Application of organic petrology and geochemistry to coal waste studies

Coal wastes produced during mining activities are commonly deposited in nearby dumps. These wastes mostly composed of minerals and variable amounts (usually 20-30%) of organic matter start to weather immediately after deposition. Oxidation of the organic matter can lead to self heating and self combustion as a result of organic and mineral matter transformations. The degree of alteration depends on the properties of the wastes, i.e., the maceral and microlithotype composition of the organic matter and its rank.Alteration of wastes also depends on the heating history, i.e., the rate of heating, final heating temperature, duration of heating, and the degree of air access. Although air is probably necessary to initiate and drive the heating processes, these usually take place under relatively oxygen depleted conditions. With slow heating, color of organic matter particles changes, irregular cracks and oxidation rims develop around edges and cracks, and bitumen is expelled. As a result, massive and detritic isotropic and strongly altered organic matter forms. On the other hand, higher heating rates cause the formation of devolatilization pores, oxidation rims around these pores and along cracks, vitrinite-bands-mantling particles, and bitumen expulsions.Organic compounds generated from the wastes include n-alkanes, iso-alkanes, alkylcyclohexanes, acyclic isoprenoids, mainly pristane, phytane and, in some cases, farnesane, sesquiterpanes, tri- and tetracyclic diterpanes, tri- and pentacyclic triterpanes, and steranes, polycyclic aromatic hydrocarbons (mostly with two- to five rings, rarely six rings), and phenols. The compounds formed change during the heating history. The fact that phenols are found in dumps where heating has not yet been completed, but are absent in those where heating ceased previously suggests the presence of water washing. The organic compounds formed may migrate within the dumps. However, when they migrate out of the dumps, they become a hazard to environment.This paper is a review on transformations of organic matter (both maceral composition and reflectance and chemical composition) in coal wastes deposited in coal waste dumps. Immediately after deposition the wastes are exposed to weathering conditions and sometimes undergo self heating processes.     

IR calibrations for water determination in olivine,r-GeO<Subscript>2</Subscript>, and SiO<Subscript>2</Subscript> polymorphs

Mineral-specific IR absorption coefficients were calculated for natural and synthetic olivine, SiO₂ polymorphs, and GeO₂ with specific isolated OH point defects using quantitative data from independent techniques such as proton–proton scattering, confocal Raman spectroscopy, and secondary ion mass spectrometry. Moreover, we present a routine to detect OH traces in anisotropic minerals using Raman spectroscopy combined with the “Comparator Technique”. In case of olivine and the SiO₂ system, it turns out that the magnitude of ε for one structure is independent of the type of OH point defect and therewith the peak position (quartz ε = 89,000 ± 15,000 textl textmol_textH2textO^-1 textcm^-2text{l},text{mol}_{{text{H}_2}text{O}}^{-1},text{cm}^{-2}), but it varies as a function of structure (coesite ε = 214,000 ± 14,000 textl textmol_textH2textO^-1 textcm^-2text{l},text{mol}_{{text{H}_2}text{O}}^{-1},text{cm}^{-2}; stishovite ε = 485,000 ± 109,000 textl textmol_textH2textO^-1 textcm^-2text{l},text{mol}_{{text{H}_2}text{O}}^{-1},text{cm}^{-2}). Evaluation of data from this study confirms that not using mineral-specific IR calibrations for the OH quantification in nominally anhydrous minerals leads to inaccurate estimations of OH concentrations, which constitute the basis for modeling the Earth’s deep water cycle.     

Implications of trace element composition of syntaxial quartz cements for the geochemical conditions during quartz precipitation in sandstones

A petrographic investigation revealed polyphase quartz cementation in the Finefrau Sandstone (Upper Carboniferous, Western Germany) and the Solling Sandstone (Lower Triassic, Central Germany). Three different cements could be distinguished in each sandstone based on their cathodoluminescence and trace element composition. The first quartz generation is suggested to have been formed during eogenesis due to dissolution and replacement of feldspar. The mesogenetic paragenesis comprises two generations of quartz and illite, which are accompanied by albite in the Solling Sandstone. Sharp luminescence zoning in quartz overgrowths points to distinct episodes of cementation in both sandstones. Significant amounts of Al, Li and H and traces of Ge and B have been detected in the quartz overgrowths. The Al‐content of the quartz cements in the Finefrau Sandstones exceeds that in the quartz cements in the Solling Sandstone by a factor of five. It is suggested that this compositional variation reflects the conditions in the pore‐water, such as temperature and pH. The Al‐concentration is generally correlated to the Li‐content with the exception of the latest quartz generation in the Finefrau Sandstones which is also most enriched in trace elements. The ratio of Li/Al varies between 0·11 and 0·25 in the two sandstones. The Li/H‐ratio, which ranges from 0·12 to 0·3, is controlled by the activity ratio of Li and H in the pore fluid. Clay minerals are the most important source for Li and high salinities favour the mobilization of Li during diagenesis. Thus, a relatively low salinity and low pH are responsible for the low Li/H‐ratio in the Finefrau Sandstone, while high salinity and neutral to alkaline pH results in a high Li/H‐ratio for the Solling Sandstone. The Ge‐contents are generally near the average of detrital quartz and indicate that pressure dissolution is a major source for quartz cementation. Different chemical compositions of distinct quartz generations indicate changes in the physico‐chemical conditions and point to mobilization of silica from different sources (for example, pressure solution and clay mineral transformations).     

Aerobic degradation of organic carbon inferred from dinoflagellate cyst decomposition in Southern Ocean sediments

Organic carbon (OC) burial is an important process influencing atmospheric CO₂ concentration and global climate change; therefore it is essential to obtain information on the factors determining its preservation. The Southern Ocean (SO) is believed to play an important role in sequestering CO₂ from the atmosphere via burial of OC. Here we investigate the degradation of organic-walled dinoflagellate cysts (dinocysts) in two short cores from the SO to obtain information on the factors influencing OC preservation. On the basis of the calculated degradation index kt, we conclude that both cores are affected by species-selective aerobic degradation of dinocysts. Further, we calculate a degradation constant k using oxygen exposure time derived from the ages of our cores. The constant k displays a strong relationship with pore-water O₂, suggesting that decomposition of OC is dependent on both the bottom- and pore-water O₂ concentrations.     

Recent insights into the dissolved and particulate fluxes from the Himalayan tributaries to the Ganga River

The Ganga River plays a major role in the transfer of materials from the Indian sub-continent to the Bay of Bengal, both in dissolved and particulate forms. To understand the present elemental dynamics of the Ganga River system, it is important to assess the hydrogeochemical contribution of its tributaries. In this paper, we present an updated database on dissolved and particulate fluxes and denudation rates of the Himalayan tributaries of the Ganga River (Ramganga, Ghaghara, Gandak and Kosi). Dissolved trace element concentrations, their fluxes and suspended sediment-associated elemental fluxes of the Himalayan tributaries have been reported for the first time. Total dissolved flux of the Ramganga, Ghaghara, Gandak and Kosi was estimated as 4, 19.1, 10.3 and 8.8 million tons year^?1 accounting for ~?5.7, ~?27.3, ~?14.7 and ~?12.6%, respectively, of the total annual dissolved load carried by the Ganga River. The total particulate flux of the Ramganga, Ghaghara, Gandak and Kosi was computed as 8.2, 81.6, 30.9 and 19.5 million tons year^?1, respectively. Compared to earlier studies, we have found a significant increase in the total dissolved flux and chemical denudation rate of the studied tributaries. The estimated particulate fluxes were found to be low in comparison to the previous studies. We suggest that a significant increase in the dissolved fluxes and a decrease in the particulate fluxes are an indication of the increasing anthropogenic disturbances in the catchment of these tributaries.     

Revising macroseismic data in Switzerland: The December 20, 1720 earthquake in the region of Lake Constance

Upgrading the Earthquake Catalog of Switzerland (ECOS) included revising the earthquake of 1720. This change has major importance for history and seismology.Although that quake has been the subject of several publications, none was based on critical methods. This re-evaluation of the event is built upon a new and more reliable database established after investigating archives and libraries. Using data from such historical sources, we assigned new site intensities, adopting the criteria established by the European macroseismic scale EMS 98 (Grünthal, 1998).We discovered that the event had been assigned an overestimated intensity, due to interpretation errors in former earthquake catalogs and compilations. We recommend reducing the intensity from I₀= VIII to I₀= VI (EMS 98). The moment magnitude is given as M_W= 4.6. Since the event had been considered the largest for its respective area, downgrading it now will influence the seismic hazard assessment for this region.     

Toxicity studies of elemental sulfur in marine sediments

Elemental sulfur(ES) is a component essential for proper development of animals, but it can be toxic for aquatic organisms. The objectives of the study reported here included determination of ES concentrations in sediment collected in the area of the Gulf of Gdansk(Baltic Sea) and search for the possible correlations with the ecotoxicity results. Sediment samples were collected from four locations: the Vistula River mouth, in the Port Basin, in the area of discharge of the treated wastewater from the Wastewater Treatment Plant(WWTP) and in the area of the sunken World War Ⅱ s/s 'Stuttgart' shipwreck. The levels of elemental sulfur were determined using a gas chromatograph coupled with a mass spectrometer(GC-MS). Toxicity of marine sediment samples was estimated for three biotest organisms-bioluminescent bacteria Vibrio fischeri, crustacean Heterocypris incongruens, and Synapis alba plant. The highest toxicity of sediments for all indicator organisms was observed in samples taken at the place of the shipwreck(2-100%). The same samples had a high sulfur content(16.7-143.2 μg/g dry weight(d.w.))therefore, it was decided to investigate whether the presence of ES in the sediment in the studied area can have an impact on the results of the ecotoxicity determination in real samples. However, the removal of sulfur from the samples resulted in no significant changes in the level of toxicity of the samples. In this research it could not be confirmed that the presence of elemental sulfur is the only factor responsible for the observed sediment toxicity. It seems that other compounds or their mixtures present in the sediment may have a significant influence on the results obtained.     

Alternating field characteristics of pseudo-single-domain (2–14 μm) and multidomain magnetite

We report normalized AF demagnetization curves of anhysteretic remanences (ARM's) produced by 1-, 10- and 40-Oe steady fields and of saturation isothermal remanence (IRM_s) in a suite of dispersed, unannealed magnetite powders with median sizes of 2, 4, 6, 10 and 14 μm (pseudo-single-domain or PSD size range) and 100 μm (multidomain or MD size). Interpreted in the light of the domain structure test first proposed by Lowrie and Fuller [12], the relative stability trend of curves for the 2 μm sample is of single-domain (SD) type, the 1-Oe ARM being most resistant to demagnetization followed by the 10-Oe and 40-Oe ARM's and IRM_s. For the 100-μm sample, the trend is exactly reversed and is of MD-type. In the 4–14 μm samples, hitherto undescribed transitional trends between SD-type and MD-type occur. At 6 μm, 1-Oe, 10-Oe and 40-Oe ARM's preserve an SD-type trend but for all AF's > 75 Oe, IRM_s is more resistant than any of these remanences. At 10 μm, this trend is unmistakable, and only at 14 μm do the 1-Oe, 10-Oe and 40-Oe ARM curves merge. We conclude (1) that the Lowrie-Fuller test distinguishes between small MD grains enhanced by PSD remanence and large MD grains lacking PSD remanence, rather than between SD and MD structures per se, and (2) that in the PSD transition region from 6 to 14 μm in magnetite, IRM_s changes over to MD-type relative stability around 6 μm, whereas 10-Oe and 40-Oe ARM's achieve an MD-type trend around 14 μm, in accord with the predicted field dependence of the PSD threshold size.Our theoretical interpretation assumes that the intrinsic (internal field) coercive force spectra of weak-field and strong-field remanences are identical but that the observed (external field) spectrum is shifted to lower fields as a result of the internal demagnetizing field — NJ_r of the remanence J_r. The effect is slight for weak-field J_r's but substantial for IRM_s. Since all coercivities, high as well as low, are shifted, the result of the Lowrie-Fuller test is determined simply by the shape of the intrinsic coercivity spectrum or the corresponding AF demagnetization curve. Depending on the model of self-demagnetization used, either subexponential or sublinear AF decay curves of weak-field remanence will automatically lead to an MD-type trend, whereas by either model the decay curves that characterize SD and PSD remanences (decaying slowly initially and then more rapidly) will always produce and SD-type trend.