Inorganic Affinity Research Articles

The Miocene coal seams in the Soma Basin (W. Turkey): Insights from coal petrography, mineralogy and geochemistry

The Neogene Soma Basin, western Turkey, hosts three coal seams (kM2, kM3 and kP1) and several altered tuff layers within the Miocene sequences. This study focuses on the evaluation of coal-petrography, mineralogical and elemental compositions, as well as the Rock-Eval pyrolysis of the three coal seams from Eynez, Işıklar and Deniş sectors, and to identify the mineralogy of altered tuff layers within kM2 and kP1 seams. The routine coal quality analyses show that coal samples from the kM2 seam are characterized by lower ash yields and total S contents, and higher gross calorific values than kM3 and kP1 seams. The mineralogical composition of the bulk coal samples varies between all three seams. The statistical treatment implies that major elements in bulk coal samples such as Al, Fe, K, Mg and Na, and the vast majority of minor and trace elements have inorganic affinity. The trace element contents and elemental enrichments in the coal samples are generally changeable from seam to seam, which could be related to differences in ash yield and mineralogy. Altered tuff layers, or tonsteins were identified in kM2 and kP1 seams. The tonsteins are clay rich, and certain trace elements (e.g. As and Zr) are enriched in the coal layers beneath the tuff layers in the kM2 seam. This might be related to penetration of leached pore water into these layers and precipitation of epigenetic minerals.The coal-petrography composition and the coal-facies diagrams show that the precursor peat of the kM2 seam was accumulating under telmatic, mesotrophic, anoxic conditions, whereas the water level was high and stable. The relatively low ash yields and thicker coal beds suggest a lower clastic input from the basin margins, and water table fluctuations resulted in calcareous intercalations in the kM3 and kP1 seams. These imply the development of limno-telmatic conditions whereas fluvial activity affected during peat accumulation of both seams. Considering the maceral composition along with the coal thickness, coal seams in the Soma Basin might display oil-generation potential; however, the pyrolysis analysis shows that the studied coal seams are mainly gas-prone and only certain coal beds have mixed-hydrocarbon generation capacity. All data presented in this study indicates that lithological features, differences in coal qualities and elemental contents in the Soma Basin were mainly controlled by changes in the depositional conditions and the detrital input during Miocene.

Mineralogical and geochemical characterization of the Saray and Pınarhisar coals, Northwest Thrace Basin, Turkey

This study investigates the mineralogical and geochemical characteristics of coals from the Saray and Pınarhisar coalfields in the Northwest Thrace Basin, using optical microscopy, scanning electron microscopy, X-ray diffraction and inductively coupled plasma mass spectrometry. The Saray and Pınarhisar coals were deposited in a limnic environment. The sulfur content of the coals ranges from 0.3 to 15.3% and high sulfur contents may originate from both seawater and volcanism. Pyritic and organic sulfur are the dominant sulfur forms (1.2% and 2.7% on average, respectively). The mineral matter of the coals consists mainly of pyrite, barite, gypsum, muscovite and kaolinite, with minor amounts of quartz, butlerite, tamarugite and rozenite. The coals are enriched in trace elements, including V (61ppm on average), Co (5.85ppm on average), Ni (79ppm on average), As (39.2ppm on average), Th (3.6ppm on average) and U (6.7ppm on average). Based on Pearson correlation coefficients, Ti, V, Cr, Fe, Co, Ni, Cu, Se, Rb, Au, Hg, Pb and Th have mainly inorganic affinities (rash-elements>+0.5) in the Pınarhisar coals; Fe, As and Au also have inorganic affinities (rash-elements≥+0.5) in the Saray coals. The element contents and correlation coefficients indicate that the Strandja Massif, the Tethyan ophiolite belt and the oldest basement sediments were included in the sediment source region for both coalfields, while the Strandja Massif was the prevailing sediment source region for Pınarhisar coalfield.

Coal characteristics, elemental composition and modes of occurrence of some elements in the İsaalan coal (Balıkesir, NW Turkey)

This study uses coal petrography, micro-FTIR, mineralogical, and geochemical analyses to determine the coal characteristics and controlling factors of elemental enrichments in the İsaalan coal (NW Turkey). The obtained data show that this subbituminous coal has a relatively low ash yield (avg. 19%), high hydrogen content (avg. 5.4%) and total S content (avg. 2.4%), on an air-dry basis. The maceral composition, along with micro-FTIR data on ulminite, suggests that lignin- and resin-rich vegetation was predominant. The coal facies data imply the precursor peat was accumulating under, mesotrophic anoxic conditions where water level was high and fluctuating. The mineralogical composition of the bulk coal samples is composed mainly of quartz, pyrite, and clay minerals and lesser amounts of feldspars and carbonates.The statistical analysis of the bulk compositional data shows the major elements, including Al, Fe, K, Na, Mg, P, and the vast majority of trace elements, have inorganic affinity, whereas B presumably has organic affinity. The trace element concentrations are variable, and especially As and elements including B, Ba, Cr, Cs, Ni, Sb, and V are enriched compared to most world coals. The enrichments and distributions of Cr, Cs, Ni, and V were controlled by clastic inputs into a palaeomire, whereas As enrichments were controlled mainly by epigenetic and, to a lesser extent, syngenetic factors. Introduced SO42− and As-rich surface- and groundwater from the basin margin area, along with anoxic conditions in the palaeomire, resulted in syngenetic formation of As-bearing pyrite. The circulating intra-seam solutions later liberated As from syngenetically formed pyrite, which resulted in As- and Ni-rich overgrowths around framboidal and massive pyrite crystals. These solutions could also easily mobilize B that was absorbed by organic matter. Therefore, B enrichment appears to be related to epigenetic factors. Tectonic activities during coalification allowed hydrothermal solutions from neighbouring epithermal mineralisation to penetrate and circulate along with underground waters that leached overlying volcanoclastic-volcanic strata and supplied a number of elements to the studied coal. Thus, infilling As-bearing pyrite and silica were formed mainly during coalification. All these results suggest that As-enrichment in the study area is more likely a combination of epigenetic factors and syngenetic-detrital rather than volcanogenic contributions, as suggested earlier for some other Turkish coal deposits.

Modes of occurrences of major and trace elements in coals from Yangquan Mining District, North China

Yangquan Mining District is a major location for anthracite coal production in China. Understanding the modes of occurrences of major and trace elements in Yangquan coal is significant both geochemically and environmentally, although most elements are more depleted than those in Chinese coal. Ten coal bench and two parting samples were collected from No. 15 Coal of Yangquan Mining District. X-ray diffraction analysis was used to determine the proportions of minerals in the Yangquan coal, and X-ray fluorescence and inductively coupled plasma mass spectrometry analyses were used to determine the contents of major element oxides and trace elements, respectively. The mineral assemblages, ash yield, and (CaO+MgO+Fe2O3)/(SiO2+Al2O3) ratio varied significantly in the vertical direction, which is attributed mainly to vertical variation in the depositional environment. The major element oxides and trace elements in the Yangquan coal were divided into four groups according to cluster analysis, which represent organic or inorganic affinity and different modes of occurrences. The coal benches underlying partings exhibited a rare-earth element and yttrium (REY) distribution pattern characterized by heavy (H)-type. This result differs from other coal benches characterized by light (L)-type REY, which is attributed to the leaching of overlying partings.

Distribution and affinity of trace elements in Samaleswari coal, Eastern India

Coal samples from a borehole in the Samaleswari open cast coal block (S-OCB) have been collected. A chemical data set (n=17) (proximate parameters, sulfur contents, mineral composition, trace and major element oxide concentrations) has been generated to evaluate the origin of trace elements in a vertical sequence through the stratigraphic column (∼300m). The variations of volatile matter and fixed carbon indicate that the rank of the coal in the stratigraphic section studied increases from lignite (∼50%VMdaf) at the top to high-volatile bituminous (∼25%VMdaf) at the base, which reflects a more or less progressive increase in metamorphism from younger to older coal horizons. The major minerals present in the samples are quartz and kaolinite, followed by illite; the minor constituents are siderite, apatite and rutile. The mineralogical variations are primarily related to depth, with depositional environment having a significant role in the succession. In the studied borehole concentrations of the three major element oxides, SiO2, Al2O3 and Fe2O3, reflect the abundance of the minerals. The study indicates a systematic increase in the concentration of some trace elements (Se, Be, Sb) with depth. These elements have no similarity in trend to ash or pyritic sulfur but have strong association with fixed carbon (dry, ash-free). Two other trace elements, Co and Mn, more or less decrease in concentration in the older coal horizons, and have a significant association with ash. Another group of trace elements (As, Pb, Cd, Cu, Ni and Zn) has a sudden increase in concentration at a particular depth. These trace elements also show a similar vertical trend to pyritic sulfur. The work is further supported by the use of statistical tools (correlation coefficient, hierarchical cluster and linear multiple regression) which suggest several possible affinities of the trace elements such as inorganic, organic and multiple. Among the analyzed trace elements Co, Mn, Cd, Pb, As, Ni, Cu, Zn display principally an inorganic affinity, whereas Be, Se and Sb show an organic affinity. The variation in concentration of some trace elements (Be, Se, Sb) appears from the study to be a consequence of rank advance.

Modes of Occurrence and Abundance of Trace Elements in Pennsylvanian Coals from the Pingshuo Mine, Ningwu Coalfield, Shanxi Province, China

The Pingshuo Mine is an important coal mine of the Ningwu coalfield in northern Shanxi Province, China. To investigate the mineralogy and geochemistry of Pingshuo coals, core samples from the mineable No. 4 coals were collected. The minerals, major element oxides, and trace elements were analyzed by scanning electron microscopy (SEM), LTA-XRD in combination with Siroquant software, X-ray fluorescence (XRF), inductively coupled plasma mass spectrometry (ICP-MS) and ICP-CCT-MS (As and Se). The minerals in the Pennsylvanian coals from the Pingshuo Mine dominantly consist of kaolinite and boehmite, with minor amounts of siderite, anatase, goyazite, calcite, apatite and florencite. Major-element oxides including SiO2 (9.54 wt %), Al2O3 (9.68 wt %), and TiO2 (0.63 wt %), as well as trace elements including Hg (449.63 ng/g), Zr (285.95 μg/g), Cu (36.72 μg/g), Ga (18.47 μg/g), Se (5.99 μg/g), Cd (0.43 μg/g), Hf (7.14 μg/g), and Pb (40.63 μg/g) are enriched in the coal. Lithium and Hg present strong positive correlations with ash yield and SiO2, indicating an inorganic affinity. Elements Sr, Ba, Be, As and Ga have strong positive correlations with CaO and P2O5, indicating that most of these elements may be either associated with phosphates and carbonates or have an inorganic–organic affinity. Some of the Zr and Hf may occur in anatase due to their strong positive correlations with TiO2.

Peptide Binding for Bio-Based Nanomaterials.

Peptide-based strategies represent transformative approaches to fabricate functional inorganic materials under sustainable conditions by modeling the methods exploited in biology. In general, peptides with inorganic affinity and specificity have been isolated from organisms and through biocombinatorial selection techniques (ie, phage and cell surface display). These peptides recognize and bind the inorganic surface through a series of noncovalent interactions, driven by both enthalpic and entropic contributions, wherein the biomolecules wrap the metallic nanoparticle structure. Through these interactions, modification of the inorganic surface can be accessed to drive the incorporation of significantly disordered surface metal atoms, which have been found to be highly catalytically active for a variety of chemical transformations. We have employed synthetic, site-directed mutagenesis studies to reveal localized binding effects of the peptide at the metallic nanoparticle structure to begin to identify the biological basis of control over biomimetic nanoparticle catalytic activity. The protocols described herein were used to fabricate and characterize peptide-capped nanoparticles in atomic resolution to identify peptide sequence effects on the surface structure of the materials, which can then be directly correlated to the catalytic activity to identify structure/function relationships.

Mineral matter, major and trace element content of the Afşin–Elbistan coals, Kahramanmaraş, Turkey

The Afşin–Elbistan coal basin is one of the most important coal deposits of Turkey. The mineral matter, major and trace element concentrations of the Afşin–Elbistan coals and their modes of occurrence are discussed in this study. The coal seam is located within the Upper Miocene–Pliocene aged Ahmetcik Formation which is represented by fluvial–lacustrine facies. Thickness of the coal zone is 80m, but it reaches 105m in the Kışlaköy sector. A total of 86 samples were taken from the Kışlaköy open-pit mine and from the 14 boreholes drilled by the General Directorate of Mineral Research and Exploration (MTA) for coal exploration. The proximate, XRD, SEM-EDS, major and trace element analyses were conducted on the samples. The studied coals are characterized by relatively high moisture, ash, total sulfur, volatile matter contents and low gross calorific values. The mineral matters of the Afşin–Elbistan coal are represented by calcite, quartz, pyrite, feldspar, aragonite, opal-CT, gypsum, jarosite and clay minerals. Strontium, Rb, Sm, Zr, Hf, Nb, Mo, U, Zn, Pb, As, Mn, Co, Cr and Ni concentrations detected by EDP-XRF are higher than the world brown coal values. Many of the trace elements showing positive correlations with ash content imply inorganic affinity. The element concentrations of the coals are mainly related to the carbonate, silicate, sulfide, phosphate, ore minerals and fossil shells. However, some elements have also organic affinities.

Hierarchically-organized, well-dispersed hydroxyapatite-coated magnetic carbon with combined organics and inorganics removal properties

Novel hierarchically-organized magnetic microspheres have been successfully developed that consist of an aqueous hollow core, a magnetic porous Fe3O4–carbon layer and a well-define hydroxyapatite (HAp) shell. The hollow magnetic carbon microspheres were prepared by ultrasonic spray pyrolysis and coated with HAp using a biomimetic approach. The resulting powders exhibit micro- and meso-porosity. The removal capacity of the composite spheres towards an antibiotic (ampicillin), a rare-earth ion (La3+) and two heavy metals (Hg2+ and Pb2+) has been studied and compared with that of the individual components. The dual organic–inorganic affinity of the magnetic HAp/carbon conjugates was demonstrated, with synergetic effects being evidenced for heavy metal removal enlightening their potentialities in wastewater treatment.

Geochemical and mineralogical evidence for a coal-hosted uranium deposit in the Yili Basin, Xinjiang, northwestern China

The petrological, geochemical, and mineralogical compositions of the coal-hosted Jurassic uranium ore deposit in the Yili Basin of Xinjiang province, northwestern China, were investigated using optical microscopy and field emission-scanning electron microscopy in conjunction with an energy-dispersive X-ray spectrometer, as well as X-ray powder diffraction, X-ray fluorescence, and inductively coupled plasma mass spectrometry. The Yili coal is of high volatile C/B bituminous rank (0.51–0.59% vitrinite reflectance) and has a medium sulfur content (1.32% on average). Fusinite and semifusinite generally dominate the maceral assemblage, which exhibits forms suggesting fire-driven formation of those macerals together with forms suggesting degradation of wood followed by burning. The Yili coals are characterized by high concentrations of U (up to 7207μg/g), Se (up to 253μg/g), Mo (1248μg/g), and Re (up to 34μg/g), as well as As (up to 234μg/g) and Hg (up to 3858ng/g). Relative to the upper continental crust, the rare earth elements (REEs) in the coals are characterized by heavy or/and medium REE enrichment. The minerals in the Yili coals are mainly quartz, kaolinite, illite and illite/smectite, as well as, to a lesser extent, K-feldspar, chlorite, pyrite, and trace amounts of calcite, dolomite, amphibole, millerite, chalcopyrite, cattierite, siegenite, ferroselite, krutaite, eskebornite, pitchblende, coffinite, silicorhabdophane, and zircon. The enrichment and modes of occurrence of the trace elements, and also of the minerals in the coal, are attributed to derivation from a sediment source region of felsic and intermediate petrological composition, and to two different later-stage solutions (a U–Se–Mo–Re rich infiltrational and a Hg–As-rich exfiltrational volcanogenic solution). The main elements with high enrichment factors, U, Se, As, and Hg, overall exhibit a mixed organic–inorganic affinity. The uranium minerals, pitchblende and coffinite, occur as cavity-fillings in structured inertinite macerals. Selenium, As, and Hg in high-pyrite samples mainly show a sulfide affinity.

Behavior study of trace elements in pulverized lignite, bottom ash, and fly ash of Amyntaio power station, Greece

The Kozani-Ptolemais-Amyntaio basin constitutes the principal coal field of Greece. Approximately 50% of the total power production of Greece is generated by five power stations operating in the area. Lignite samples, together with the corresponding fly ash and bottom ash were collected, over a period of 3 months, from the power plant of Amyntaio and analyzed for their content in 16 trace elements. The results indicate that Y, Nb, U, Rb, Zr, Ni, Pb, Ba, Zn, Sr, Cu, and Th demonstrate an organic affinity during the combustion of lignite, while V has an inorganic affinity. Three elements (Co, Cr, and Sc) show an intermediate affinity.

Borated Titania, a New Option for the Selective Enrichment of cis‐Diol Biomolecules

As low abundance cis-diol biomolecules are of great significance in biological organisms, preparation of materials for the selective enrichment of such compounds is highly favorable for the development of the related proteomics and metabolomics. To this end, we have prepared monolithic borated titania by a non-aqueous sol-gel strategy as a new inorganic affinity material for the specific capture of nucleosides, glycopeptides and glycoproteins. Benefiting from the inorganic framework, this material prevented the hydrophobic interference, which was somewhat inevitable for the mainstream organic-based boronate affinity materials. The prepared material was carefully characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and nitrogen-sorption experiments to investigate the morphology and elemental composition. The excellent performance of borated titania on enrichment of cis-diol biomolecules was demonstrated by extracting the glycopeptides from horseradish peroxidase (HRP) digestion, standard glycoproteins, and nucleosides from a human-urine matrix. This kind of inorganic affinity material offers a new option for selective enrichment or separation of cis-diol biomolecules.

Geochemistry of terrestrial oil shale from the Lunpola area, northern Tibet, China

Abstract The Lunpola oil shale is the largest oil shale resource in Tibet. Twenty-four samples of oil shale, mudstone, and dolomite were collected from the Lunpola oil shale for mineralogical and trace element analyses. The vertical distribution and mode of occurrence of trace elements in this terrestrial oil shale were also discussed. Oil shale samples from the Lunpola area have high TOC contents (5.1–10.6%), high ash yields (74.8–84.7%), low total sulfur contents (0.19–1.03%), and high shale oil contents (5.0–10.3%). The major minerals in the oil shale samples are clays, quartz, calcite and dolomite, with minor quantities of feldspar, siderite, hematite, magnesite and pyrite. Other minerals such as halite, zeolite, barite, anhydrite, and mirabilite were detected in some oil shale samples. The contents of As, Ba, Be, Bi, Cd, Ce, Cs, Hg, La, Li, Mo, Nd, Pb, Pr, Rb, Se, Sm, Th, U, W, and Zr are enriched from 1.30 to 125 times as compared to their average crust abundance (Clarke values), whereas the other elements are slightly higher or lower than their respective Clarke values. Compared to common Australian oil shale, the Lunpola oil shales contain higher As, Ba, Be, Ce, Co, Cs, Ga, Gd, Hf, Nb, Nd, Pb, Pr, Rb, Sc, Sm, Sn, Th, and Zr, but lower Cd, Cu, Lu, Mo, Ni, Se, Sr, U, V, and Zn. Elements associated with organic matter and/or Fe-sulfides are highly enriched in all oil shale deposits, suggesting that their speciation in oil shale is governed by general processes (e.g., high organic matter content and anoxic environment), whereas elements associated with clay minerals exhibit various enrichments indicating that their speciation in oil shale is governed by individual geochemical mechanisms (e.g., source rocks). The elements in the Lunpola oil shale may be classified into three groups of associations according to their modes of occurrence. Group A elements (TiO 2 , Sc, Hf, Zr, Be, Li, W, V, Zn, SiO 2 , Al 2 O 3 , Rb, Ga, Sn, Cr, Ta, Cs, K 2 O, Th, Na 2 O, REEs, and ash yield) have high positive correlations with ash yield and a mainly inorganic affinity. Group B elements (As, TOC, MnO, Ni, Fe 2 O 3 , Cd, Co, Cu, Mo, Se, MgO, Bi, Pb, and Hg) show a negative correlation with ash yield, and most elements possibly have a likely organic affinity and/or Fe-sulfide affinity. Group C elements (Sr, CaO, U, and P 2 O 5 ) show a weak or negligible correlation with ash yield (with the exception of CaO). Elements of environmental concern (As, Bi, Hg, Mo, Pb, Se, and U) are present in high contents, and are clustered in the second association, i.e. they are hosted mainly in Fe-sulfides and/or organic matter.

Distribution of selected trace elements in density fractionated Waterberg coals from South Africa

Abstract The Waterberg Coalfield, located in the Limpopo Province (north-western area) of South Africa, contains a significant proportion of the South African coal resource. This Permian coalfield typically contains high vitrinite, high ash coals in the Kungurian Grootegeluk Formation, and high inertinite, low ash coals in the Artinskian Vryheid Formation. Four run-of-mine coals and density fractioned samples were analysed to determine their trace element content. The concentrations of most trace elements in the run-of-mine coals exceed the global averages and certain global ranges, and generally exceed values reported for other South African coalfields. Specifically, Hg concentrations are high to very high in all the coals (up to 2.43 ppm in a sample from the Vryheid Formation), Cd and Se concentrations are comparable to or lower than global averages, and As is very low in the Vryheid Formation (1.57 ppm). A sample from the Grootegeluk Formation is enriched in siderophile elements, and a sample from the Vryheid Formation is depleted in chalcophile elements. Studies of the density fractionated samples indicate that Cd exhibits an organic affinity in the Grootegeluk Formation samples, and possibly a pyritic (or sulphide) affinity in the Vryheid Formation sample. Selenium has a greater affinity for the middle, clay-rich density fractions in all samples. Arsenic reports to the mineral-rich sink fractions, specifically the fractions enriched in pyrite. Mercury reports to both the float and sink fractions, indicating an organic and inorganic affinity in these coals, although there is more enrichment in the sink fractions in the Grootegeluk Formation samples, and a definite organic correlation in the Vryheid Formation sample.

ORIGIN AND MODE OF OCCURRENCE OF TRACE ELEMENTS IN MARINE OIL SHALE FROM THE SHENGLI RIVER AREA, NORTHERN TIBET, CHINA

With the aim of better understanding of geochemistry of marine oil shale, 25 samples from the Shengli River area were studied. The concentrations of Sr, U, Rb, Pb, and Th were 1.22 to 3.66 times higher compared to the average concentrations in the crust (Clarke values), while the concentrations of other elements were slightly higher/lower compared to the respective Clarke values. Trace elements including U, Pb and Th are important from the environmental point of view. The elements in the Shengli River oil shale may be divided into three groups according to their modes of occurrence, i.e. group A, B, and C. Group A exhibits a relatively high affinity with organic matter. Group B has weakly positive or slightly negative correlation coefficients with ash yield, while Group C shows high positive correlation coefficients with ash yield and possibly has an inorganic affinity. Elements related to terrigenous origin in the oil shale seams in the Shengli River oil shale have originated from two sources: the Nadi Kangri Formation felsic volcanic rocks and the Suowa Formation limestone.

Concentration and mode of occurrence of trace elements in marine oil shale from the Bilong Co area, northern Tibet, China

Abstract The Bilong Co oil shale zone is located in the South Qiangtang depression. This zone, together with the Shengli River-Changshe Mountain oil shale zone in the North Qiangtang depression, northern Tibet plateau, represents a potentially large marine oil shale resource in China. With the aim of better understanding geochemistry of marine oil shale, 18 samples from the Bilong Co area are studied and 56 elements in them are determined. The contents of Mo, Se, Cd, Cs, As, Bi, U Rb, Pb, Th, Li, Sr, and Zn are enriched from 1.3 to 35.0 times as compared with the average concentration in the crust (Clarke values), whereas the other elements are slightly higher/lower than the respective Clarke values. Compared to common Australian oil shales, the contents of Ce, Co, Cs, F, Ga, Hf, Nb, Nd, Pb, Pr, Rb, Sc, Sn, Th, and Zr in the Bilong Co oil shale samples exhibit relatively high levels, whereas As, Br, Cd, Cr, Cu, Dy, Er, Eu, Ho, Lu, Mo, Ni, Se, Tb, Tm, U, V, Y, Yb, and Zn are relatively depleted. However, the distribution patterns of trace elements are quite similar indicating that trace-element speciation in oil shale is governed by general processes rather than by individual geochemical mechanisms within one particular sample. The elements in the Bilong Co oil shale may be classified into three groups of association according to their modes of occurrence, i.e. Groups A, B, and C. Group A (Si–Al–K–Na–Ti–Zr–Sc–Th–Sn–Nb–Ga–Ta–Be–Hf–Cs–Li–Rb–ash–REEs) is strongly correlated with ash yield and mainly has an inorganic affinity. Group B (Cr–W–Mg–Mn–Br–F–Sr–Ba) has weakly or negatively positive correlation coefficients (with an exception of F) with ash yield. Group C (Zn–Bi–Cd–Ca–Fe–Pb–Hg–Co–Cu–Ni–P–Mo–Se–U–As–V) shows negative correlation coefficients with ash yield (with an exception of Bi) and possibly has an organic affinity.

석조문화재를 위한 아크릴계 보존처리제의 무기친화성 개선

Applying acrylic silane monomer for determent of weathering damage of stone cultural assets from various sources was investigated to improve inorganic affinity of polymer impregnated to the stone for conservation treatment using impregnation of acrylic polymers under pressure. Radical polymerization was carried out with various mixture ratios of methacrylate (MMA), as the base monomer, and vinyl trimethoxy silane (VTMS). Subsequently, according to the changes of glass transition temperatures, average molecular weights, and storage moduli of the obtained copolymers, the case of adding 1 wt% of benzoyl peroxide, polymerization for 8 hrs, and mixing 5 mol% of VTMS to MMA was the optimum condition of monomer ratio and polymerization. Practically, fresh granites collected in domestic site and weathered stones were treated by following the obtained result above, and then, the moisture absorption, impact, acid resistance, and adhesion properties of the treated stones were compared to those of the corresponding stones treated with MMA only. It was found that those properties of the stones treated with PMV5 were considerably improved.

Mineralogy and geochemistry of boehmite-rich coals: New insights from the Haerwusu Surface Mine, Jungar Coalfield, Inner Mongolia, China

Abstract Boehmite-rich coal of Pennsylvanian age was discovered earlier at the Heidaigou Surface Mine, Jungar Coalfield, Inner Mongolia, China. This paper reports new results on 29 bench samples of the no. 6 coal from a drill core from the adjacent Haerwusu Surface Mine, and provides new insights into the origin of the minerals and elements present. The results show that the proportion of inertinite in the no. 6 coal is higher than in other Late Paleozoic coals in northern China. Based on mineral proportions (boehmite to kaolinite ratio) and major element concentrations in the coal benches of the drill core, the no. 6 coal may be divided into five sections (I to V). Major minerals in Sections I and V are kaolinite. Sections II and IV are mainly kaolinite with a trace of boehmite, and Section III is high in boehmite. The boehmite is derived from bauxite in the weathered surface (Benxi Formation) in the sediment-source region. The no. 6 coal is rich in Al2O3 (8.89%), TiO2 (0.47%), Li (116 μg/g), F (286 μg/g), Ga (18 μg/g), Se (6.1 μg/g), Sr (350 μg/g), Zr (268 μg/g), REEs (172 μg/g), Pb (30 μg/g), and Th (17 μg/g). The elements are classified into five associations by cluster analysis, i.e. Groups A, B, C, D, and E. Group A (ash–SiO2–Al2O3–Na2O–Li) and Group B (REE–Sc–In–Y–K2O–Rb–Zr–Hf–Cs–U–P2O5–Sr–Ba–Ge) are strongly correlated with ash yield and mainly have an inorganic affinity. The elements that are negatively or less strongly correlated with ash yield (with exceptions of Fe2O3, Be, V, and Ni) are grouped in the remaining three associations: Group C, Se–Pb–Hg–Th–TiO2–Bi–Nb–Ta–Cd–Sn; Group D, Co–Mo–Tl–Be–Ni–Sb–MgO–Re–Ga–W–Zn–V–Cr–F–Cu; and Group E, S–As–CaO–MnO–Fe2O3. Aluminum is mainly distributed in boehmite, followed by kaolinite. The high correlation coefficients of the Li–ash, Li–Al2O3, and Li–SiO2 pairs indicate that Li is related to the aluminosilicates in the coal. The boehmite-rich coal is high in gallium and F, which occur in boehmite and the organic matter. Selenium and Pb are mainly in epigenetic clausthalite fillings in fractures. The abundant rare earth elements in the coal benches were supplied from two sources: the bauxite on the weathered surface of the Benxi Formation and from adjacent partings by groundwater leaching during diagenesis. The light rare earth elements (LREEs) are more easily leached from the partings and incorporated into the organic matter than the heavy REEs, leading to a higher ratio of LREEs to HREEs in the coal benches than in the overlying partings.

Petrological, organic geochemical and geochemical characteristics of coal from the Soko mine, Serbia

A petrological, organic geochemical and geochemical study was performed on coal samples from the Soko Mine, Soko Banja basin, Serbia. Ten coal and two carbonaceous clay samples were collected from fresh, working faces in the underground brown coal mine from different parts of the main coal seam. The Lower Miocene, low-rank coal of the Soko Mine is a typical humic coal with huminite concentrations of up to 76.2 vol.%, liptinite less than 14 vol.% and inertinite less than 11 vol.%. Ulminite is the most abundant maceral with variable amounts of densinite and clay minerals. Sporinite and resinite are the most common macerals of the liptinite group. Inertodetrinite is the most abundant maceral of the inertinite group. The mineral-bituminous groundmass identified in some coal samples, and carbonaceous marly clay, indicate sub-aquatic origin and strong bacterial decomposition. The mean random huminite reflectance (ulminite B) for the main coal seam is 0.40 ± 0.05% Rr, which is typical for an immature to early mature stage of organic matter. The extract yields from the coal of the Soko Banja basin ranges from 9413 to 14,096 ppm, in which alkanes constituted 1.0–20.1%, aromatics 1.3–14.7%, asphaltenes 28.1–76.2% and resins 20.2–43.5%. The saturated hydrocarbon fractions included n-C15 to n-C32, with an odd carbon number that predominate in almost all the samples. The contents of n-C27 and n-C29 alkanes are extremely high in some samples, as a contribution of epicuticular waxes from higher plants. Acyclic isoprenoid hydrocarbons are minor constituents in the aliphatic fraction, and the pristane/phytane (Pr/Ph) ratio varies between 0.56 and 3.13, which implies anaerobic to oxic conditions during sedimentation. The most abundant diterpanes were abietane, dehydroabietane and 16α(H)-phyllocladane. In samples from the upper part of the coal seam, diterpanes are the dominant constituents of the alkane fraction. Polycyclic alkanes of the triterpane type are important constituents of alkane fractions. The occurrence of ββ- and αβ-type hopanes from C27 to C31, but without C28, is typical for the Soko Banja coals. The major and trace elements in the coal were analysed using X-ray fluorescence (XRF), and inductively coupled plasma-mass spectrometry (ICP-MS). In comparison with world lignites, using the geometric mean value, the coal from the Soko Banja Basin has a high content of strontium (306.953 mg/kg). Higher values than the world lignites were obtained for Mo (3.614 mg/kg), Ni (8.119 mg/kg), Se (0.884 mg/kg), U (2.642 mg/kg) and W (0.148 mg/kg). Correlation analysis shows inorganic affinity for almost all the major and trace elements, except for S, which has an organic affinity.

Trace elements in the Goze Delchev coal deposit, Bulgaria

Abstract The geochemistry of trace elements in the underground and open-pit mine of the Goze Delchev subbituminous coal deposit have been studied. The coals in both mines are highly enriched in W, Ge and Be, and at less extent in As, Mn and Y as compared with the world-wide Clarkes for subbituminous coals. Ni and Ti are also enhanced in the underground coals, and Zr, Cr and Mo in the open-pit mine coals. Characteristic for the trace element contents in the deposit is a regular variation with depth. The following patterns were distinguished for profile I: a — the element content decreases from the bottom to the top of the bed paralleling ash distribution (Fe, Co, As, Sb, V, Y, Mo, Cs, REE, Hf, Ta, Th, P and Au); b — Ge and W are enriched in the near-bottom and near-top coals; c — in the middle part of the bed the content of K and Rb is maximal, while that of U is slightly enriched; d — Ba content decreases from the top to the bottom of the bed. In profile II, W and Be contents decrease from the bottom to the top. The near-bottom, and especially the near-roof samples of profile IV are highly enriched in Ge, while for W the highest is the content of the near-bottom sample. Ge, Be, As, Mn, Cl and Br are mainly organically associated. The organic affiliation is still strong for Co, B, Sr, Ba, Sb, U, Th, Mo, La, Ce, Sm, Tb and Yb in the underground coals, and Fe, Co, Na, W, Sr, Y and Ag in the coals from the open-pit mine. K, Rb, Ti, Zr, Hf and Ta are of dominant inorganic affinity. The chalcophile and siderophile elements correlate positively with Fe and each other and may be bound partly with pyrite or other sulphides and iron containing minerals. Compared statistically by the t-criteria, the elements Na, Li, Cu, Zn, Pb, Cr, Ni, Co, Mo, Fe and Be are of higher content in the open-pit mine. Tungsten is the only element of higher concentration in the underground mine. The contents of Ge, As, Sr, V, Mn, Y, Zr and P are not statistically different in both mines. It was supposed that there were multiple sources of the trace elements in the deposit. The source of the highly enriched elements (W, Ge, Be, and As) most probably were the thermal waters in the source area. The contemporary mineral springs are of high content of these elements. Another source were the hosting Mesta volcanic rocks, which are enriched in Sb, Mo, Hf, U, Th, As, Li and Rb. Some of the volcanics were hydrothermally altered and enriched or depleted of many elements. Thus, the hydrothermal solutions were also suppliers of elements for the coals. It is obvious that the contents, distribution and paragenesis, of the trace elements in both Goze Delchev coals reflect the geochemical specialization of the source area, including rocks, paleo- and contemporary thermal waters.