The stable isotope geochemistry of Australian coals

D/H, ¹³C/¹²C, ¹⁸O/¹⁶O and ³⁴S/³²S ratios in the organic matrix and organic solvent extracts of Australian coals, and in the fluids and minerals associated with these coals, are reported and reviewed against similar isotopic data for coals from other regions.Where coals are immature, original isotopic differences between macrolithotypes, and between solvent extracts (lipid concentrates) and insoluble residues, are largely preserved. However, with increasing maturity these characteristic differences, particularly those between macrolithotypes, are rapidly erased. Conversely, where, as indicated by low total sulfur contents, coals of Cretaceous to Permian age were deposited under essentially freshwater conditions, δ³⁴S values^* for the organically-bound sulfur remain remarkably constant at +4 ± 3‰ relative to meteoritic sulfur. In similar, younger Tertiary coals, the organic sulfur is markedly enriched in ³⁴S.Five distinctive isotopic patterns, which may be interpreted in terms of the environment of sulfate reduction, can be recognized from ³⁴S/³²S ratio measurements on the various forms of sulfur in Australian coals.Isotopic studies of seam gas hydrocarbons collected in situ show these to be unexpectedly strongly depleted in the heavier isotopes of hydrogen and carbon relative to natural gases from proposed humic sources. Furthermore, no pronounced increase in the ¹³C content in methane with increase in rank of the parent coal was observed. In addition, several sources of associated carbon dioxide have been delineated, including normal maturation processes, invasion of the seams by magnetic carbon dioxide, and interaction of the coal with intrusive magma.Isotopic exchange between free seam gases is not accepted as an explanation for some unusual isotopic fractionations seen, rather the data suggest that these gases may be formed in a state approaching isotopic equilibrium. This argument also satisfactorily explains the isotopic compositions of primary siderite and secondary calcite associated with bituminous coal seams. However, where seams are invaded and permeated with externally derived carbon dioxide, usually of magnetic origin, carbonates are frequently absent, presumably as a result of the action of carbonic acid.     

Early generation of 20S-5α(H),14α(H),17α(H)- and 5α(H),14β(H),17β(H)-steranes in low salinity lacustrine shales

A quantitative sterane biomarker study was conducted on a series of paralic freshwater lacustrine shale samples ranging in maturity from immature to near oil window maturity taken from Section 3 of the Shahejie Formation (Es3) in the Liaohe Basin, N.E. China. Concentrations of 5α(H),14α(H),17α(H)-20S and 5α(H),14β(H),17β(H)-steranes remain nearly constant throughout the sample suite. However, the decrease in the absolute concentrations of the 20R-5α(H),14α(H),17α(H)-C₂₉ steranes with increasing maturity results in an increase in the conventionally defined maturity parameters, 20S/(20S + 20R)-ααα and αββ/(ααα + αββ) sterane ratios. In addition, the data suggest that relatively early generation of 5α(H),14α(H),17α(H)-20S and 5α(H),14β(H),17β(H)-steranes has occurred in lacustrine sediments with a vitrinate reflectance 0.3% (R_o). The data provide strong support for the major importance of relative thermal stability of epimers, but do not exclude the possibility of isomerization as a viable mechanism for production.     

Progression in sulfur isotopic compositions from coal to fly ash: Examples from single-source combustion in Indiana

Sulfur occurs in multiple mineral forms in coals, and its fate in coal combustion is still not well understood. The sulfur isotopic composition of coal from two coal mines in Indiana and fly ash from two power plants that use these coals were studied using geological and geochemical methods. The two coal beds are Middle Pennsylvanian in age; one seam is the low-sulfur (< 1%) Danville Coal Member of the Dugger Formation and the other is the high-sulfur (> 5%) Springfield Coal Member of the Petersburg Formation. Both seams have ash contents of approximately 11%. Fly-ash samples were collected at various points in the ash-collection system in the two plants. The results show notable difference in δ³⁴S for sulfur species within and between the low-sulfur and high-sulfur coal. The δ³⁴S values for all sulfur species are exclusively positive in the low-sulfur Danville coal, whereas the δ³⁴S values for sulfate, pyritic, and organic sulfur are both positive and negative in the high-sulfur Springfield coal. Each coal exhibits a distinct pattern of stratigraphic variation in sulfur isotopic composition. Overall, the δ³⁴S for sulfur species values increase up the section in the low-sulfur Danville coal, whereas they show a decrease up the vertical section in the high-sulfur Springfield coal. Based on the evolution of δ³⁴S for sulfur species, it is suggested that there was influence of seawater on peat swamp, with two marine incursions occurring during peat accumulation of the high-sulfur Springfield coal. Therefore, bacterial sulfate reduction played a key role in converting sulfate into hydrogen sulfide, sulfide minerals, and elemental sulfur. The differences in δ³⁴S between sulfate sulfur and pyritic sulfur is very small between individual benches of both coals, implying that some oxidation occurred during deposition or postdeposition.The δ³⁴S values for fly ash from the high-sulfur Springfield coal (averaging 9.7‰) are greatly enriched in ³⁴S relative to those in the parent coal (averaging 2.2‰). This indicates a fractionation of sulfur isotopes during high-sulfur coal combustion. By contrast, the δ³⁴S values for fly-ash samples from the low-sulfur Danville coal average 10.2‰, only slightly enriched in ³⁴S relative to those from the parent coal (average 7.5‰). The δ³⁴S values for bulk S determined directly from the fly-ash samples show close correspondence with the δ³⁴S values for SO₄^− 2 leached from the fly ash in the low-sulfur coal, suggesting that the transition from pyrite to sulfate occurred via high-temperature oxidation during coal combustion.     

Identification of some diterpenoid hydrocarbons in petroleum

19-Norisopimarane and isopimarane have been synthesized from isopimara-9(11), 15-diene-3β, 19-diol. Analysis of the alkane fractions of an Australian crude oil by GC-MS showed the presence of nine diterpenoid hydrocarbons (diterpanes), of which one was bicyclic two were tricyclic and six were tetracyclic.19-Norisopimarane and isopimarane were identified by comparison of their mass spectra and GC retention times with those of the synthetic standards. ent-Beyerane, 16a(H)-phyllocladane, 16)β(H)-phyllocladane, ent-16α(H)-kaurane and labdane were also identified by comparison with authentic reference compounds. The remaining two compounds were tentatively identified as rimuane and as a 17-nortetracyclic diterpane on the basis of mass spectral evidence. The diterpanes are probably derived from conifer resins.     

Stable isotope geochemistry of coals, humic kerogens and related natural gases

Isotope systematics are well defined for conventional sapropelic, Type I/II kerogens and their associated bacterial and thermogenic natural-gas products. These geochemical tools are used to estimate source type, maturity and depositional environment, and as a correlation technique. In many cases the natural gas signatures in near-surface samples and drill cuttings can be used to classify or predict a deeper lying source rock or reservoir.Corresponding interpretative schemes for coals, Type III kerogens and their associated hydrocarbons are progressing quickly. The shift in attention to humic sources is driven primarily by depletion of conventional oil and gas resources and the economic and societal requirements of coal and coal-bed methane.Carbon, hydrogen and nitrogen stable isotope variations can be large between different coals and humic kerogens. These differences can often be recognized in their bulk δ¹³C_org, δD_org and δ¹⁵N_org values. Isotope signatures of coals can be diagnostic of several factors, including deposit age, type, geographic location, maturity and generation history. However, these characteristic isotopic variations are substantially better defined by the C-, H- and N-isotope ratios of the separate maceral groups, such as vitrinite, exinite and inertinite. This new application of stable isotopes, at the maceral and compound levels, have great potential to improve the interpretative precision over conventional whole coal or bulk techniques.Hydrocarbon gases, including coal gases, derived from coals and humic kerogens can be distinguished from Type I/II sources, based on their molecular rations, i.e., C₁/(C₂ + C₃) and by comparing their stable isotope compositions, especially δ¹³C_CH4 and δD_CH4. The δ¹³C_C2H6 can also be valuable, but ethane is generally present in small amount (<1 vol. %) and requires     

Sulphur and carbon isotopic composition of power supply coals in the Pannonian Basin, Hungary

The present work is an attempt to establish the stable isotope database for Mesozoic to Tertiary coals from the Pannonian Basin, Hungary. Maceral composition, proximate analysis, sulphur form, sulphur isotopes (organic and pyritic), and carbon isotopes were determined. This database supports the assessment of the environmental risks associated with energy generation, the characterization of the formation and the distribution of sulphur in the coals used.The maceral composition, the sulphur composition, the C, S isotopic signatures, and some of the geological evidences published earlier show that the majority of these coals were deposited in freshwater and brackish water environments, despite the relatively high average sulphur content. However, the Upper Cretaceous, Eocene, and Lower Miocene formations also contain coal seams of marine origin, as indicated by their maceral composition and sulphur and carbon chemistry.The majority of the sulphur in these coals occurs in the organic form. All studied sulphur phases are relatively rich in ³⁴S isotopes (δ³⁴S_organic = + 12.74‰, δ³⁴S_pyrite = + 10.06‰, on average). This indicates that marine bacterial sulphate reduction played a minor role in their formation, in the sense that isotopic fractionation was limited. It seems that the interstitial spaces of the peat closed rapidly during early diagenesis due to a regime of high depositional rate, leading to a relative enrichment of the heavy sulphur isotopes.     

Classification of torbanite and cannel coal: II. Insights from pyrolysis-GC/MS and multivariate statistical analysis

Petrographic and megascopic criteria have traditionally been used as the basis for the classification of torbanite and cannel coal. For this study, it was hypothesized that modern analytical organic geochemical and multivariate statistical techniques could provide an alternative approach. Towards this end, the demineralized residues of 14 torbanite (rich in Botryococcus-related alginite) and cannel (essentially, rich in organic groundmass and/or sporinite) coal samples were analyzed by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Cluster analysis performed on the Py-GC/MS data clearly distinguished the torbanite from the cannel coal, demonstrating a consistency between the chemical properties and the petrographic composition. All the torbanite samples group into one cluster, their pyrolyzates having an overwhelming predominance of straight chain hydrocarbons, a characteristic typical of Botryococcus. The presence of the C₉–C₂₆ n-α,ω-alkadiene series is the key feature distinguishing the torbanites from the other samples. The cannel coals exhibit more chemical diversity, reflecting their greater variability in petrographic composition. The Breckinridge cannel, dominated by a highly aliphatic lamalginitic groundmass, chemically fits the torbanite category. The bituminitic groundmass-dominated cannel coals fall into a cannel sub-cluster, their pyrolyzates having a characteristic predominance of n-alk-1-enes and n-alkanes (particularly the long-chain homologues), with no detectable alkadienes. The vitrinitic groundmass-dominated Ohio Linton cannel and the sporinite-rich Canadian Melville Island cannel are readily distinguishable from the other cannels by the relatively abundant aromatic and phenolic compounds in their pyrolyzates. The internal distribution patterns of alkylaromatic and alkylphenolic isomers are shown to be less significant in the classification of this sample set. Multivariate statistical analysis of the pyrolysis data not only successfully discriminated torbanites from cannel coals, but recognized subtler differences between the examples of these two coal types, in substantial agreement with the petrographic characterization. As such, these methods can substitute for or supplement the traditional microscope-based approach.     

Changes in bulk properties and molecular compositions within New Zealand Coal Band solvent extracts from early diagenetic to catagenetic maturity levels

The bulk properties and bitumen molecular compositions of a rank-series of 38 humic coals from the New Zealand Coal Band (Cretaceous–Cenozoic) have been analysed to investigate early maturation processes affecting coaly organic matter through diagenesis to moderate catagenesis (Rank(S_r) 0.0–11.8, R_o 0.23–0.81%). The samples comprise a relatively restricted range of vitrinite rich coal types formed largely from higher land plant material under relatively oxic conditions, but with a significant contribution from microbial biomass. With increasing rank, total organic carbon contents show a general increase, whereas moisture and asphaltene contents decrease. Bitumen yields also decrease through the stages of diagenesis and early catagenesis (Rank(S_r) < 9, R_o < 0.55%), indicating partial loss of initial bitumen during early maturation. Thermal generation of hydrocarbons begins slowly at Rank(S_r)  5–6 (R_o  0.40%) as indicated by the constant occurrence and gradual increase of isoprenoids (e.g., pristane and phytane) and hopanoids in their more mature αβ configuration. This early phase of catagenesis, not previously recognised in New Zealand coals, is followed at Rank(S_r)  9 (R_o  0.55%) by the main catagenesis phase characterised by a more rapid increase in the generation of hydrocarbons, including total n-alkanes, isoprenoids and αβ-hopanes. Changes in the maturity of New Zealand coals can be traced by the Carbon Preference Index and several hopane maturity parameters, including 22S/(22S + 22R), αβ/(αβ + βα) and ββ/(αβ + βα + ββ).     

Brecciated and mineralized coals in Union County, Western Kentucky coal field

Coals from the D-2 and D-3 boreholes in the Grove Center 7 1/2 min quadrangle, Union County, KY, have been found to be highly brecciated and mineralized. The mineralization is dominated by a carbonate assemblage with minor sulfides and sulfates. Included among the secondary minerals is the lead selenide, clausthalite. Overall, the emplacement of secondary vein minerals was responsible for raising the rank of the coals from the 0.6–0.7% R_max range found in the area to as high as 0.95–0.99% R_max.A 1.3-m-thick coal found in one of the boreholes is unique among known Western Kentucky coals in having less than 50% vitrinite. Semifusinite and fusinite dominate the maceral assemblages. The coal is also low in sulfur coal, which is unusual for the Illinois Basin. It has an ash yield of less than 10%; much of it dominated by pervasive carbonate veining. The age of the thick coal in core D-2 is similar to that of the Elm Lick coal bed, found elsewhere in the Western Kentucky coalfield. The coals in D-3 are younger, having Stephanian palynomorph assemblages.     

Molecular and carbon isotopic analysis of individual biological markers: evidence for sources of organic matter and paleoenvironmental conditions in the Upper Ordovician Maquoketa Group, Illinois Basin, U.S.A.

Variations in the carbon isotopic composition (δ¹³C) of pristane, phytane, n-heptadecane (n-C₁₇), C₂₉ ααα 20R sterane, and aryl isoprenoids provide evidence for a diverse community of algal and bacterial organisms in organic matter of the Upper Ordovician Maquoketa Group of the Illinois Basin. Carbon isotopic compositions of pristane and phytane from the Maquoketa are positively covariant (r = 0.964), suggesting that these compounds were derived from a common source inferred to be primary producers (algae) from the oxygenated photic zone. A variation of 3‰ in δ¹³C values (−31 to −34‰) for pristane and phytane indicates that primary producers utilized variable sources of inorganic carbon. Average isotopic compositions of n-C₁₇ (−32‰) and C₂₉ ααα 20R sterane (−31‰) are enriched in ¹³C relative to pristane and phytane (−33‰) suggesting that these compounds were derived from a subordinate group of primary producers, most likely eukaryotic algae. In addition, a substantial enrichment of ¹³C in aryl isoprenoids (−14 to −18‰) and the identification of tetramethylbenzene in pyrolytic products of Maquoketa kerogen indicate a contribution from photosynthetic green sulfur bacteria to the organic matter. The presence of anaerobic, photosynthetic green sulfur bacteria in organic matter of the Maquoketa indicates that anoxic conditions extended into the photic zone.The δ¹³C of n-alkanes and the identification of an unusual suite of straight-chain n-alkylarenes in the m/z 133 fragmentograms of Ordovician rocks rich in Gloeocapsomorpha prisca (G. prisca) indicate that G. prisca did not contribute to the organic matter of the Maquoketa Group.     

Sterane isomerisation and moretane/hopane ratios in crude oils derived from Tertiary source rocks

The extent of sterane isomerisation reactions and the moretane/hopane ratios of 234 crude oils, taken world wide, from a wide variety of source rocks of differing geological ages, have been measured.This data indicates that in 78 crude oils derived from Tertiary source rocks, sterane isomerisation reactions as determined by the 20S/(20S + 20R) ration of the C₂₉ 5α(H), 14α(H), 17α(H) normal-steranes and the C₂₉ iso/(iso + normal) ratio [iso = 5α (H), 14β(H), 17β(H)] are mainly incomplete and sometimes considerably so. In addition, the same crude oils have 17β(H), 21α(H)-moretane/17α(H), 21β(H)-hopane ratios which are significantly greater (predominantly in the range 0.10–0.30) than those of crude oils derived from older, mature source rocks (mainly less than 0.1).This data, for crude oils, lends support to the hypothesis, proposed by Mackenzie and McKenzie (1983) for source rock extracts, that the time/temperature constraints of sterane isomerisation reactions are such that the time available for isomerisation in Tertiary sediments is generally insufficient, despite generation of crude oil at relatively high temperatures.An alternative hypothesis is that the incomplete sterane isomerisation of Tertiary crude oils may be due to generation of these crude oils from their deltaic, land plant-containing source rocks under low heating conditions.A third hypothesis proposes that the Tertiary crude oils may have picked up the incompletely isomerised steranes from immature sediments during migration. Although possible in particular instances, such a mechanism does not appear to be generally applicable since, in that case, the phenomenon would then appear to be restricted to the Tertiary.The higher moretane/hopane ratios of the Tertiary crude oils could suggest that constraints, similar to those applying in sterane isomerisation, also operate in the conversion of moretane to 17α(H)-hopane.     

A review of coal properties pertinent to carbon dioxide sequestration in coal seams: with special reference to Victorian brown coals

This paper presents reviews of studies on properties of coal pertinent to carbon dioxide (CO₂) sequestration in coal with specific reference to Victorian brown coals. The coal basins in Victoria, Australia have been identified as one of the largest brown coal resources in the world and so far few studies have been conducted on CO₂ sequestration in this particular type of coals. The feasibility of CO₂ sequestration depends on three main factors: (1) coal mass properties (chemical, physical and microscopic properties), (2) seam permeability, and (3) gas sorption properties of the coal. Firstly, the coal mass properties of Victorian brown coal are presented, and then the general variations of the coal mass properties with rank, for all types of coal, are discussed. Subsequently, coal gas permeability and gas sorption are considered, and the physical factors which affect them are examined. In addition, existing models for coal gas permeability and gas sorption in coal are reviewed and the possibilities of further development of these models are discussed. According to the previous studies, coal mass properties and permeability and gas sorption characteristics of coals are different for different ranks: lignite to medium volatile bituminous coals and medium volatile bituminous to anthracite coals. This is important for the development of mathematical models for gas permeability and sorption behavior. Furthermore, the models have to take into account volume effect which can be significant under high pressure and temperature conditions. Also, the viscosity and density of supercritical CO₂ close to the critical point can undergo large and rapid changes. To date, few studies have been conducted on CO₂ sequestration in Victorian brown coal, and for all types of coal, very few studies have been conducted on CO₂ sequestration under high pressure and temperature conditions.     

Place vs. time and vegetational persistence: a comparison of four tropical mires from the Illinois Basin during the height of the Pennsylvanian Ice Age

Coal balls were collected from four coal beds in the southeastern part of the Illinois Basin. Collections were made from the Springfield, Herrin, and Baker coals in western Kentucky, and from the Danville Coal in southwestern Indiana. These four coal beds are among the principal mineable coals of the Illinois Basin and belong to the Carbondale and Shelburn Formations of late Middle Pennsylvanian age. Vegetational composition was analyzed quantitatively. Coal-ball samples from the Springfield, Herrin, and Baker are dominated by the lycopsid tree Lepidophloios, with lesser numbers of Psaronius tree ferns, medullosan pteridosperms, and the lycopsid trees Synchysidendron and Diaphorodendron. This vegetation is similar to that found in the Springfield and Herrin coals elsewhere in the Illinois Basin, as reported in previous studies. The Danville coal sample, which is considerably smaller than the others, is dominated by Psaronius with the lycopsids Sigillaria and Synchysidendron as subdominants.Coal balls from the Springfield coal were collected in zones directly from the coal bed and their zone-by-zone composition indicates three to four distinct plant assemblages. The other coals were analyzed as whole-seam random samples, averaging the landscape composition of the parent mire environments. This analysis indicates that these coals, separated from each other by marine and terrestrial-clastic deposits, have essentially the same floristic composition and, thus, appear to represent a common species pool that persisted throughout the late Middle Pennsylvanian, despite changes in baselevel and climate attendant the glacial–interglacial cyclicity of the Pennsylvanian ice age. Patterns of species abundance and diversity are much the same for the Springfield, Herrin, and Baker, although each coal, both in the local area sampled, and regionally, has its own paleobotanical peculiarities. Despite minor differences, these coals indicate a high degree of recurrence of assemblage and landscape organization. The Danville departs dramatically from the dominance–diversity composition of the older coals, presaging patterns of tree–fern and Sigillaria dominance of Late Pennsylvanian coals of the eastern United States, but, nonetheless, built on a species pool shared with the older coals.     

Petrologic studies of terrestrial organic matter in Carpathian flysch sediments, southern Poland

In the Carpathian Flysch, coal is present either as exotics of Carboniferous coal deposits or as autochthonous, thin layers of lustrous coal. This paper present the results of the studies of coal-bearing rocks that are coeval with the enclosing flysch sediments. These coals form lenses up to 0.15 m thick. Their morphology precludes an exotic origin. The main petrographic component is collinite with admixtures of poorly fluorescing telinite. Minor components are: exudatinite, sporinite, fusinite, micrinite and sclerotinite. Mineral matter consists of framboidal pyrite clay minerals and quartz.The random reflectance of telocollinite varies from 0.38% to 0.72%, which corresponds to subbituminous and bituminous ranks. Correlation between chemical analysis, coking properties and relfectance measurements, leads to the conclusion that boundary between subbituminous and bituminous coals should be defined by the following values: C=80wt%, VOLATILES=43wt%; calorific VALUE=32.3 MJ/kg; and R^o=0.56–0.57%.Atypical properties, such as: upper C value (75–80wt%); high volatile matter contents (over 43wt%) and low random reflectance (^o about 0.38–0.57%) in subbituminous coals; low C value (about 80–82wt%); low reflectance (0.56–0.72%); and good coking properties, of the bituminous coals are attributed to quick coalification during increasing temperature as a result of tectonic stress.     

Organic geochemical characteristics and depositional environments of the Jurassic coals in the eastern Taurus of Southern Turkey

In this study, organic matter content, type and maturity as well as some petrographic and physical characteristics of the Jurassic coals exposed in the eastern Taurus were investigated and their depositional environments were interpreted.The total organic carbon (TOC) contents of coals in the Feke–Akkaya, Kozan–Gedikli and Kozan–Kizilinc areas are 24.54, 66.78 and 49.15%, respectively. The Feke–Akkaya and Kozan–Kizilinc coals have low Hydrogen Index (HI) values while the Kozan–Gedikli coals show moderate HI values. All coal samples display very low Oxygen Index (OI) values. The Kozan–Gedikli coals contain Type II organic matter (OM), the Feke–Akkaya coals contain a mixture of type II and type III OM; and the Kozan–Kizilinc coals are composed of Type III OM. Sterane distribution was calculated as C₂₇ > C₂₉ > C₂₈ from the m/z 217 mass chromatogram for all coal samples.T_max values for the Feke–Akkaya, Kozan–Gedikli and Kozan–Kizilinc coals are 439, 412 and 427 °C. Vitrinite reflectance values (%R_o) for the Feke–Akkaya and Kozan–Kizilinc coal samples were measured as 0.65 and 0.51 and these values reveal that the Feke–Akkaya and Kozan–Kizilinc coals are at subbituminous A or high volatile C bituminous coal stage. On the basis of biomarker maturity parameters, these coals have a low maturity.The pristane/phytane (Pr/Ph) ratios for the Feke–Akkaya, Kozan–Gedikli and Kozan–Kizilinc coals are 1.53, 1.13 and 1.25, respectively. In addition, all coals show a homohopane distribution which is dominated by low carbon numbers, and C₃₅ homohopane index is very low for all coal samples. All these features may indicate that these coals were deposited in a suboxic environment.The high sterane/hopane ratios with high concentrations of steranes, low Pr/Ph ratios and C₂₅/C₂₆ tricyclic ratios > 1 may indicate that these coals formed in a swamp environment were temporarily influenced by marine conditions.     

An evaluation of Rock-Eval pyrolysis for the study of Australian coals including their kerogen and humic acid fractions

Rock-Eval pyrolysis was performed on lithotype and depth profiles of Tertiary brown coals and a coalification profile of Permian bituminous coals. The humic acid and kerogen fractions from the coals are also investigated by this technique along with the effect of base extraction on the kerogen fraction. Structural variations between brown coal lithotypes are primarily reflected by changes in Oxygen Index Value. This result was supported by the results from the depth profile (same lithotype). A wide range of Hydrogen Indices (independent of depth) but similar Oxygen Indices were observed. The results from the Qualification profile show that the Oxygen Indices varied with rank, whereas Hydrogen Indices show a greater dependence on coal type. A plot of $\text{H}\text{C}$versus Hydrogen Index produced good correlations with the brown (0.77) and bituminous (0.90) samples lying on two separate lines intersecting at high H/C. This result (and higher correlation for bituminous samples) reflects the expected dependence of hydrogen index on oxygen content (present primarily as hydroxyl groups). A high correlation (0.95) between quantitative IR data (K 2920 cm mg^?1) and Hydrogen Indices supports previous conclusions regarding the dependence of Hydrogen Indices on the aliphatic structure of the samples.     

Extended saturated and monoaromatic tricyclic terpenoid carboxylic acids found in Tasmanian tasmanite

A series of tricyclic terpenoid carboxylic acids (C₂₀–C₄₀) was found in the acidic fraction of Tasmanian tasmanite bitumen, occurring as a mixture of stereoisomers with mainly the 13β(H), 14α(H)-and 13α(H),14α(H)-configurations. These dominant acidic tricyclic constituents have the same carbon skeleton as the ubiquitous tricyclic terpane biomarkers. A novel series of ring-C monoaromatic tricyclic terpenoid carboxylic acids was also characterized. The series ranges from C₁₉ to C₃₉ and is the acidic counterpart of the recently described series of monoaromatic tricyclic terpanes.     

The petroleum generation potential and effective oil window of humic coals related to coal composition and age

A worldwide data set of more than 500 humic coals from the major coal-forming geological periods has been used to analyse the evolution in the remaining (Hydrogen Index, HI) and total (Quality Index, QI) generation potentials with increasing thermal maturity and the ‘effective oil window’ (‘oil expulsion window’). All samples describe HI and QI bands that are broad at low maturities and that gradually narrow with increasing maturity. The oil generation potential is completely exhausted at a vitrinite reflectance of 2.0–2.2%R_o or T_max of 500–510 °C. The initial large variation in the generation potential is related to the original depositional conditions, particularly the degree of marine influence and the formation of hydrogen-enriched vitrinite, as suggested by increased sulphur and hydrogen contents. During initial thermal maturation the HI increases to a maximum value, HI_max. Similarly, QI increases to a maximum value, QI_max. This increase in HI and QI is related to the formation of an additional generation potential in the coal structure. The decline in QI with further maturation is indicating onset of initial oil expulsion, which precedes efficient expulsion. Liquid petroleum generation from humic coals is thus a complex, three-phase process: (i) onset of petroleum generation, (ii) petroleum build-up in the coal, and (iii) initial oil expulsion followed by efficient oil expulsion (corresponding to the effective oil window). Efficient oil expulsion is indicated by a decline in the Bitumen Index (BI) when plotted against vitrinite reflectance or T_max. This means that in humic coals the vitrinite reflectance or T_max values at which onset of petroleum generation occurs cannot be used to establish the start of the effective oil window. The start of the effective oil window occurs within the vitrinite reflectance range 0.85–1.05%R_o or T_max range 440–455 °C and the oil window extends to 1.5–2.0%R_o or 470–510 °C. For general use, an effective oil window is proposed to occur from 0.85 to 1.7%R_o or from 440 to 490 °C. Specific ranges for HI_max and the effective oil window can be defined for Cenozoic, Jurassic, Permian, and Carboniferous coals. Cenozoic coals reach the highest HI_max values (220–370 mg HC/g TOC), and for the most oil-prone Cenozoic coals the effective oil window may possibly range from 0.65 to 2.0%R_o or 430 to 510 °C. In contrast, the most oil-prone Jurassic, Permian and Carboniferous coals reach the expulsion threshold at a vitrinite reflectance of 0.85–0.9%R_o or T_max of 440–445 °C.     

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.     

Thermodynamic stability of various alkylated, dealkylated and rearranged 17α- and 17β-hopane isomers using molecular mechanics calculations

The thermodynamic stability of selected alkylated, dealkylated and rearranged 17α- and 17β-hopane isomers in the C₂₇, C₂₈, C₂₉, C₃₀ and C₃₁ families were calculated using molecular mechanics (MM2) methods and, where possible, calculated equilibrium ratios of certain isomers were compared with observed ratios of isomers in thermally mature crude oil samples. Those calculated and observed ratios having similar values include: (1) the relative distributions among 17β(H)/17α(H) and 21β(H)/21α(H)-hopanes including the absence of the 17β(H),21β(H)- and 17α(H),21α(H)-hopanes; (2) the 22R/22S ratios in 30-methyl-17α-hopane and 30-methyl-17β-moretane; (3) the relative distributions among 17α(H)/17β(H)- and 21α(H)/21β(H)-28,30-bisnorhopanes and among 25,28,30-trisnorhopanes, including the relatively greater stability of 17β(H) isomers in contrast to the regular hopane series; and (4) the ratios of 28(18−17S)abeo hopanes with respect to their unrearranged counterparts including the C₂₇ compounds, Ts/Tm.