Trace elements in the Goze Delchev coal deposit, Bulgaria

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.     

Geochemical characteristics of REY,Li, Ga trace elements in the No. 9 coal seam of the Daheng mine,Ningwu coalfield,Shanxi Province,China

To understand the geochemical characteristics of the No.9 coal in the Daheng Mine of the Ningwu coalfield, the trace element analysis was conducted through X-ray fluorescence spectroscopy (XRF) and inductively coupled plasma mass spectrometry (ICP-MS). The sedimentary environment was discussed according to the element geochemical parameters. The results show that Li, Ga, Hf, Zr, Nb, Th, and Ta are slightly enriched in the No. 9 coal of Daheng Mine. The average value of the rare earth elements and yttrium (∑REY) in coal here is 144.20 μg/g (excluding parting), which is higher than the average value of ∑REY in the world ’s coal and China ’s coal. The light rare earth elements (LREY) are enriched. The content of Eu was 0.12–2.10 μg/g with an average of 0.57 μg/g, and the Eu is obviously negatively abnormal. Most of the trace elements in the coal are positively correlated with the ash content, which shows that the occurrence of these trace elements is related to inorganic minerals. The results of sequential chemical extraction experiments show that rare earth elements mainly exist in coal in the form of aluminosilicate. The value of the Sr/Ba and the content of S reflect that the coal-forming environment was influenced by seawater. The values of V/Cr and Ni/Co reflect that the peat swamp is in an anaerobic environment and a strongly reducing environment during the coal-forming period.     

LA-ICP-MS trace element analysis of pyrite from the Xiaoqinling gold district, China: Implications for ore genesis

The Xiaoqinling district, the second largest gold producing district in China, is located on the southern margin of the North China Craton. It consists of three ore belts, namely, the northern ore belt, the middle ore belt and the southern ore belt. Pyrite from the Dahu gold deposit in the northern ore belt and Wenyu and Yinxin gold deposits in the southern ore belt were investigated using a combination of ore microscopy and in-situ laser-ablation inductively-coupled plasma-mass spectrometry (LA-ICP-MS). A range of trace elements was analyzed, including Au, Te, Ag, Pb, Bi, Cu, Co, Ni, Zn, Mo, Hg, As and Si. The results show that there are no systematic differences between the trace element compositions of pyrite in the three deposits from different ore belts. In general, Au concentrations in pyrite are low (from < 0.01 ppm to 2.2 ppm) but Ni concentrations are rather high (up to 8425 ppm). A four-stage mineralization process is indicated by microscopic and field observations and this can be related to the systematic trace element differences between distinct generations of pyrite. Stage I precedes the main gold mineralization stage; pyrite of this stage has the lowest Au concentrations. Stages II and III contributed most of the gold to the ore-forming system. The corresponding pyrite yielded the highest concentrations of Au and Ni. Our microscopic observations suggest that pyrite in the main gold mineralization stage precipitated simultaneously with molybdenite that has been previously dated as Indosinian (~ 218 Ma by Re–Os molybdenite dating), indicating the Indosinian as the main gold mineralization stage. The Indosinian mineralization age and the geological and geochemical features of these gold deposits (e.g., low salinity, CO₂-rich ore fluids; spatial association with large-scale compressional structures of the Qinling orogen; δ¹⁸O and δD data suggestive of mixing between metamorphic and meteoric waters; δ³⁴S and Pb-isotopic data that point to a mixed crustal-mantle source) all point to typical orogenic-type gold deposits. High Ni concentrations (up to 8425 ppm) of pyrite possibly linked to deep-seated mafic/ultramafic metamorphic rocks provide further evidence on the orogenic gold deposit affinity, but against the model of a granitic derivation of the mineralizing fluid as previously suggested by some workers. Generally low Au concentration in pyrite is also consistent with those from worldwide orogenic gold deposits. Therefore, the gold mineralization in the Xiaoqinling district is described as orogenic type, and is probably related to Indosinian collision between the North China Craton and the Yangtze Craton.     

Rare earth element sources and modification in the Lower Kittanning coal bed, Pennsylvania: implications for the origin of coal mineral matter and rare earth element exposure in underground mines

In this study, we examine the variations in rare earth elements (REE) from the Lower Kittanning coal bed of eastern Ohio and western Pennsylvania, USA, in an attempt to understand the factors that control mineral matter deposition and modification in coal, and to evaluate possible REE mixed exposure hazards facing underground mine workers. The results of this study suggest that the Lower Kittanning coal mineral matter is derived primarily from a clastic source similar to that of the shale overburden. While highly charged cations like silicon, aluminum, and titanium remained relatively immobile within the coal mineral matter, iron (primarily as pyrite) was added from nonclastic sources, either during deposition of the coal mire vegetation or subsequent to burial. Other mobile cations (e.g., alkali and alkaline earth elements) appear to have been added to and/or leached from the originally deposited clastic mineral matter. Most of the sulfur in the Lower Kittanning coal bed is bound as FeS₂ in the mineral matter, but a majority of samples contain a small excess of S that is most likely organically bound.In general, the total rare earth element content (TREE) in coal ash is greater than that in the shale overburden. If the primary source of mineral matter is the same as that for the overlying shale, then REE must have been enriched in the coal mineral matter subsequent to deposition. The total rare earth element content of Lower Kittanning coals correlates strongly with Si concentration ([TREE]≈0.0024 [Si]), which provides a threshold for evaluating possible mixed exposure health effects. Chondrite-normalized REE patterns reveal a shale-like light rare earth element (LREE) enrichment for the coal, similar to that of the shale overburden, again suggesting a primarily clastic REE source. However, when normalized to the shale overburden, most of the coal ash samples display a small but distinct heavy rare earth element (HREE) enrichment. We surmise that the HREE were added and/or preferentially retained during epigenesis, possibly associated with groundwater flow through the coal unit, but not necessarily in close association with the addition of iron. At least some of the “excess” HREE could be organically bound within the Lower Kittanning coal.     

Geochemistry of rare earth elements in a marine influenced coal and its organic solvent extracts from the Antaibao mining district, Shanxi, China

Twenty-six samples including roof, bottom and coal plies of a marine influenced coal bed were collected from the Antaibao mining district, Shanxi, China. The rare earth elements (REEs) were determined in solids and organic solvent extracts. The distribution pattern showed three distinct patterns: shale-like, LREE-rich and HREE-rich. This is attributed to the variable microenvironment of peat-forming swamp, the degree of marine influences and different REE sources. REEs in the coal are mainly controlled by detrital minerals but also affected by seawater. The chondrite-normalized REE patterns of the organic solvent extracts are distinctly different from those of corresponding original coal samples, which show a negative Eu anomaly, a depletion of middle REEs and an enrichment of HREEs. The LREEs in coal extracts are likely adsorbed by hydrogen-containing functional groups, and HREEs are likely bonded to carbon atoms.     

Notes on the marginal enrichment of Germanium in coal beds

Germanium distribution in coal has long been a topic of interest. The enrichment of Ge near margins of coals, including the margins of partings within the coal, has been noted in many coals from numerous coalfields throughout the world. In this paper, a summary of literature on Ge geochemistry on the upper and lower margins of coal seams, with special emphasis on the literature of Russia, and the former Soviet Union, and Japan, is presented.     

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

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.     

兖州矿区山西组 3煤层中微量元素的特征分析

通过对兖州矿区山西组3煤层21个样品中全硫、硫化物硫、有机硫和具有环境意义的微量元素Cu、Pb、Zn、As、U、Th含量的测试，分析了微量元素在研究区煤层垂直方向上的变化特征及主要形成原因，并发现煤层中所选的微量元素、硫化物琉及全硫在煤层顶、底或煤层夹矸样品中含量相对较高。微量元素与硫化物硫、全硫的相关系数表明，所研究的微量元素与硫化物硫和全硫有明显的正相关关系，而且研究区3煤层中全硫的含量取决于硫化物硫的含量。同时还研究了原煤中微量元素的含量与灰产率的关系，并将研究区微量元素同世界和中国同类煤中的微量元素的含量进行了比较。     

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, R_r=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 μg/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 μg/g, respectively. Sequential extraction showed a high PGE content in the silicate fraction, up to 10.4 μg/g Pd, 1.23 μg/g Pt, and 0.05 μg/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.     

Geochemistry of trace and rare earth elements during weathering of black shale profiles in Northeast Chongqing,Southwestern China: Their mobilization,redistribution, and fractionation

In this study, the mobilization, redistribution, and fractionation of trace and rare earth elements (REE) during chemical weathering in mid-ridge (A), near mountaintop (B), and valley (C) profiles (weak, weak to moderate, and moderate to intense chemical weathering stage, respectively), are characterized. Among the trace elements, U and V were depleted in the regolith in all three profiles, Sr, Nb, Ta, Zr, and Hf displayed slight gains or losses, and Th, Rb, Cs, and Sc remained immobile. Mn, Ba, Zn, Cu, and Cr were enriched at the regolith in profiles A and B, but depleted in profile C. Mn, Pb, and Co were also depleted in the saprock and fractured shale zones in profiles A and B and enriched in profile C. REEs were enriched in the regolith and depleted at the saprock zone in profiles A and B and depleted along profile C. Mobility of trace and REEs increased with increasing weathering intensity. Normalized REE patterns based on the parent shale revealed light REE (LREE) enrichment, middle REE (MREE), and heavy REE (HREE) depletion patterns. LREEs were less mobile compared with MREEs and HREEs, and this differentiation increased with increasing weathering degree. Positive Ce anomalies were higher in profile C than in profiles A and B. The Ce fractionated from other REE showed that Ce changed from trivalent to tetravalent (as CeO₂) under oxidizing conditions. Minimal REE fractionation was observed in the saprock zone in profiles A and B. In contrast, more intense weathering in profile C resulted in preferential retention of LREE (especially Ce), leading to considerable LREE/MREE and LREE/HREE fractionation. (La/Yb)_N and (La/Sm)_N ratios displayed maximum values in the saprock zone within low pH values. Findings demonstrate that acidic solutions can mobilize REEs and result in leaching of REEs out of the highly acidic portions of the saprock material and transport downward into fractured shale. The overall behavior of elements in the three profiles suggests that solution pH, as well as the presence of primary and secondary minerals, play important roles in the mobilization and redistribution of trace elements and REEs during black shale chemical weathering.     

黔中—渝南铝土矿含矿岩系微量元素区域分布特征及物质来源探讨

黔中—渝南成矿带石炭纪铝土矿含矿岩系,分别形成于修文、息烽—遵义和黔北—渝南三个沉积区,大多数铝土矿属产于碳酸盐岩侵蚀面上的、少数为产于泥页岩侵蚀面上的硬水铝石沉积型铝土矿床。修文沉积区铝土矿中Zr、RE₂O₃含量最多,息烽—遵义沉积区铝土矿中Ga含量最多,黔北—渝南沉积区Li含量最多,各有特色。修文沉积区铝土矿含矿岩系的母岩,是其下伏寒武系碳酸盐岩与下奥陶统页岩、灰岩、白云岩;息烽—遵义沉积区含矿岩系的母岩为下伏下奥陶统页岩、灰岩及白云岩;黔北—渝南沉积区含矿岩系的母岩,是下伏下志留统泥、页岩和上石炭统石灰岩。碳酸盐岩中Al₂O₃与稳定的微量元素含量甚少,要演变成大面积铝土矿,必须要配以足够的含Al₂O₃和微量元素较多的泥、页岩,才可能满足形成大规模铝土矿的物质需求。     

Geochemistry and petrology of selected coal samples from Sumatra, Kalimantan, Sulawesi, and Papua, Indonesia

Indonesia has become the world's largest exporter of thermal coal and is a major supplier to the Asian coal market, particularly as the People's Republic of China is now (2007) and perhaps may remain a net importer of coal. Indonesia has had a long history of coal production, mainly in Sumatra and Kalimantan, but only in the last two decades have government and commercial forces resulted in a remarkable coal boom. A recent assessment of Indonesian coal-bed methane (CBM) potential has motivated active CBM exploration. Most of the coal is Paleogene and Neogene, low to moderate rank and has low ash yield and sulfur (generally < 10 and < 1 wt.%, respectively). Active tectonic and igneous activity has resulted in significant rank increase in some coal basins. Eight coal samples are described that represent the major export and/or resource potential of Sumatra, Kalimantan, Sulawesi, and Papua. Detailed geochemistry, including proximate and ultimate analysis, sulfur forms, and major, minor, and trace element determinations are presented. Organic petrology and vitrinite reflectance data reflect various precursor flora assemblages and rank variations, including sample composites from active igneous and tectonic areas. A comparison of Hazardous Air Pollutants (HAPs) elements abundance with world and US averages show that the Indonesian coals have low combustion pollution potential.     

The role of sulphide and carbonate minerals in the concentration of chalcophile elements in the bituminous coal seams of a paralic series (Upper Carboniferous) in the Upper Silesian Coal Basin (USCB), Poland

Sulphide and carbonate minerals from nine bituminous coal seams of a Paralic Series were investigated by means of polished-section microscopy, scanning electron microscopy and absorption spectral analyses. In addition to syngenetic accumulations of kaolinite, illite and quartz, diagenetic veinlets of subhedral pyrite and marcasite most often occur in vitrinite clast fissures and in post-tectonic fissures, nests and lenses with fusinite. Epigenetic anhedral and subhedral grains of ankerite, dolomite, siderite and calcite are also frequently found in post-tectonic veins. Pyrite replaced some of the marcasite grains and it dominates in older coal seams in the Flora Beds as compared with the Grodziec Beds. Occasionally there are anhedral and subhedral galena, sphalerite and chalcopyrite grains among coal macerals as well as cerussite among post-tectonic carbonate veins. They all represent the only minerals that are abundant in definite chalcophile elements (Cd, Co, Cu, Ni, Pb, Zn). In addition to the minerals just mentioned, the elements occurred in pyrite and ankerite grains, which contained inclusions of fusinite and other minerals (among others, clay and carbonate minerals in pyrite, pyrite in carbonates). Although there is a low content of minerals accumulating Cd, Co, Cu, Ni, Pb and Zn, the minerals significantly influence the average concentration of elements in the coal seams. In the Grodziec Beds, mineral matter, especially carbonates and sulphides, determines (>50%) the concentration of Cd, Cu, Pb and Zn in coal. The basic part of Cd, Co and Ni in the coal seams of the Grodziec Beds and of Co, Cu, Ni, Pb and Zn in coal seams of the Flora Beds originates from organic matter. These regularities can be important, from an ecological perspective, in stating whether the coals investigated are useful for combustion and in chemical processing.     

Mineral and inorganic chemical composition of the Pernik coal, Bulgaria

The mineral and inorganic chemical composition of five types of samples from the Pernik subbituminous coals and their products generated from the Pernik preparation plant were studied. They include feed coal, low-grade coal, high-grade coal, coal slime, and host rock. The mineral matter of the coals contains 44 species that belong mainly to silicates, carbonates, sulphates, sulphides, and oxides/hydroxides, and to a lesser extent, chlorides, biogenic minerals, and organic minerals. The detrital minerals are quartz, kaolinite, micas, feldspars, magnetite, cristobalite, spessartine, and amphibole. The authigenic minerals include various sulphides, silicates, oxihydroxides, sulphates, and carbonates. Several stages and substages of formation were identified during the syngenetic and epigenetic mineral precipitations of these coals. The authigenic minerals show the greatest diversity of mineral species as the epigenetic mineralization (mostly sulphides, carbonates, and sulphates) dominates qualitatively and quantitatively. The epigenetic mineralization was a result of complex processes occurring mostly during the late development of the Pernik basin. These processes indicate intensive tectonic, hydrothermal and volcanic activities accompanied by a change from fresh to marine sedimentation environment. Thermally altered organic matter due to some of the above processes was also identified in the basin. Most of the trace elements in the Pernik coals (Mo, Be, S, Zr, Y, Cl, Ba, Sc, Ga, Ag, V, P, Br, Ni, Co, Pb, Ca, and Ti) show an affinity to OM and phases intimately associated with OM. Some of the trace elements (Sr, Ti, Mn, Ba, Pb, Cu, Zn, Co, Cr, Ni, As, Ag, Yb, Sn, Ga, Ge, etc.) are impurities in authigenic and accessory minerals, while other trace elements (La, Ba, Cu, Ce, Sb, Bi, Zn, Pb, Cd, Nd, etc.) occur as discrete phases. Elements such as Sc, Be, Y, Ba, V, Zr, S, Mo, Ti, and Ga exceed Clarke concentrations in all of the coal types studied. It was also found that a number of elements in the Pernik coals (F, V, As, Pb, Mo, Li, Sr, Ti, Ga, Ni, Ge, Cr, Mn, etc.) reveal mobility in water and could have some environmental concerns.     

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

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

Composition and quality of coals in the Huaibei Coalfield, Anhui, China

The Huaibei Coalfield, Anhui Province, China, is one of the largest coalfields in China. The coals of Permian age are used mainly for power generation. Coal compositions and 47 trace elements of the No. 10 Coal of the Shanxi Formation, the No. 7, 5, and 4 Coals of the Lower Shihezi Formation, and the No. 3 Coal of the Upper Shihezi Formation from the Huaibei Coalfield were studied. The results indicate that the Huaibei coals have low ash, moisture, and sulfur contents, but high volatile matter and calorific value. The ash yield increases stratigraphically upwards, but the volatile matter and total sulfur contents show a slight decrease from the lower to upper seams. Magmatic intrusion into the No. 5 Coal resulted in high ash, volatile matter, and calorific value, but low moisture value in the coal. Among the studied 47 trace elements, Ba, Co, Cr, Cu, Hg, Mo, Ni, Pb, Sb, Th, U, V, and Zn are of environmental concerns. Four elements Hg, Mo, Zn, and Sb are clearly enriched in the coals as compared with the upper continental crust.     

重庆南川晚二叠世凝灰岩的元素地球化学特征

运用电感耦合等离子体质谱(ICP MS)、X射线荧光光谱(XRF)、X射线衍射（XRD）、带能谱的扫描电镜（SEM EDX）等方法对重庆南川晚二叠世凝灰岩的元素地球化学特征进行了研究。研究发现,凝灰岩中富集Al、Ti、Li、Cu、V、Cr、Co、Ni、Nb、Ta、Zr、Hf、Ga、Sc、Th、U和稀土元素（REE）,其中Ti、Nb、Ga和REE异常富集,达到了伴生矿产的工业品位,其综合利用价值值得关注。凝灰岩自底部至顶部微量元素含量有明显增加的趋势,稀土元素（REE）在垂向上分异明显,凝灰岩上部富集轻、中稀土,向下逐渐过渡到富集重稀土类型。凝灰岩中元素的组合特征表明其原始物质可能来源于峨眉山玄武岩岩浆,属于基性火山灰成因。     

A comparative evaluation of minerals and trace elements in the ashes from lignite, coal refuse, and biomass fired power plants

Coal being a limited source of energy, extraction of energy from other sources like lignite, coal-refuse, and biomass is being attempted worldwide. The minerals and inorganic elements present in fuel feeds pose different technological and environmental concerns. Lignite ash, refuse ash, and biomass ash collected from Indian power plants burning lignite, coal-refuse, and mustard stalk, respectively, were analyzed for physico-chemical characteristics and trace elements. The lignite ash has high SiO₂, CaO, MgO, Al₂O_3, and SO₃; the refuse ash has high SiO₂ and Fe₂O₃, but low SO₃; the biomass ash has high SiO₂ (but low Al₂O₃), and high CaO, MgO, K₂O, Na₂O, SO₃, and P₂O₅. A substantial presence of chloride (2.1%) was observed in the biomass ash. Quartz is the most abundant mineral species. Other minerals are mullite, hematite, gehlenite, anhydrite, and calcite in the lignite ash; orthoclase in the refuse ash; albite, sanidine, gehlenite, anhydrite, and calcite in the biomass ash. Ashes with high concentrations (> 100 mg/kg) of trace elements are: lignite ash (V < La < Mn < Cr < Ni < Nd < Ba < Ce, Zn < Sr); refuse ash (Cr < Ce < V < Rb < Mn < Sr, Zn < Ba); biomass ash (Cu < Zn < Ba, Sr). Based on Earth crust normalization, Co, Ni, As, Se, Mo, Zn, Pb, U, and REEs (except Pr and Er) are enriched in the lignite ash; molybdenum, Zn, Cs, Pb, Th, U, La, Ce, and Lu in the refuse ash; and Mo, Zn, Sr, Cs, Pb, and Lu in the biomass ash. Elements As, Zn, Mo, Ni, Pb, Rb, Cr, V, Ba, Sr, and REEs are correlated with Al, indicating the possibilities of their association with aluminum silicates minerals. Similarly, barium, Cs, Th, and U are correlated with iron oxides; molybdenum and Sr may also be associated with sulfates and chlorides. Due to the alkaline nature of these ashes, the high concentrations of As and Se in the lignite ash; molybdenum in the biomass ash; and Se in the refuse ash may pose environmental concerns.     

A New Family of Galeaspids (Jawless Stem-Gnathostomata) from the Early Silurian of Chongqing, Southwestern China

A new genus and species of agnathan Eugaleaspidiformes (Galeaspida), Yongdongaspis littoralis gen. et sp. nov., is described from the Llandovery (lower Silurian) Huixingshao Formation at Yongdong Town, Xiushan County, Chongqing, southwestern China. This new Telychian taxon morphologically exhibits some transitional states between Sinogaleaspidae and a cluster of higher eugaleaspidiforms containing Tridensaspidae, Eugaleaspidae, Yunnanogaleaspis, and Nochelaspis, which we term here as the ‘eugaleaspid cluster’. Phylogenetic analysis of an extended character matrix of Galeaspida reveals Yongdongaspis, on which Yongdongaspidae fam. nov. is erected, as the sister taxon of this ‘eugaleaspid cluster’, supported by two synapomorphies, the presence of one median transverse canal, and two lateral transverse canals leaving from the infraorbital canal. As the first fish described from the Llandovery Huixingshao Formation in Chongqing, Yongdongaspis provides new fossil evidence for the subdivision and correlation of the Upper Red Beds in South China.     

Mineralogical and elemental variation of coal from Alberta, Canada: an example from the No. 2 seam, Genesee Mine

Mineralogy and elemental contents were determined on 18 samples from a vertical profile of the No. 2 seam, Genesee mine, AB. The samples analyzed consist of coal, coaly shale, shaly coal, carbonaceous shale, shale, mudstone and siltstone. Proximate analysis was determined on all samples. Elemental analyses were determined by instrumental neutron activation analysis (INAA) for all elements except As, B, Cd, Hg, Mo, Pb, Se (Atomic Absorption) and B, Ba, Be, Co, Cr, Cu, Li, Mn, Nb, Sr and V (inductively coupled plasma-emission spectroscopy, ICP-ES). Samples were low temperature ashed (LTA), X-ray diffraction (XRD) and X-ray fluorescence (XRF) were used to determine quantitative major mineralogy. Accessory mineralogy was determined with Scannining Electron microscope/energy dispersive X-ray analyzer (SEM/EDX) on four samples. In general, the coals in the Genesee mine are within the low end of the range for trace element contents given by Swaine [Swaine, D.J., 1990. Trace Elements in Coal. Butterworths, London, 278 pp.] for most coals. High contents of Cr (9–2620 ppm) and Ni (1–1440 ppm) can be related to an increased amount of a Cr–Ni–Fe oxide (chromite–magnetite?) likely derived from ultrabasic diatremes in the Golden-Columbia Icefields, BC area. The No. 2 seam of the Genesee mine can be divided into two geochemical cycles on the basis of mineralogy, trace element contents and rare earth element (REE) behavior. Cycle I consists of quartz, calcite and kaolinite, lower trace element contents, REE slightly enriched in high rare earth elements (HREE), and thick coal with few partings. Cycle II consists of quartz, calcite, kaolinite, illite, mixed layer and/or expandable lattice clays, feldspar, gypsum, calcium aluminum sulfate hydrate, clinoptilolite, calcite and diopside, higher trace element contents, REE slightly enriched in light rare earth elements (LREE) and thin coal with a greater frequency of partings. The differences between the two geochemical cycles can be accounted for by a decreasing stability of the peat-forming environment resulting from an increasing fluvial influence and volcanogenic input.