51 samples from the Middle Triassic black shales (organic carbon−rich silt− stones; up to 4.9% TOC – Total Organic Carbon) from the stratotype section of the Bravaisberget Formation (western Spitsbergen) were analyzed with respect to isotopic composition of pyritic sulphur (34S) and TOC. Isotopic composition of syngenetic py− rite−bound sulphur shows wide (34S from −26‰ to +8‰ VCDT) and narrow (34S from −4‰ to +17‰ VCDT) variation of the 34S in upper and lower part of the section, respec− tively. Range of the variation is associated with abrupt changes in dominant lithology. Wide 34S variation is found in lithological intervals characterized by alternation of black shales and phosphorite−bearing sandstones. The narrow 34S variation is associated with the lithological interval dominated by black shales only. Wide and narrow variation of the #2;34S values suggests interplay of various factors in sedimentary environment. These fac− tors include oxygen concentration, clastic sedimentation rate, bottom currents and bur− rowing activity. Biological productivity and rate of dissimilatory sulphate reduction had important impact on the 34S variation as well. Wide variation of the 34S values in the studied section resulted from high biological productivity and high rate of dissimilatory sulphate reduction. Variable degree of clastic sedimentation rate and burrowing activity as well as the activity of poorly oxygenated bottom currents could also cause a co−occurrence of isotopically light and heavy pyrite in differentiated diagenetic micro−environments. Occurrence of organic matter depleted in hydrogen could also result in a wide variation of the 34S values. Narrow variation of the #2;34S values was due to a decrease of biological productivity and low rate of dissimilatory sulphate reduction. Low organic matter supply, low oxygen concentration and bottom currents and burrowing activity were also responsible for narrow variation of the 34S. The narrow range of the 34S variation was also due to occurrence of hydrogen−rich organic matter. In the studied section the major change in range of the 34S variation from wide to narrow appears to be abrupt and clearly associated with change in lithology. The change of lithology and isotopic valuesmay sug− gest evolution of the sedimentary environment from high− to low−energy and also facies succession from shallow to deeper shelf. The evolution should be linked with the Late Anisian regional transgressive pulse in the Boreal Ocean.
The demand for a net reduction of carbon dioxide and restrictions on energy efficiency make thermal conversion of biomass a very attractive alternative for energy production. However, sulphur dioxide emissions are of major environmental concern and may lead to an increased corrosion rate of boilers in the absence of sulfatation reactions. Therefore, the objective of the present study is to evaluate the kinetics of formation of sulphur dioxide during switchgrass combustion. Experimental data that records the combustion process and the emission formation versus time, carried out by the National Renewable Energy Institute in Colorado (US), was used to evaluate the kinetic data. The combustion of switchgrass is described sufficiently accurate by the Discrete Particle Method (DPM). It predicts all major processes such as heating-up, pyrolysis, combustion of switchgrass by solving the differential conservation equations for mass and energy. The formation reactions of sulphur dioxide are approximated by an Arrhenius-like expression including a pre-exponential factor and an activation energy. Thus, the results predicted by the Discrete Particle Method were compared to measurements and the kinetic parameters were subsequently corrected by the least square method until the deviation between measurements and predictions was minimised. The determined kinetic data yielded good agreement between experimental data and predictions.
Pyrite framboids occur in loose blocks of plant−bearing clastic rocks related to volcano−sedimentary succession of the Mount Wawel Formation (Eocene) in the Dragon and Wanda glaciers area at Admiralty Bay, King George Island, West Antarctica. They were investigated by means of optical and scanning electron microscopy, energy−dispersive spectroscopy, X−ray diffraction, and isotopic analysis of pyritic sulphur. The results suggest that the pyrite formed as a result of production of hydrogen sulphide by sulphate reducing bacteria in near surface sedimentary environments. Strongly negative #2;34SVCDT values of pyrite (−30 – −25 ‰) support its bacterial origin. Perfect shapes of framboids resulted from their growth in the open pore space of clastic sediments. The abundance of framboids at cer− tain sedimentary levels and the lack or negligible content of euhedral pyrite suggest pulses of high supersaturation with respect to iron monosulphides. The dominance of framboids of small sizes (8–16 μm) and their homogeneous distribution at these levels point to recurrent development of a laterally continuous anoxic sulphidic zone below the sediment surface. Sedimentary environments of the Mount Wawel Formation developed on islands of the young magmatic arc in the northern Antarctic Peninsula region. They embraced stagnant and flowing water masses and swamps located in valleys, depressions, and coastal areas that were covered by dense vegetation. Extensive deposition and diagenesis of plant detritus in these environments promoted anoxic conditions in the sediments, and a supply of marine and/or volcanogenic sulphate enabled its bacterial reduction, precipitation of iron mono− sulphides, and their transformation to pyrite framboids.