COALIFICATION, RANK and TYPE

Coal begins as plant matter deposited in wet peat swamps which whilst undergoing chemical, physical and biogenically aided changes, passes through a series of stages known as coalification. Obviously, the nature of the original plant material will have some influence on the degree of alteration that takes place. The terms rank and type were introduced to distinguish between those features are related to the coalification path, rank, and those features which are associated with the differences in the coal composition, type, remembering of course that chemical changes will occur as coalification takes place. Type is related to the forms of primary plant matter, and the characteristics of each, rather than the chemical changes that take place during coalification. Once the plant matter has been deposited, it may be covered over with clastic sediment or additional plant matter and gelification commences. 1. TYPE Type refers to the nature of the organic matter found in a coal or sedimentary rock and is thus a function of both the type of precursor organic matter that was deposited as peat and the nature and degree of alteration that the peat components underwent during the early stages of diagenesis. On a gross scale, the type of plant matter, that is, whether the plants are forest trees, swamp herbs or marsh reeds, will determine the type of coal that is formed. For example, if considering coals of brown coal rank, marsh reeds give rise to light brown coals without vitrinite derived from woody stems and the phyterals in the coal are small; vitrodetrinite is abundant. Woody forests give rise to dark brown coals with an abundance of large coalified trunks and branches; telinite is abundant. On a smaller scale the type of plant detritus derived from each of the plant communities will determine the composition of the resulting coal. For example, an abundance of resins, fats, waxes and oils will give rise to resinite-rich coals whereas an abundance of pollen and spores will give sporinite-rich coals. If the plant matter is continually covered with water, little oxygen is available as a reagent and the coal tends to be vitrinite-rich. If the plant matter is periodically exposed, the plant matter may oxidize giving rise to inertinite-rich coal. On a large scale, coals which form in troughs of rapidly subsiding basins will tend to be covered continually with water and the coals will be rich in vitrinite (and the microlithotype vitrite). Australian coals of Permian and Triassic age belong to this category. In fluvio-deltaic environments in cratonic basins, coals tend to be vitrinite poor. The composition of coal may change within a seam. This occurs where the water level changes. For example, some Australian Permian coals have a vitrinite-rich base and inertinite-rich top. This is taken to indicate more exposure to an oxidizing environment while the later stages of the plant matter was deposited. iessel (1982) reported that the term coal type was introduced by White in 1909 to distinguish between types of coals that were initially determined by the nature of the ingredient matter, the conditions of deposition, and the extent of operation of the first or biological process of coal making. He thus distinguished between spore coal, resinous coal, humus coal, leaf coal and bark coal. Because each of the lithotypes have different compositions, each lithotype can be regarded as a coal type. 1.1 Coal Types through the Ages Evolution of flora and climatic changes throughout geological time has resulted in diversity of plant types through the ages and a corresponding change in the type of coals formed. The following is a very brief summary to give some idea of the changes in coal types throughout geological time. It should be viewed as a general summary with many other types of coals, having formed in specific environments, in some parts of the world at various times.

Carboniferous (Pennsylvanian) Mostly these are Northern Hemisphere coals which are generally vitrinite>inertinite>liptinite; liptinite occurs either with vitrinite and minor inertinite to give clarains or with inertinite, especially macrinite, to form durains; some coals contain thin relatively continuous fusain layers. In the USA there are a large number of cannel coals which have dominantly vitrinite (detrovitrinite) with abundant sporinite, micrinite and semifusinite or vitrinite-bituminite-telalginite. Permian Mostly Southern Hemisphere coals which are vitrinite- and inertinite-rich, especially fusinite and semifusinite; vitrain and fusain are common lithotypes; liptinite is much less abundant than in Carboniferous coals, commonly rare and constituting less than 2%; sporinite; rarely abundant; localized algal-rich torbanites in Australia and South Africa. Triassic Two main coal types generally related to different tectonic settings; vitrinite>inertinite>liptinite in areas of subsidence (sequences are commonly thick) and inertinite>vitrinite>liptinite which are typical of stable shelf or fault bounded basins; liptinite commonly crassicutinite. Jurassic Vitrinite>liptinite>inertinite coals where liptinite is commonly suberinite, cutinite and resinite; latter probably a function of floral types whereas Triassic inertinite versus liptinite types may be a function of environment; few inertinite-rich coals. Cretaceous Vitrinite>inertinite>liptinite coals mostly with cutinite and suberinite the dominant liptinite; some Northern Hemisphere coals, such as Canadian Rocky Mountains, are inertinite-rich; the Cretaceous also has numerous marine oil shales, for example, Julia Creek in Australia; these have characteristic alginate-bituminite maceral assemblage. Tertiary Typically vitrinite>liptinite>inertinite (with suberinite common liptinite, especially Indonesia) and some inertinite>liptinite>liptinite coals; inertinite commonly sclerotinite (both slerotia and fungal spores); minor low reflecting semifusinite; detrovitrinite is much more abundant than telovitrinite; many coals have abundant secondary liptinite such as exsudatinite. 2. RANK

After deposition the plant matter changes into peat that in turn changes through the brown coal stage, bituminous coal stage to anthracite. This change, which is generally gradational rather than a stepwise change as the peat anthracite model suggests, is known as coalification and the stage that a coal has reached is referred to as the rank. Thus rank refers to the stage in the coalification path (peat brown coal sub-bituminous coal bituminous coal anthracite) that has been reached by the organic matter or the degree to which the primary plant matter has been changed as a consequence of temperature, time and possibly pressure, although the influence of the latter is much debated. Thus rank is determined by the extent to which physico-chemical and biogenically aided reactions have coalified the organic matter. As rank increases the reflectance of the macerals increases and they become more anisotropic, that is the bireflectance increases. Bireflectance is defined as the difference between, on rotation of the stage, the maximum reflection and minimum reflectance measured at the same spot. Inertinite macerals have weak bireflectance at low ranks whereas vitrinite and liptinite generally do not. Vitrinite in low volatile bituminous coals or anthracite generally have quite strong anisotropy.

Although the results are equivocal, there is evidence that anisotropy may be induced by factors other than rank, for example, stress. Figure 1 shows the increase in reflectance of macerals as a function of the increase in vitrinite reflectance. During coalification, the changes in vitrinite tend to change more regularly than for other macerals, almost linearly and vitrinite, is commonly the maceral on which rank parameters are measured. During coalification, some marked physical changes occur. Low rank brown coal generally has an open texture with cell lumen (cell cavities remaining after the cell contents have been removed) large and uncompacted. As rank increases the texture is less open and the lumen become smaller and porosity decreases. Higher rank coals, have a distinctive layering (not equivalent to plies) which is less marked in coals of lower rank. If macerals fluoresce, the fluorescence intensity is reduced and the wavelength of the emitted energy increases (that is colours change from the green end of the spectrum to the red end). Note that coalification is not the same as carbonisation which is the process that takes place when coal is heated at high temperatures in the absence of air to form a char or a coke. The volatile components are volatilized leaving essentially carbon. A char forms when the carbonized material has little or no viscosity during heating, usually forming a material that shrinks considerably, forming numerous shrinkage cracks. A coke is formed when the carbonized material passes through a plastic phase and a vesicular structure with commonly an anisotropic mosaic. 3. COALIFICATION

Coalification is the process whereby organic matter that has been covered by sediment, usually clastic sediment, gradually changes to anthracite under the influence of time, temperature and pressure although the effects of the latter are debatable. It is generally considered that, all other things being equal, organic matter will be further along the coalification path if it has been exposed to higher temperatures or has been buried for a longer period. As many as 100 techniques have been used to determine rank, some more reliable than others. Some of the common ones are: Optical methods Reflectance (in air and in water) Bireflectance Refractive Index Brewster Angle Infra-red Spectroscopy Spore/Pollen Translucence Conodont Coloration Liptinite Fluorescence Microhardness Moisture Geochemical Methods Free Radical Count Modal n-Alkane Pristane to Phytane Ratio Gasoline Range Hydrocarbons Rock Eval Tmax Methyl Phenanthrene Index Proximate Analysis Volatile Matter Fixed Carbon Ultimate Analysis C H 0 H/C Ratio, O/C Ratio

4.

COALIFICATION PROCESSES

Two stages are recognized in the coalification path biochemical stage (peatification), which is primarily a digenetic process and geochemical stage which is primarily catagenic and metagenic processes (= metamorphism). 4.1 Biochemical Stage Numerous studies have been carried on the composition of peat, factors affecting the accumulations of peat and the biological, physical and chemical changes that occur within peat the literature does not discuss the change the alteration of plant matter to peat. The point at which plant matter becomes peat is poorly defined. Concensus is that the most important changes in peat occur within the top 0.5 m of the peat (called the peatigenic layer, Stach et al., 1982) and are biochemical in nature, that is, they are chemical reactions brought about by the activity of biological organisms particularly bacteria, fungi and actinomyces. Within the peatigenic layer, the organisms are aerobic (require oxygen) but below this layer the organisms are anaerobic (do not require oxygen). Below 10 m, the biogenic activity stops and all changes are physico-chemical. The dominant chemical change in the peat swamp is humification or the formation of humic material (Stach et al, 1982). This reaction is controlled by the oxygen supply, temperature and alkaline environments. It is a facies influenced process not a depth related process. Humification processes started in the peat stage probably continue into the soft brown coal stage. Plants cells contain various compounds within the cell walls and cell contents. According to Bustin et al. (1983) the degree of susceptibility of compounds and parts of plants are: protoplasm chlorophyll coats pigments cuticle oils carbonhydrates (cellulose, starch, lignin) spores/pollens waxes resins epidermis/seed

The protoplasm and chlorophyll rapidly decay to produce carbon dioxide, ammonia, methane and water and little is incorporated in the peat. Lignin, cellulose, amino acids, tannins and possibly some resins and waxes are the substrates for the micro-organisms which progressively change these components into humic acids. Cuticle, spores/pollen, waxes and resins are lipid-rich and are resistant to both aerobic and anaerobic degradation and thus do not readily undergo humification. With progressive burial and compaction of peat and the resultant continued coalification, free cellulose content and moisture content decrease; the carbon content and calorific value increase. Stach et al. (1982) give the following differences between peat and brown coal. % moisture % C (daf) free cellulose able to be cut Solubility in KOH 4.2 Geochemical Stage Peat >75 mostly <70 present yes yes Brown Coal <75 mostly >70 absent no no

In this stage, the alteration to the organic matter is controlled by physico-chemical reactions that further decrease the hydrogen and oxygen levels, partly through the loss of the functional groups of hydroxyl (-OH), carboxyl (-COOH), methoxyl (-OCH3), carbonyl (C=O) and rings containing O, especially in the brown coal stage. The volatile content of the coal decreases through the loss of aliphatic and alicyclic carbon compounds accompanied by increases aromatization of the remaining carbon. Products of coalification are methane, carbon dioxide and water. Most of the water is lost during the early stages of coalification, and as a consequence, during the latter stages the ratio of

methane to hydrogen increases. Bustin et al. (1983) reported one publication quoting methane production of 200 1 of methane per 100 kg of coal. The relative increase in carbon content during coalification is manifested as increases in the carbon content of the three maceral groups. This change has been shown on the van Krevelen diagram (Fig. 4.4). As can be seen from the diagram, the changes in vitrinite are more constant throughout the coalification path than the changes for liptinite and inertinite which are less constant. This is the reason vitrinite is the maceral type on which rank parameters are measured where possible. The rank is estimated predominantly by chemical parameters, such as C, O, H and volatile matter or optical properties such as vitrinite reflectance (which is a function of chemistry). During the brown coal stage, the most significant change is in the moisture content (with a resultant increase in calorific value) with the liptinite macerals showing few changes in this stage. In German literature distinction is made between three brown coal stages (soft brown coal (Weichbraunkohle), dull brown coal (Mattbraunkohle) and bright brown coal (Glanzbraunkohle). The latter two categories are collectively known as hard brown coal (Hartbraunkohle). In the soft brown coal stage, moisture decreases by 4% per 100 m depth but this reduces to 1% per 100 m) in the hard brown coal stage. In the hard brown coal stage, any remaining free cellulose is rapidly changed in humic matter and the humic molecules condense into larger molecules losing any acid character and becoming alkali-insoluble humines. Significant petrographic changes are said to occur at the dull brown coal-bright brown coal boundary. The colour of the coal changes from brown to black and becomes lustreous as a result of gelification (vitrinitization) of the humic matter. Coalification during the bituminous (Steinkohle) and anthracite stages follow the same general pattern as that in the brown coal stage, particularly an increase in calorific value as a consequence of moisture decreases. In the bituminous coal stage, the volatile matter decreases rapidly as a result of the continued removals of aliphatic and alicyclic compounds. It is generally accepted that the changes in vitrinite (or huminite-vitrinite under the ICCP nomenclature) properties undergo four jumps. The first is during the high-volatile bituminous stage (corresponds to the timing of oil generation in petroleum source rocks), the second during the medium-volatile bituminous stage (corresponds to a marked reduction in oxygen, the beginning of methane formation and the end of the oil generation zone), the third between the semianthracite/anthracite stages (corresponds to release of large amounts of hydrogen as methane and is accompanied by strong aromatization and ring condensation) and the fourth at the anthracite/metaanthracite boundary (corresponds to further hydrogen release as methane and increased aromatization). Petrographically, a number of changes can be documented through the geochemical stage of alteration. The reflectance progressively increases as does the bireflectance and in transmitted light the macerals become darker and opacity increases. Cell structure which is clearly visible in soft brown coal stage become more compacted and much harder to recognize so that by the low volatile bituminous stage etching and specialized immersion oils are needed. Up to the sub-bituminous stage little change is observed in liptinite but it is generally agreed that a significant jump in liptinite coalification occurs at the sub-bituminous/bituminous boundary (commencement of the oil generation zone in source rocks); liptinite loses volatiles and hydrogen and relative carbon content increases. Up to the sub-bituminous stage, liptinite fluorescence does not alter significantly but after that there is a decrease in fluorescence intensity and a colour change towards the red end of the spectrum occurs. With continued coalification, the liptinite becomes progressively darker and more opaque in reflected light and fluorescence diminishes even more. Further losses in volatiles and hydrogen (with corresponding increases in relative carbon content) occur during the medium-volatile bituminous stage. During the hard brown coal/sub-bituminous coal stage, secondary liptinite macerals such as exsudatinite form.

Inertinite, which is thought to form in an oxidizing environment, has a high aromatized carbon content initially and the changes in this group, in general, are less pronounced during coalification. However, because of the wide variation in the chemical composition of inertinite, especially semifusinite, and thus the optical properties significant changes, including fluorescence, can occur in some semifusinite. It should be noted that all changes during coalification are relative, especially reflectance and fluorescence. There are always macerals with anomalous properties and these may be related to either local variations in conditions within the local area or more laterally or vertically spread properties related to specific aspects of temperature regime or environment of deposition, which are atypical. For example, in Indonesian Tertiary coals, exsudatinite is abundant in coal with a vitrinite reflectance of 0.35%. At the low volatile bituminous stage, liptinite has similar properties to vitrinite can only be ditinguished from the latter by etching and then it is difficult in many cases. By the anthracite stage, the three maceral groups have similar optical and chemical properties. Whereas the vitrinite reflectance graph shows a constant change with rank, the inertinite reflectance graphs shows little increase during the early stages of coalification and more rapid changes in the later stages. Liptinite shows the opposite trend. 4.3 Humification

Humification reactions are those which convert primarily cellulose, lignin and tannin but other compounds as well, into humic acids. Bustin et al (1983) reported that it has been suggested that the degradation of cellulose produces reactive ketoacids that show a strong tendency toward aromatization. With increasing depth, under reducing conditions, humification of lignin and cellulose continues by intramolecular-reduction processes during which oxidized humic acids form as well as strongly reduced compounds. Tissot and Welte (1978) reported that humification occurs in two stages. Plant tissue is mechanically disintegrated and depolymerised by biogenic activity into aromatic, phenolic and carboxylic groups. The humic polymers also undergo random repolymerization and polycondesation. With progressive diagenesis humic acids lose acid groups to form humins that are insoluble in alkalies (for example, KOH). Humification is followed by gelification that is a physico-chemical process in which the organic matter passes through a swollen, plastic gel phase to form huminite