The properties of macerals in Czechoslovak coals rich in inertinite

Czechoslovak bituminous coals rich in inertinite contain a considerable amount of inertinite with a reflectance range displaced towards and partly overlapping that of the vitrinite reflectance. Together with the existence of the transitional maceral group of semivitrinite, this causes difficulties in maceral analysis as well as in the technological evaluation of these coals. The relationship between the volatile matter of vitrinite and its reflectance is very close for both vitrinite- and inertinite-rich coals. The analogous relationship between the vitrinite reflectance and the volatile matter of inertinite displays a considerable scatter due to the effects of some higher values of the volatile matter of inertinite — related to the presence of inertinite with relatively low reflectance. The results of investigations into the coking properties of coals rich in inertinite, however, do not supply any proof of a higher fusibility of these coals.     

Properties, origin and nomenclature of rodlets of the inertinite maceral group in coals of the central Appalachian basin, U.S.A.

Resin rodlets, sclerenchyma strands and woody splinters, which are collectively called rodlets, were studied by chemical, optical petrographic, and scanning-electron microscopic (SEM) techniques. A study was made of such rodlets from the bituminous coal beds of the central Appalachian basin (Pennsylvanian; Upper Carboniferous) of the United States. Comparisons were made with rodlets from coal beds of the Illinois basin, the Southern Anthracite Field of Pennsylvania, the St. Rose coal field of Nova Scotia, and European and other coal fields. In order to determine their physical and chemical properties, a detailed study was made of the rodlets from the Pomeroy coal bed (high volatile A bituminous coal; Monongahela Formation; Upper Pennsylvanian) of Kanawha County, West Virginia. The origin of the rodlets was determined by a comparative analysis of a medullosan (seed fern) stem from the Herrin (No. 6) coal bed (high volatile C bituminous coal; Carbondale Formation) from Washington County, Illinois. Rodlets are commonly concentrated in fusain or carbominerite layers or lenses in bituminous coal beds of the central Appalachian basin. Most of the rodlets examined in our study were probably derived from medullosan seed ferns. The three types of rodlets are distinguished on the basis of cellularity, morphology and fracture.The resin rodlets studied by us are noncellular and appear to be similar in properties and origin to those found in coal beds of the Middle and Upper Pennsylvanian of the Illinois basin. The resin rodlets extracted from the Pomeroy coal bed exhibit high relief and high reflectance when polished and viewed in reflected light; they are opaque in transmitted light. In cross section, the resin rodlets are oval to round and have diameters ranging from 60 to 450 μm. Many are solid, but some have vesicles, canals or cavities, which are commonly filled with clay, probably kaolinite. Typically, they have distinct fracture patterns (“kerfs”) in longitudinal and cross sections and many are characterized by dense (probably oxidized) rims. The orientation and amounts of void space and mineralization of resin rodlets in coal have resulted in much confusion in their recognition and classification. The resin rodlets are petrographically recognized as sclerotinites of the inertinite maceral group. We here propose that resin rodlets be assigned to the maceral variety of sclerotinites termed “resino-sclerotinite” because of their presumable resinous origin. Other investigators have confused some fusinitized resin rodlets with fungal masses, which have different morphological properties and which probably have different chemical properties. We here propose that such fungal masses be assigned to the maceral variety of sclerotinites termed “fungo-sclerotinite.”The sclerenchyma strands examined in our study are cellular, thick-walled, and crescent-shaped in cross section. They exhibit high reflectance and high relief and belong to semifusinite and fusinite of the inertinite maceral group. Sclerenchyma strands are commonly associated with resin canals in Medullosa and related seed-fern genera, which are common in coal balls of the Illinois basin. We here propose adoption of the maceral varietal terms “sclerenchymo-fusinite” and “sclerenchymo-semifusinite” for these bodies.The woody splinters in the Pomeroy coal bed are cellular and thin-walled and have scattered pits as much as a few microns in diameter. They are dark brown to black in transmitted light and commonly have a lower reflectance than the resino-sclerotinite and sclerenchymo-fusinite of the Pomeroy coal. The woody splinters belong to semifusinite and fusinite of the inertinite maceral group. The maceral varietal terms “xylemo-semifusinite” and “xylemo-fusinite” are here proposed for these bodies.Elemental chemical data for the resin rodlets of the Pomeroy coal bed of the central Appalachian basin indicate that resin rodlets have significantly lower atomic H/C and O/C ratios than do sclerenchyma strands and woody splinters. The lower atomic H/C and O/C ratios of the resin rodlets correlate with the highest reflectance. In the coal ball medullosan seed-fern stem from the Herrin (No. 6) coal bed of the Illinois basin, the reflectances of the resin rodlets, woody splinters and sclerenchyma strands are similar and comparable to those of associated vitrinite in the coal ball stem and in the attached coal. However, resin rodlets and sclerenchyma strands in the attached coal have significantly higher reflectances, similar to those of the Pomeroy coal.     

山西繁衍峙第三纪煤中丝质体生烃演化特征

丝质体是煤中的主要组分之一 ,其在煤中含量的多少、生烃潜力的大小、生烃特性等直接影响煤成烃资源的评价。本文采用岩石热解、热解气相色谱以及开放体系下热模拟等方法 ,对山西繁峙老第三纪 (E3)煤中丝质体的生烃潜力、烃类组成特征、成烃演化规律进行了研究 ,并与贵州水城晚二叠世 (P2 1 )含树皮体煤中的主要组分 -树皮体进行比较。结果表明 :丝质体的生烃潜力、氢指数 (2 6 .18m g/ g、35 mg/ g· TOC)远低于树皮体的生烃潜力、氢指数 (2 97mg/ g、491mg/ g· TOC) ;丝质体有两个生烃高峰 ,所对应的 VR0 (% )分别为 1.1%和 2 .0 % ;丝质体产烃范围较宽 ,从 2 0 0℃可以延续到 6 0 0℃ ,甚至超过6 0 0℃还有少量的烃类物质生成 ;丝质体的烃类组成以轻质烃为主 ,湿气次之     

Observations on low-temperature oxidation of minerals in bituminous coals

Mineral matter in three naturally weathered coals from Pennsylvania strip mines and in two laboratory-oxidized coals has been characterized by ⁵⁷Fe Mössbauer spectroscopy, scanning electron microscopy and other techniques to determine mineralogical trasnformations that occur in coals during weathering. Pyrite was found to be the most readily oxidized mineral, forming a variety of iron sulfates initially and geethite eventually. The iron sulfates formed were different in the two laboratory-oxidized coals, despite identical oxidation treatments. Calcite disappeared from one calcite-rich coal with increasing oxidation, but was not replaced by an equivalent amount of gypsum. A severely weathered strip-mine coal was enriched in calcium, which was dispersed through the oxidized macerals. Extended X-ray absorption fine-structure spectroscopy indicated that this dispersed calcium was most likely present as salts of carboxylic acids. Siderite was suprisingly resistant to oxidation at room temperature. Less direct evidence indicates that clay minerals also take part in the alteration to some extent.The coals oxidized in the laboratory showed alteration behavior that differed in a number of respects from that of the strip-mine coals. For example, iron sulfates were much less common in the latter coals; also, the formation of geothite appeared to be controlled to a large extent by the pyrite particle size in the strip-mine coals, but not in the laboratory-oxidized coals.The oxidation of an individual pyrite grain is not only a function of general conditions (temperature, humidity, oxygen partial pressure), but also the immediate local (< 1 mm) chemistry, as a variety of iron sulfates were observed in the coals, often in close proximity. Also, assemblages of gypsum and goethite were observed in otherwise slightly oxidized coal, which indicates that the alteration of pyrite and calcite, when in close contact, proceeds most rapidly.     

Mineral matter in coals: cleat minerals and their origin in some coals from the english midlands

In four coal seam profiles from the Cannock Coalfield, West Midlands, the cleat (joint) frequency is a function of lithotype (greatest in vitarin) and is inversely related to bed thickness. The cleat minerals were studied: (1) under the microscope (optical and electron); (2) by X-ray diffraction; and (3) chemically. The minerals present are pyrite, marcasite, sphalerite, galena (sulphides), quartz, kaolinite (silicates), ankerite, calcite (carbonates) and apatite. This sequence has features in common with diagenetic sequences recorded in other rock types and it is concluded that the cleat minerals in coal form in response to pore fluid evolution and movement during burial diagenesis. The elements are thought to originate from both the coal and the associated sediments, mainly mudrocks. Similarities in diagenetic sequences are in part a reflection of the importance of organic maturation reactions in all the rock types in the sequence, whereas differences are attributed to the dominance of these reactions in the coal itself.     

Chemical composition of macerals in bituminous coals of the Gunnedah Basin, Australia, using electron microprobe analysis techniques

The chemical composition of the organic matter in the principal macerals of high-volatile bituminous coals from the Gunnedah Basin, New South Wales (Rv_max of telocollinite between 0.6 and 1.1%) has been evaluated from polished section specimens using an electron microprobe technique. Highest proportions of carbon occur in the inertinite macerals, especially fusinite and secretinite (formerly resino-sclerotinite), as well as in sporinite; lowest proportions of carbon occur in the different macerals of the vitrinite group. Oxygen shows the reverse trend, being most abundant in vitrinite and least abundant in the inertinite components, whereas sulphur is lowest in the inertinites and highest in the liptinite (mainly sporinite) present. Evaluations of maceral composition, using the carbon content of telocollinite as a rank indicator, show that carbon is more abundant in both sporinite and semifusinite, relative to vitrinite, in low-rank high-volatile bituminous coals. The difference decreases with increasing rank, and the proportion of carbon in telocollinite becomes essentially the same as that in sporinite and semifusinite at carbon contents of about 89 and 91%, respectively. The carbon content of fusinite and secretinite, on the other hand, does not seem to vary appreciably with rank advance. No significant difference in composition occurs in the rank range studied between the three vitrinite varieties present, desmocollinite, telocollinite and a more highly reflecting telocollinite resembling pseudovitrinite. No evidence was found to indicate a higher hydrogen content, relative to telocollinite, for the vitrinite matrix of desmocollinite.     

A study of the kinetic parameters of individual macerals from Upper Permian coals in South China via open-system pyrolysis

A unique Upper Permian coal, Leping coal, is widely distributed in South China. The coal samples studied in the paper were collected from two mines in the Shuicheng coalfield of Guizhou Province, southwest China. The geochemical works including coal petrography, maceral content, Rock–Eval pyrolysis, and kinetic modelling of hydrocarbon-generating have been carried out on whole coal and individual macerals. The higher contents of volatile matter, elemental hydrogen, and tar yield, and the high hydrocarbon generation potential of the Leping coals are attributed to their high content of “barkinite”, a special liptinite maceral.The hydrocarbon generation potential of “barkinite” (S₂=287 mg/g, hydrogen index (HI)=491 mg/g TOC) is greater than that of vitrinite (S₂=180 mg/g, HI=249 mg/g TOC), and much higher than that of fusinite (S₂=24 mg/g, HI=35 mg/g TOC). At the same experimental conditions, “barkinite” has a higher threshold and a narrower “oil window” than those of vitrinite and fusinite, and consequently, can generate more hydrocarbons in higher coalification temperature and shorter geological duration. Data from the activation energy distributions indicate that “barkinite” has a more homogenous chemical structure than that of vitrinite and fusinite. The above-mentioned characteristics are extremely important for exploring hydrocarbon derived from the Leping coals in South China.     

Geochemistry and origin of elements in some UK coals

Twenty-four UK coals ranging in rank with 4.6%–37.6% volatile matter were analysed for 46 major and trace elements. The samples were obtained from the UK Coal Bank and are representative of the major UK coal fields. The major element distributions are interpreted in terms of the mineralogical variations—quartz and kaolinite are largely responsible for the Si and Al, carbonates for Ca and Mg and pyrite for Fe. Also exerting an influence in some samples are siderite, Al-phosphate minerals and illite. Based on statistical relationships with the major elements, Rb, Cr, Th, Ce, Zr, Y, Ga, La, Ta, Nb and V are thought to be mainly present in the clay minerals, and As, Mo, Sb, Tl, Se and Bi and Pb are probably present in pyrite. Strontium and Ba are concentrated in a restricted number of samples related to the phosphate minerals. Germanium is the only element for which a major organic association can be demonstrated. Elements with an indirect association with the organic matter are Na, Cl, and Br in porefluids and possibly Te. The ash content is controlled mainly by the detrital input and the trace elements related to the ash content are therefore those elements associated with the clay minerals. Variations with rank would appear to be mainly related to the moisture content (porefluids). The trace elements associated with the quartz and clay minerals are thought to be dominantly detrital in origin. The non-detrital elements, essentially those contained in pyrite, are thought to have been incorporated in the depositional environment from waters with enhanced salinities through seawater ingress, hence there are positive relationships between S and trace element concentrations.     

Structure and origin of terpenoid hydrocarbons in some German coals

Hydrocarbon extracts of coal samples from major coal fields in West Germany have been investigated by gas chromatography-mass spectrometry (GC/MS). The samples are of Carboniferous and Tertiary age and derive from limnic and paralic environments, the Saar District, the Ruhr Area and the Lower Rhine Basin.Differences in facies, maturity and age reflected in the distribution patterns of the extracted alkylcyclohexanes. An unexpected occurrence of cyclic diterpenoid hydrocarbons in some samples of Carboniferous age has been found. The tetracyclic compounds mainly show phyllocladane type structures and can serve as source indicators.Hydrocarbons obtained from chemical degradation of the macromolecular material of the samples also revealed phyllocladane-type compounds which are normally associated to resins of modern and extinct familes of conifers. Origin and structural variations of this class of hydrocarbons are discussed in terms of maturity and palaeobotanical implications.     

Distribution, isotopic variation and origin of sulfur in coals in the Wuda coalfield, Inner Mongolia, China

This paper describes coal petrographic characteristics, sulfur abundance, distribution and isotopic signature in coals in the Wuda coalfield, Inner Mongolia, northern China. Petrographic studies suggest that depositional environment influences petrographic composition. The No. 9 and No. 10 coal seams, which are thought to have formed on a tidal delta plain, have high collodetrinite contents (up to 66.1%) indicating enhanced gelification and bacteria activity during coal accumulation, and also have the highest sulfur content (3.46% and 3.42%). Both organic and pyritic sulfur isotope values (−12.3‰ to 5.8‰ and −18.7‰ to 1.1‰, respectively) are variable and generally tend to be more negative in high-sulfur coals than those in low-sulfur coals in the Wuda coalfield. The negative sulfur isotope values indicate that a large portion of sulfur in the high-sulfur coals has a bacterial origin. Sulfur isotopic compositions and variations within the section were used to propose a model to explain the origin of sulfur in these coals. The presence of pyritized rod-like bacteria, cyanophyte's gelatinous sheaths and degraded algae organic matter suggests that bacteria, and perhaps algae, may play an important role in the formation of these high-sulfur coals.     

煤中显微组分的成烃演化实验

热解模拟实验揭示,镜质组的生烃作用与其起始成熟度有关,如果初次生烃中止,成熟度 (再次生烃起始成熟度)尚未超过生油高峰阶段 (R=0.9%),则再次生烃有可能显著提高煤的生烃潜量,且以起始成熟度在生烃高峰处的升高幅度为最大。在有机显微组分中:壳质组的生烃量最大,生烃范围最集中;镜质组次之;惰质组最少。     

Application of reflectance micro-Fourier transform infrared analysis to the study of coal macerals: an example from the late jurassic to early cretaceous coals of the Mist Mountain Formation, British Columbia, Canada

The applicability of the reflectance micro-Fourier Transform infra-red spectroscopy (FTIR) technique for analyzing the distribution of functional groups in coal macerals is discussed. High quality of spectra, comparable to those obtained using other FTIR techniques (KBr pellet and transmission micro-FTIR), indicate this technique can be applied to characterizing functional groups under most conditions. The ease of sample preparation, the potential to analyze large intact samples, and ability to characterize organic matter in areas as small as 20 μm are the main advantages of reflectance micro-FTIR. The quantitative aspects of reflectance micro-FTIR require further study.The exaples from the coal seams of the Mist Mountain Formation, British Columbia show that at high volatile bituminous rank, reflectance micro-FTIR provides valuable information on the character of aliphatic chains of vitrinite and liptinite macerals. Because the character of aliphatic chains influences bond disassociation energies, such information is useful from a hydrocarbon generation viewpoint. In medium volatile bituminous coal liptinite macerals are usually not detectable but this technique can be used to study the degree of oxidation and reactivity of vitrinite and semifusinite.     

黔西晚二叠世煤地球化学性质变异及特殊组构的火山灰成因

运用仪器中子活化分析(INAA)、电感耦合等离子体原子发射光谱(ICP—AES)、X射线衍射(XRD)、带能谱仪的扫描电镜(SEM—EDX)及光学显微镜等手段，对黔西晚二叠世煤地球化学性质变异及其特殊组构的火山灰成因进行了研究。结果表明，贵州西部织金矿区9煤层中异常高含量的Fe(4．24％)、Cu(369．90μg／g)、U(49．6μg／g)、Mo(63．10μg／g)、Zn(33．97μg／g)等是来源于同沉积基性火山灰降落到泥炭沼泽中所致；高含量的Fe、Cu并非以通常意义的煤中硫化物状态存在；除煤中有机质和陆源碎屑外，发现了由火山灰、有机质和陆源碎屑所形成的煤层中的特殊组构，暂定名为沉碳质火山胶凝物，它是一种有机—无机高度混合物质，根据沉碳质火山胶凝物的形态特征和物质组成，厘定出6种组构类型，分别是：网状组构、细屑组构、基质组构、孔腔组构、均质组构和碎屑组构。     

Diagenetic mineralization in Pennsylvanian coals from Indiana, USA: C/C and O/O implications for cleat origin and coalbed methane generation

Cleats and fractures in southwestern Indiana coal seams are often filled with authigenic kaolinite and/or calcite. Carbon- and oxygen-stable isotope ratios of kaolinite, calcite, and coalbed CO₂ were evaluated in combination with measured values and published estimates of δ¹⁸O of coalbed paleowaters that had been present at the time of mineralization. δ¹⁸O_mineral and δ¹⁸O_water values jointly constrain the paleotemperature of mineralization. The isotopic evidence and the thermal and tectonic history of this part of the Illinois Basin led to the conclusion that maximum burial and heat-sterilization of coal seams approximately 272 Ma ago was followed by advective heat redistribution and concurrent precipitation of kaolinite in cleats at a burial depth of < 1600 m at  78 ± 5 °C. Post-Paleozoic uplift, the development of a second generation of cleats, and subsequent precipitation of calcite occurred at shallower burial depth between  500 to  1300 m at a lower temperature of 43 ± 6 °C. The available paleowater in coalbeds was likely ocean water and/or tropical meteoric water with a δ¹⁸O_water  − 1.25‰ versus VSMOW. Inoculation of coalbeds with methanogenic CO₂-reducing microbes occurred at an even later time, because modern microbially influenced ¹³C-enriched coalbed CO₂ (i.e., the isotopically fractionated residue of microbial CO₂ reduction) is out of isotopic equilibrium with ¹³C-depleted calcite in cleats.     

贵州煤中某些金属元素异常富集研究进展

煤层能在特定的地质条件下富集多种关键金属元素,形成具有综合利用价值的“煤型关键金属矿床”,随着煤中共伴生金属元素提取技术日益成熟,研究煤中金属元素的富集与分布特征、查明具有成矿潜力的富集区具有十分重要的资源意义。本研究基于近20年以来前人发表的有关贵州煤地球化学的研究成果及作者自测数据,统计了贵州省23个主要产煤县(市)的1002个样品数据,揭示了贵州煤中Li、Zr、Hf、Nb、Ta、U和稀土元素(REY,即REE+Y)等关键金属元素的总体分布富集特征。研究表明,贵州煤中Li、Zr、Nb、REY等关键金属元素较为富集并具有共伴生成矿潜力的区域为黔北煤田和黔西南兴义煤田两个区域。其中,金沙、桐梓、普安等地煤中Li平均含量换算为灰基Li₂O分别为1254μg/g、1214μg/g和724.4μg/g,务川和正安煤种Zr平均含量换算为灰基ZrO₂分别为4749μg/g和4168μg/g,务川煤中Nb平均含量换算为灰基Nb₂O₅为484.4μg/g,金沙、桐梓、务川及凯里煤中REY含量换算为灰基稀土氧化物R...     

贵州煤中某些金属元素异常富集研究进展

煤层能在特定的地质条件下富集多种关键金属元素,形成具有综合利用价值的“煤型关键金属矿床”,随着煤中共伴生金属元素提取技术日益成熟,研究煤中金属元素的富集与分布特征、查明具有成矿潜力的富集区具有十分重要的资源意义。本研究基于近20年以来前人发表的有关贵州煤地球化学的研究成果及作者自测数据,统计了贵州省23个主要产煤县（市）的1002个样品数据,揭示了贵州煤中Li、Zr、Hf、Nb、Ta、U和稀土元素（REY）等关键金属元素的总体分布富集特征。研究表明,贵州煤中Li、Zr、Nb、REY等关键金属元素较为富集并具有共伴生成矿潜力的区域为黔北煤田和黔西南兴义煤田两个区域。其中,金沙、桐梓、普安等地煤中Li平均含量换算为灰基Li2O 分别为1254 μg/g、1214 μg/g和724.4 μg/g,务川和正安煤种Zr平均含量换算为灰基ZrO2分别为4749 μg/g和4168 μg/g,务川煤中Nb平均含量换算为灰基Nb2O5为484.4 μg/g,金沙、桐梓、务川及凯里煤中REY含量换算为灰基稀土氧化物REO含量分别为2175 μg/g、2429 μg/g、2875 μg/g和2604 μg/g,这些含量均超过了相应矿种的最低工业品位或文献建议的可回收利用指标。贵州煤中多种金属元素具有较高的含量背景值,尤其以黔西南兴义煤田和黔北煤田最为显著,作者建议应进一步加强对上述两个区域的煤地球研究,查清煤中微量元素的时空分布与富集规律,为煤型关键金属矿床的找矿勘查提供更可靠科学依据。贵州晚二叠世煤中异常富集的Li、U、Nb、Ta、Zr、Hf和REY等元素的富集主要受峨眉山玄武岩风化产物的供给、同沉积火山灰的混入以及成煤期后低温热液作用的影响。其中REE的富集,不仅与玄武岩风化产物有关,还可能受到长英质—中性物质输入的影响。     

Metalliferous coals: A review of the main genetic and geochemical types

This paper presents a review of the genetic types and geochemical processes that have formed ‘metalliferous’ coals around the world. Primary attention is given to elements in coal that are currently being extracted from coal as raw material (Ge and U) or have, in our opinion, the best chance for such use (REE, Ag, Au, and PGE). Coals with anomalously high concentrations of other metals having potential for economic by-product recovery (Be, Sc, V, Ga, Sb, Cs, Mo, W, and Re) are briefly considered. Original data and a survey of the literature indicate that metalliferous coals are in many coal basins. Ore formation in coal-bearing structures may occur during peat accumulation, during diagenesis of the organic matter, or by epigenesis. Various metals are supplied to sedimentary basins as minerals that are transported by water and wind or as ionic species in surface water and descending and ascending underground water and may be incorporated into peat or coals. The modes of occurrence of metals in the enriched coals are diverse. The data presented in this review indicates that metalliferous coals should be regarded as promising for economic recovery for by-products in the course of coal mining and combustion.     

Study on the suitability of New Zealand coals for hydrogen production

Internationally there is considerable interest in utilizing hydrogen as an energy carrier. The use of hydrogen offers considerable potential benefits such as reducing greenhouse emissions, reducing urban pollution, increased energy security and increased efficiencies from the use of advanced energy conversion technologies.One of the most important questions when considering the development of a hydrogen economy is “where will the hydrogen come from?” Possible answers include electrolysis of water, steam reforming of methane and the gasification of coal. Given the high costs associated with electrolysis of water, and the increase in the cost of methane predicted over time, the gasification of coal is viewed by many as being the cheapest method of hydrogen production in the foreseeable future. These considerations are particularly relevant to New Zealand where gas supplies are dwindling but where there is sufficient coal to last for many centuries at present utilization rates. This, along with the current high international interest in hydrogen energy, has been recognized by the New Zealand Government in the form of a six-year [2002–2008] research project “Hydrogen Energy for the Future of New Zealand”.One important coal property that, in particular, determines the suitability of a particular coal for use in a fluidised bed gasifier is its reactivity towards the gasification reaction. It was found that a high percentage of New Zealand's coal resource is particularly well-suited towards fluidised bed gasification, reacting at anywhere between 0.9 to 1.75 times the rate of Australian brown coals. It was found the New Zealand lignites contained significant levels of organically bound calcium, which was shown to be responsible for not only the high reactivity of the New Zealand lignites, but also a product gas composition with higher than expected hydrogen concentrations. These findings are discussed along with their implications for the gasifier and gas clean-up design.