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Abstract

The focus of this study is to investigate the applicability of natural mineral iron disulfide (pyrite) in degradation of aromatic compounds including benzene and several chlorinated benzenes (from mono-chlorinated benzene (CB), di-chlorinated benzenes (di-CBs) to tri-chlorobenzenes (tri-CBs) in aerobic pyrite suspension by using laboratory batch experiments at 25°C and room pressure. At first, chlorobenzene was studied as a model compound for all considered aromatic compounds. CB was degraded in aerobic pyrite suspension, transformed to several organic acids and finally to CO2 and Cl-. Transformations of remaining aromatic compounds were pursued by measuring their degradation rates and CO2 and Cl- released with time. Transformation kinetics was fitted to the pseudo-first-order reactions to calculate degradation rate constant of each compound. Degradation rates of the aromatic compounds were different depending on their chemical structures, specifically the number and position of chlorine substituents on the benzene ring in this study. Compounds with the highest number of chlorine substituent at m-positions have highest degradation rate (1,3,5-triCB > 1,3-diCB > others). Three chlorine substituents closed together (1,2,3-triCB) generated steric hindrance effects. Therefore 1,2,3-triCB wasthe least degraded compound. The degradation rates of all compounds were in the following order: 1,3,5-triCB > 1,3-diCB > 1,2,4-triCB ≅ 1,2-diCB ≅ CB ≅ benzene > 1,4-diCB > 1,2,3-triCB. The final products of the transformations were CO2 and Cl-. Oxygen was the common oxidant for pyrite and aromatic compounds. The presence of aromatic compounds reduced the oxidation rate of pyrite, which reduced the amount of ferrous and sulfate ions release to aqueous solution.
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Abstract

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.
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