Chemical functionalities of high and low sulfur Australian coals : a case study using micro attenuated total reflectance–fourier transform infrared (ATR–FTIR) spectrometry

The macerals in bituminous coals with varying organic sulfur content from the Early Permian Greta Coal Measures at three locations (Southland Colliery, Drayton Colliery and the Cranky Corner Basin), in and around the Sydney Basin (Australia), have been studied using light-element electron microprobe (EMP) analysis and micro-ATR–FTIR. Electron microprobe analysis of individual macerals reveals that the vitrinite in both the Cranky Corner Basin and Drayton Colliery (Puxtrees seam) samples have similar carbon contents (ca. 78% C in telocollinite), suggesting that they are of equivalent rank. However, the Cranky Corner coals have anomalously low vitrinite reflectance (down to 0.45%) vs. the Drayton materials (ca. 0.7%). They also have very high organic S content (3–6.5%) and lower O content (ca. 10%) than the equivalent macerals in the Drayton sample (0.7% S and 15.6% O). A study was carried out to investigate the impacts of the high organic S on the functional groups of the macerals in these two otherwise iso-rank, stratigraphically-equivalent seams. An iso-rank low-S coal from the overlying Wittingham Coal Measures near Muswellbrook and coals of slightly higher rank from the Greta Coal Measures at Southland Colliery near Cessnock were also evaluated using the same techniques to extend the data set. Although the telocollinite in the Drayton and Cranky Corner coals have very similar carbon content (ca.78% C), the ATR–FTIR spectra of the vitrinite and inertinite macerals in these respectively low S and high S coals show some distinct differences in IR absorbance from various aliphatic and aromatic functional groups. The differences in absorbance of the aliphatic stretching bands (2800–3000 cm−1) and the aromatic carbon (CC) peak at 1606 cm−1 are very obvious. Compared to that of the Drayton sample (0.7% S and 15% O), the telocollinite of the Cranky Corner coal (6% S and 10% O) clearly shows: (i) less absorbance from OH groups, represented by a broad region around 3553 cm−1, (ii) much stronger aliphatic C–H absorbance (stretching modes around 3000–2800 cm−1 and bending modes around 1442 cm−1) and (iii) less absorbance from aromatic carbon functional groups (peaking at 1606 cm−1). Evaluation of the iso-rank Drayton and Cranky Corner coals shows that: (i) the aliphatic C–H absorbances decrease with increasing oxygen content but increase with increasing organic S content and (ii) the aromatic H to aliphatic H ratio (Har/Hali) for the telocollinite increases with (organic) O%, but decreases progressively with increasing organic S. The high organic S content in the maceral appears to be accompanied by a greater proportion of aliphatic functional groups, possibly as a result of some of the O within maceral ring structures in the high S coal samples being replaced.

Micrinite in Southern Hemisphere sub-bituminous and bituminous coals : redefined as fine grained kaolinite

A range of complementary analytical techniques including SEM/EDS, TEM/EDS and conventional optical microscopy has been rigorously applied to precisely defined areas of micrinite in polished coal samples from Australia and New Zealand. Elemental analyses of micrinite regions showed a high abundance of Al, Si and O and high resolution images of micrinite revealed a grain size < 1μm. Electron diffraction and elemental analyses from individual grains within the optically and electron-optically correlated micrinite regions are consistent with the occurence of fine-grained kaolinite. The optical properties of "dark clay" and "micrinite" (i.e. fine-grained kaolinite) can be understood in terms of the diffuse scattering of visible light from the surfaces of materials with different grain sizes in single-phase or multi-phase mixtures.

Petrography and geochemistry of organic matter at DSDP Holes 80-549 and 80-550B

Three lower Barremian to middle/upper Cenomanian samples from DSDP Hole 549 and three lower Cenomanian to lower Maestrichtian samples from DSDP Hole 550B were investigated by organic geochemical and organic petrographic methods. The samples came from wells drilled in the area of the Goban Spur in the northeastern Atlantic; they represent gray to greenish gray carbonaceous mud or siltstones from the deeper parts of the Cretaceous sequences penetrated and light-colored chalks from the shallower ones. The total amount of organic carbon is below 1% in all samples; it is especially low in the Cenomanian to Maestrichtian chalks. Terrigenous organic matter predominates; only the Barremian sample shows a moderate number of marine phytoclasts. As indicated by several parameters, the maturity of the organic matter is low, corresponding to about 0.4% vitrinite reflectance.

Carbon chemistry of ODP Leg 105 sites

The quantity and quality of organic carbon of Eocene to Holocene sediments from ODP Sites 645, 646, and 647 were investigated to reconstruct depositional environments. Results were based on organic-carbon and nitrogen determinations, Rock-Eval pyrolysis, and kerogen microscopy. The sediments at Site 645 in Baffin Bay are characterized by relatively high organic-carbon values, most of which range from 0.5% to almost 3%, with maximum values in the middle Miocene. Distinct maxima of organic-carbon accumulation rates occur between 18 and 12.5 Ma and between 3.4 and 0 Ma. At Sites 646 and 647 in the Labrador Sea, organic-carbon contents vary between 0.1% and 0.75%. Cyclic 'Milankovitch-type' changes in organic-carbon deposition imply climate-controlled mechanisms that cause these fluctuations. The composition of organic matter at Site 645 is dominated by terrigenous components throughout the entire sediment sequence. An increased content of marine organic carbon was recorded only in the late-middle Miocene. At Sites 646 and 647, the origin of the organic matter most probably is marine. Oceanic paleoproductivity values were estimated, based on the amount of marine organic carbon. During most of the Neogene time interval at Site 645, productivity was low, i.e., similar or less than that measured in Baffin Bay today. Higher values of up to 150 (200) gC/m**2/y may have occurred only in the Miocene. At Sites 646 and 647, mean paleoproductivity values vary between 90 and 170 gC/m**2/y; i.e., these are also similar to those measured in the Labrador Sea today. Lower values of 40 to 70 gC/m**2/y were estimated for the early Eocene and (middle) Miocene.

Organic geochemistry of ODP Sites 128-798 and 128-799

Miocene to Quaternary sediments from the Oki Ridge (Site 798) and the Kita-Yamato Trough (Site 799) in the Japan Sea contain organic carbon ranging from about 0.6% in light-colored layers to almost 6% in dark layers. The organic matter consists of a variable mixture of marine and terrigenous contributions, the ratio of which is not correlated to the total organic carbon content. Marine organic particles clearly dominate in the deeper section of Hole 799B. The extractable bitumen is strongly dominated by long-chain alkenones from microalgae in the shallower sediments, whereas bishomohopanoic acid (C32) of eubacterial origin is the single most abundant compound in deeper samples. Normal alkanes and straight-chain carboxylic acids, both of which show a bimodal distribution with odd and even carbon-number predominance, respectively, are two other groups of compounds which are important constituents of the extracts. The deepest samples at Site 799 contain a considerable amount of short-chain components, which probably migrated upward from thermally more altered deeper sediments.