Fe, B and S, appear to be controlled by depositional setting, with increasing values in coal seams overlain by brackish/marine strata. Hierarchical cluster analysis identified three groups of major minerals and seven groups of trace elements based on similarity levels. On a regional scale, the coalfields can be separated by the differences in rank (Candiota and Le&atilde;o-Buti&aacute; versus Santa Terezinha) and by applying discriminant analysis based on 4 trace elements (Li, As, Sr, Sb). Highest Rb and Sr values occur at Candiota and are linked to syngenetic volcanism of the area, whereas high Y and Sr values at Santa Terezinha can be related to the frequent diabase intrusions in that area.

International Journal of Coal Geology↗

Mineralogical and compositional characteristics of Late Permian coals from an area of high lung cancer rate in Xuan Wei, Yunnan, China: Occurrence and origin of quartz and chamosite

Some townships in Xuan Wei County, Yunnan Province, have one of the highest lung cancer mortality rates in China and the epidemic disease in the area has generally been attributed to the polycyclic aromatic hydrocarbons (PAHs) released from domestic coal burning. However, the cancer-causing culprit is not settled as Tian [Tian, L., 2005. Coal Combustion Emissions and Lung Cancer in Xuan Wei, China. Ph.D. thesis, University of California, Berkeley.] found nanometer quartz in these coals, soot emissions, and lung cancer tissues. We have conducted mineralogical and geochemical studies of the coals from Xuan Wei for the purpose of shedding light on the minerals which may be related to the epidemic lung cancer. In this paper, abundances, modes of occurrence, and origins of minerals and elements in the coals from two mines in Xuan Wei have been studied using optical microscope, low-temperature ashing, X-ray diffraction analysis, scanning electron microscope equipped with energy-dispersive X-ray spectrometer, and inductively-coupled plasma mass spectrometry. The minerals in the coals are mainly composed of quartz, chamosite, kaolinite, and calcite. The particle size of quartz is rather small, mostly less than 20????m and it is of authigenic origin. Chamosite occurs mainly as cell-fillings. The occurrence of quartz and chamosite indicates that they were derived from the hydrothermal fluids. Epigenetic calcite is derived from calcic fluids. Kaolinite is derived mainly from sediment source region of Kangdian Oldland to the west of coal basin. The composition of Xuan Wei coal is high in SiO2, Fe2O3, TiO2, CaO, MnO, V, Co, Ni, Cu, and Zn. The high SiO2 content is attributed to quartz, and the Fe2O3 content to chamosite. The high Mn and low Mg contents in the coal indicate the inputs of hydrothermal fluids. CaO occurs mainly in epigenetic calcite. Elements Ti, Co, Ni, Cu, Zn, and rare earth elements were derived from the basaltic rocks at sediment source region. ?? 2008 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

A high-pyrite semianthracite of Late Permian age in the Songzao Coalfield, southwestern China: Mineralogical and geochemical relations with underlying mafic tuffs

The No. 12 Coal (Late Permian) in the Songzao Coalfield, Chongqing, southwestern China, is characteristically high in pyrite and some trace elements. It is uniquely deposited directly above mafic tuff beds. Samples of coal and tuffs have been studied for their mineralogy and geochemistry using inductively coupled plasma-mass spectrometry, X-ray fluorescence, plasma low-temperature ashing plus powder X-ray diffraction, and scanning electron microscopy equipped with energy-dispersive X-ray analysis.The results show that the minerals of the No. 12 Coal are mainly composed of pyrite, clay minerals (kaolinite, chamosite, and illite), ankerite, calcite, and trace amounts of quartz and boehmite. Kaolinite and boehmite were mainly derived from sediment source region of mafic tuffs. Chamosite was formed by the reaction of kaolinite with Fe-Mg-rich fluids during early diagenesis. The high pyrite (Sp,d=8.83%) in the coal was related to marine transgression over peat deposits and abundant Fe derived from the underlying mafic tuff bed. Ankerite and calcite were precipitated from epigenetic fluids.Chemical compositions of incompatible elements indicate that the tuffs were derived from enriched mantle and the source magmas had an alkali-basalt character. Compared to other coals from the Songzao Coalfield and common Chinese coals, the No. 12 Coal has a lower SiO2/Al2O3 (1.13) but a higher Al2O3/Na2O (80.1) value and is significantly enriched in trace elements including Sc (13.5??g/g), V (121??g/g), Cr (33.6??g/g), Co (27.2??g/g), Ni (83.5??g/g), Cu (48.5??g/g), Ga (17.3??g/g), Y (68.3??g/g), Zr (444??g/g), Nb (23.8??g/g), and REE (392??g/g on average). Above mineralogical compositions, as well as similar ratios of selected elements (e.g., SiO2/Al2O3 and Al2O3/Na2O) and similar distribution patterns of incompatible elements (e.g., the mantle-normalized diagram for incompatible elements and chondrite-normalized diagram for rare earth elements) of coal and tuff, indicated that enriched trace elements above were largely derived from mafic tuffs, in addition to a minor amount from the Kandian Oldland. ?? 2010 Elsevier B.V.

International Journal of Coal Geology↗

Pore-types and pore-network evolution in Upper Devonian-Lower Mississippian Woodford and Mississippian Barnett mudstones: Insights from laboratory thermal maturation and organic petrology

Pore-evolution models from immature organic-matter (OM) -rich Barnett (0.42%R o ) and Woodford (0.49%R o ) mudstones were compared with models previously developed from low-maturity OM-lean Boquillas (Eagle Ford-equivalent) mudstones to investigate whether (1) different mineralogy (siliceous vs. calcareous) exerts different catalytic and sorption effects and influences OM-pore origin and evolution; and (2) different types of macerals show different OM pore evolution history. Laboratory gold-tube pyrolysis, scanning electron microscopy (SEM) and thin-section petrography, organic petrography, and geochemical characterization were used to investigate the role of bulk mineralogy, maceral type, and thermal maturation on OM-pore evolution. Results suggest that mineralogy has little impact on OM-pore development and evolution. Macerals, identified using both SEM (platy OM, particulate OM, organic–mineral admixtures, Tasmanites ) and organic petrology (vitrinite, inertinite, amorphous organic matter [AOM]/bituminite, telalginite [ Leiosphaeridia , Tasmanites ]), do affect the origin and evolution of OM pores owing to differences in chemical compositions, generation kinetics, and activation-energy distributions between Tasmanites , matrix bituminite, and other types of macerals. Leiosphaeridia and Tasmanites in Woodford mudstone samples exhibit a delay in onset and a shorter period of petroleum generation and pore development compared to the matrix bituminite in the Barnett and Woodford mudstone samples. Pre-oil solid bitumen was observed to have migrated into initial primary mineral pore networks at the bitumen generation stage in both Barnett and Woodford samples. At higher levels of thermal maturation, the volume of primary mineral pores decreases and the pore volume composed of modified mineral pores and OM pores becomes greater. Pore evolution and pore-type heterogeneity in these mudstones is a function of the initial mineral pore network, types of kerogen and macerals, and generation kinetics of individual macerals upon thermal maturation.

Oklahoma↗

A review of spatially resolved techniques and applications of organic petrography in shale petroleum systems

This review examines new techniques and applications of organic petrography in source-rock reservoir petroleum systems that have occurred along with development of the global ‘shale revolution’ in energy resources. The review is limited to techniques and instrumentation that provide spatially resolved information, typically at or below microscales, for dispersed organic matter occurring in situ in samples of shale and mudrock. A brief summary of ion beam sample preparation is followed by discussion of the most common analytical techniques and applications. Advantages and limitations of each technique, including requisite sample preparation, types of information generated [e.g., molecular or elemental (isotopic) abundance], sensitivity, and resolution are discussed. In a few cases, techniques not yet applied to organic petrology of shale or mudrock are described (e.g., X-ray photoelectron spectroscopy imaging), in anticipation of near-term future application. The most common in situ techniques applied for characterization of organic matter in shale and mudrock include optical (including fluorescence) and electron microscopies, Raman, fluorescence, and infrared spectroscopies, and surficial measurements via force microscopy. Techniques that show growing application to organic petrography of shale include tip-enhanced photothermal infrared spectroscopy, mass spectrometry imaging, and synchrotron-based spectroscopies, among others. It is anticipated that the future of dispersed organic matter petrography will hold continued development of integrated instrument techniques (e.g., simultaneous or sequential correlative microscopies and/or spectroscopies of the same location), increased instrumental resolution, increased use of multiscale and multimodal organic petrography investigations, and three-dimensional imaging and chemical speciation mapping applications via multiple analytical approaches.

International Journal of Coal Geology↗

Relating systematic molecular and textural properties of graptolite pyrolyzed via gold tube hydrous pyrolysis: Implications for thermal proxies in lower Paleozoic marine shales

A series of gold tube pyrolysis experiments (72 h, 300–550 °C, 50 MPa) conducted on a graptolite-rich lower Paleozoic marine shale generated pyrolysis residues for a comprehensive evaluation of the molecular and structural variability of three types of graptolite periderm. Organic petrology, Raman spectroscopy, and field emission scanning electron microscopy (FE-SEM) with energy dispersive spectroscopy (EDS) were combined to evaluate the thermal evolution process. The three types of graptolite periderm, namely granular, non-granular, and nodular graptolite, were analyzed by Raman spectroscopy wherein point measurements were obtained after the maceral was identified and the location verified by organic petrology. Distinct thermal evolution pathways among non-granular, granular, and nodular graptolite periderms were recorded. The evolution patterns of the Raman parameters, particularly D1 and G bands, highlight the differences in geochemical composition of the graptolite periderm types and the alteration of molecular structure with increasing thermal maturity. Raman parameters D1 (position of the D1 peak), G-FWHM (full width at half maximum of the G peak), and ratios D1-FWHM/G-FWHM (full width at half maximum of the D1 peak ratioed to G-FWHM) and A D1 /A G (ratio of D1 and G peak intensities) showed effectiveness in assessing thermal maturity. Bireflectance with increasing gold tube pyrolysis temperature followed a hierarchy: non-granular > granular > nodular, reflecting different molecular alignment intensities. Qualitative FE-SEM evaluation showed that fine-grained mineral inclusions (primarily Fe-sulfide as determined via EDS) were associated with the graptolite populations, with granular graptolite containing greater amounts of coarser-grained (e.g., ∼300–1400 nm) mineral inclusions relative to non-granular and nodular graptolite, which contain finer-grained (e.g., ∼100–200 nm) inclusions difficult to resolve with optical microscopy. These findings are investigated to highlight the mechanisms that drive organic matter evolution within graptolite during thermal maturation, as well as to explore some of the limitations of using spectroscopic parameters as thermal maturity proxies.

International Journal of Coal Geology↗

Potential involvement of rainbow trout thrombocytes in immune functions: a study using a panel of monoclonal antibodies and RT-PCR

The functional relationship between fish and mammalian thrombocytes is relatively unknown. In this study, a panel of monoclonal antibodies (mAbs) was used to investigate the functional properties of rainbow trout thrombocytes. The mAbs recognize cell-surface molecules on thrombocytes with molecular weights ranging from 17 to 160 kDa. Flow cytometric and immuno-electron microscopic analyses demonstrate that these molecules are expressed at different levels and that surface expression increased upon activation with bovine collagen. Two of these cell-surface molecules (17 and 21 kDa) were directly involved in collagen-induced aggregation of thrombocytes since aggregation was blocked upon pre-treatment with mAbs that recognize the two surface markers. Interestingly, the percentage of thrombocytes in blood increased after stimulation using different antigens. The transcriptional profile of trout thrombocytes was then examined after immuno-magnetic enrichment using the described mAbs to assess potential roles of trout thrombocytes in immune functions. Trout thrombocytes express components of the MHC class Ia pathway, IL1&beta;, TNF&alpha;, TGF&beta;, the interleukin receptor common &gamma; chain as well as CXC and CC chemokines. MHC class IIB and TNF&alpha; were expressed at low levels in resting thrombocytes. No evidence was found for the expression of TCR&alpha;&beta;, Ig heavy chain, CD8&alpha; or CK1 mRNA. Taken together, these results suggest that rainbow trout thrombocytes express molecules involved in activation, aggregation and genes encoding proteins, that are involved in antigen presentation and immune regulation.

Developmental and Comparative Immunology↗