Thermogravimetric determination of the carbon dioxide reactivity of char from some New Zealand coals and its association with the inorganic geochemistry of the parent coal

Thermogravimetrically-determined carbon dioxide reactivities of chars formed from New Zealand coals, ranging in rank from lignite to high volatile bituminous, vary from 0.12 to 10.63 mg/h/mg on a dry, ash-free basis. The lowest rank subbituminous coal chars have similar reactivities to the lignite coal chars. Calcium content of the char shows the strongest correlation with reactivity, which increases as the calcium content increases. High calcium per se does not directly imply a high char reactivity. Organically-bound calcium catalyses the conversion of carbon to carbon monoxide in the presence of carbon dioxide, whereas calcium present as discrete minerals in the coal matrix, e.g., calcite, fails to significantly affect reactivity. Catalytic effects of magnesium, iron, sodium and phosphorous are not as obvious, but can be recognised for individual chars. The thermogravimetric technique provides a fast, reliable analysis that is able to distinguish char reactivity differences between coals, which may be due to any of the above effects. Published by Elsevier Science B.V.

Organic and inorganic geochemistry of Ljubija siderite deposits, NW Bosnia and Herzegovina

The Ljubija siderite deposits, hosted by a Carboniferous sedimentary complex within the Inner Dinarides, occur as stratabound replacement-type ore bodies in limestone blocks and as siderite-sulfides veins in shale. Three principal types of ore textures have been recognized including massive dark siderite and ankerite, siderite with zebra texture, and siderite veins. The ore and host rocks have been investigated by a combination of inorganic (major, trace, and rare earth element concentrations), organic (characterization of hydrocarbons including biomarkers), and stable isotope geochemical methods (isotope ratios of carbonates, sulfides, sulfates, kerogen, and individual hydrocarbons). New results indicate a marine origin of the host carbonates and a hydrothermal-metasomatic origin of the Fe mineralization. The differences in ore textures (e.g., massive siderite, zebra siderite) are attributed to physicochemical variations (e.g., changes in acidity, temperature, and/or salinity) of the mineralizing fluids and to the succession and intensity of replacement of host limestone. Vein siderite was formed by precipitation from hydrothermal fluids in the late stage of mineralization. The equilibrium fractionation of stable isotopes reveals higher formation temperatures for zebra siderites (around 245A degrees C) then for siderite vein (around 185A degrees C). Sulfur isotope ratios suggest Permian seawater or Permian evaporites as the main sulfur source. Fluid inclusion composition confirms a contribution of the Permian seawater to the mineralizing fluids and accord with a Permian mineralization age. Organic geochemistry data reflect mixing of hydrocarbons at the ore site and support the hydrothermal-metasomatic origin of the Ljubija iron deposits.

Inorganic geochemistry, epoch and water content in sediments at DSDP Hole 91-595A

This chapter summarizes the principal results of drilling at Deep Sea Drilling Project (DSDP) Site 595, where the Ngendei Seismic Experiment and the emplacement of DARPA's Marine Seismic System (MSS) were carried out. Background and objectives for this work are presented in the introductory chapter to this volume. Interpretation of the seismic experiment and drilling results are presented in subsequent parts of this volume. The chapter also provides a detailed operational summary of the successful deployment of the MSS during Leg 91.

Inorganic geochemistry, epoch and water content in sediments at DSDP Site 91-596

Originally, we had planned to piston core at Site 595 in order to meet the sedimentologic and biostratigraphic objectives outlined in the introductory chapter. However, consultation with our colleagues, Thomas Jordan and John Orcutt on board Melville, indicated that coring near the ocean bottom seismometer (OBS) array around Hole 595B could alter the programmed signal to noise ratio above which teleseisms trigger recording in the OBSs. They requested that we core no closer than about 8 km from three OBSs nearest Hole 595B, and selected a target for us about that distance to the west. Since a new beacon was required at this distance, a new site number, 596, was designated. Briefly, we planned to obtain oriented hydraulic piston cores to the top of the cherts, then core through the cherts using the extended core barrel (XCB) to basement. With improved recovery, we hoped to reach the sediment/basalt contact, and thus obtain a reliable biostratigraphic determination of the basement age. We planned to obtain at least one core in basement, perhaps more, with time permitting. We planned no geophysical program for the hole.

Mineralogy and inorganic geochemistry of sediments at DSDP Leg 65 Holes

During Leg 65, 15 holes were drilled at four sites located on young crust in the mouth of the Gulf of California. Quaternary to upper Pliocene hemipelagic sediments above and interlayered within the young basaltic basement were cored. The influence of hot lava, high temperature gradients, and hydrothermal activity on the mineralogy and geochemistry of the terrigenous sediments near contacts with basalts might therefore be expected. The purpose of the present study was to determine the mineralogy and inorganic geochemistry of these sediments and to analyze the nature and extent of low temperature alteration. To this end we studied the mineralogy and inorganic geochemistry of 75 sediment samples, including those immediately overlying uppermost basalts and those from layers alternating with basalts within the basement. We separated three size fractions - <2 µm (clay), 2-20 µm (intermediate), and >20 µm (coarse) - and applied the following mineralogical determinations: x-ray diffraction (XRD), infrared spectroscopy, transmission and scanning electron microscopy, and optical microscopy (for coarse fractions, using thin sections and smear slides). We calculated the percentages of clay minerals using Biscaye's (1964) method, and used routine wet chemical analyses to determine bulk composition and quantitative spectral analyses for trace elements.

Organic and inorganic geochemistry and archaeal community composition of hypersaline sediments from Orca Basin, RV Atlantis Expedition AT18-02

Among the most extreme habitats on Earth, dark, deep, anoxic brines host unique microbial ecosystems that remain largely unexplored. As the terminal step of anaerobic degradation of organic matter, methanogenesis is a potentially significant but poorly constrained process in deep-sea hypersaline environments. We combined biogeochemical and phylogenetic analyses as well as incubation experiments to unravel the origin of methane in hypersaline sediments of Orca Basin in the northern Gulf of Mexico. Substantial concentrations of methane (up to 3.4 mM) coexisted with high concentrations of sulfate (16-43 mM) in two sediment cores retrieved from the northern and southern parts of Orca Basin. The strong depletion of 13C in methane (-77 to -89 per mill) pointed towards a biological source. While low concentrations of competitive substrates limited the significance of hydrogenotrophic and acetoclastic methanogenesis, the presence of non-competitive methylated substrates (methanol, trimethylamine, dimethyl sulfide, dimethylsulfoniopropionate) supported the potential for methane generation through methylotrophic methanogenesis. Thermodynamic calculations demonstrated that hydrogenotrophic and acetoclastic methanogenesis were unlikely to occur under in situ conditions, while methylotrophic methanogenesis from a variety of substrates was highly favorable. Likewise, carbon isotope relationships between methylated substrates and methane supported methylotrophic methanogenesis as the major source of methane. Stable isotope tracer and radiotracer experiments with 13C bicarbonate, acetate and methanol as well as 14C-labeled methylamine indicated that methylotrophic methanogenesis was the predominant methanogenic pathway. Based on 16S rRNA gene sequences, halophilic methylotrophic methanogens related to the genus Methanohalophilus dominated the benthic archaeal community in the northern basin but also occurred in the southern basin. High abundances of methanogen lipid biomarkers such as intact polar and polyunsaturated hydroxyarchaeols were detected in sediments from the northern basin, with lower abundances in the southern basin. Strong 13C-depletion of saturated and monounsaturated hydroxyarchaeol were consistent with methylotrophic methanogenesis as the major methanogenic pathway. Collectively, the availability of methylated substrates, thermodynamic calculations, experimentally determined methanogenic activity as well as lipid and gene biomarkers strongly suggested methylotrophic methanogenesis as predominant pathway of methane formation in the presence of sulfate in Orca Basin sediments.

Rare earth element fractionation in authigenic illite–smectite from Late Permian clastic rocks, Bowen Basin, Australia: implications for physico-chemical environments of fluids during illitization

REE analyses were performed on authigenic illitic clay. minerals from Late Permian mudrocks, sandstones and bentonites from the Bowen Basin (Australia). The mixed-layer illite-smectite exhibit REE patterns with an obvious fractionation of the HREE from the LREE and MREE, which is an apparent function of degree of illitization reaction. The highly illitic (R greater than or equal to 3) illite-smectite from the northern Bowen Basin show a depletion of LREE relative to the less illitic (R=0 and 1) clays. In contrast, an enrichment of HREE for the illite-rich clays relative to less. illitic clays is evident for the southern Bowen Basin samples. The North American Shale Composite-normalized (La/Lu)(sn) ratios show negative correlations with the illite content in illite-smectite and positive correlations with the delta(18)O values of the clays for both the northern and southern Bowen Basin samples. These correlations indicate that the increasing depletion of LREE in hydrothermal fluids is a function of increasing water/rock ratios in the northern Bowen Basin. Good negative correlations between (La/Lu)(sn) ratios and illite content in illite-smectite from the southern Bowen Basin suggest the involvement of fluids with higher alkalinity and higher pH in low water/ rock ratio conditions. Increasing HREE enrichment with delta(18)O decrease indicates the effect of increasing temperature at low water/rock ratios in the southern Bowen Basin. Results of the present study confirm the conclusions of some earlier studies suggesting that REE in illitic clay minerals are mobile and fractionated during illitization and that this fact should be considered in studies of sedimentary processes and in identifying provenance. Moreover, our results show that REE systematic of illitic clay minerals can be applied as an useful technique to gain information about physico-chemical conditions during thermal and fluid flow events in certain sedimentary basins. (C) 2003 Elsevier Science B.V. All rights reserved.

Weathering geochronology by (U-Th)/He dating of goethite

Nine samples of supergene goethite (FeOOH) from Brazil and Australia were selected to rest the suitability of this mineral for (U-Th)/He dating. Measured He ages ranged from 61 to 8 Ma and were reproducible to better than a few percent despite very large Variations in [U] and [Th]. In all Samples with internal stratigraphy or independent age constraints, the He ages corroborated the expected relationship's. These data demonstrate that internally consistent He ages can be obtained on goethite. but do not prove quantitative 4 He retention. To assess possible diffusive He loss, stepped-heating experiments were performed on two goethite samples that were subjected to proton irradiation to produce a homogeneous distribution of spallogenic He-3. The He-3 release pattern indicates the presence of at least two diffusion domains, one with high helium retentivity and the other with very low retentivity at Earth surface conditions. The low retentivity domain, which accounts for similar to 5% of He-3, contains no natural He-4 and may represent poorly crystalline or intergranular material which has lost all radiogenic He-4 by diffusion in nature. Diffusive loss of He-3 from the high retentivity domain is independent of the macroscopic dimensions of the analyzed polycrystalline aggregate, so probably represents diffusion from individual micrometer-size goethite crystals. The He-2/He-3 evolution during the incremental heating experiments shows that the high retentivity domain has retained 90%-95% of its radiogenic helium. This degree of retentivity is in excellent agreement with that independently predicted from the helium diffusion coefficients extrapolated to Earth surface temperature and held for the appropriate duration. Considering both the high and low retentivity domains, these data indicate that one of the samples retained 90% of its radiogenic He-4 over 47.5 Ma and the other retained 86% over 12.3 Ma. Thus while diffusive-loss corrections to supergene goethite He ages are required. these initial results indicate that the corrections are not extremely large and can be rigorously quantified using the proton-irradiation He-4/He-3 method. Copyright (C) 2005 Elsevier Ltd.