First-principles study of illite-smectite and implications for clay mineral systems

Illite-smectite interstratified clay minerals are ubiquitous in sedimentary basins and they have been linked to the maturation, migration and trapping of hydrocarbons(1), rock cementation(2), evolution of porewater chemistry during diagenesis(3) and the development of pore pressure(4). But, despite the importance of these clays, their structures are controversial. Two competing models exist, each with profoundly different consequences for the understanding of diagenetic processes: model A views such interstratified clays as a stacking of layers identical to endmember illite and smectite layers, implying discrete and independently formed units (fundamental particles)(5), whereas model B views the clays as composed of crystallites with a unique structure that maintains coherency over much greater distances, in line with local charge balance about interlayers(6). Here we use first-principles density-functional theory to explore the energetics and structures of these two models for an illite-smectite interstratified clay mineral with a ratio of 1:1 and a Reichweite parameter of 1. We find that the total energy of model B is 2.3 kJ atom(-1) mol(-1) lower than that of model A, and that this energy difference can be traced to structural distortions in model A due to local charge imbalance. The greater stability of model B requires re-evaluation of the evolution of the smectite-to-illite sequence of clay minerals, including the nature of coexisting species, stability relations, growth mechanisms and the model of fundamental particles.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/62760/1/nature01155.pd

Prograde and retrograde history of the Junction School eclogite, California, and an evaluation of garnet-phengite-clinopyroxene thermobarometry

Quantitative thermobarometry of inclusions in zoned garnet from a Franciscan eclogite block record a counter-clockwise P–T path from blueschist to eclogite and back. Garnet retains prograde zoning from inclusion-rich Alm52Grs30Pyp6Sps12 cores to inclusion-poor Alm62Grs25Pyp12Sps1 mantles, with overgrowths of highly variable composition. Barometry using the Waters–Martin version of the garnet–phengite–omphacite thermobarometer yields conditions of 7–15 kbar, 400–500°C (garnet cores), 18–22 kbar, ∼550°C (mantles), and 10–14 kbar, 350–450°C (overgrowths), in agreement with clinozoisite–sphene–rutile–garnet–quartz barometry. These pressures are ∼10–15 kbar less than those obtained using more recent, fully thermodynamic calibrations of the phengite–omphacite–garnet thermobarometer. Low early temperatures suggest that the block was subducted in a thermally mature subduction zone and not at the inception of subduction when prograde temperature is expected to be higher. Franciscan high-grade blocks likely represent crust subducted throughout the history of this convergent margin, rather than only at the inception of the subduction zone

Metamorphic Fluids In The Deep Crust - Evidence From The Adirondacks

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/62547/1/301226a0.pd

Young High-temperature Granulites From The Base Of The Crust In Central Mexico

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/62945/1/342265a0.pd

Lightning-Induced Reduction of Phosphorus Oxidation State

Phosphorus is frequently the limiting nutrient in marine and terrestrial ecosystems, largely owing to its poor solubility and slow movement through the rock cycle1, 2. Phosphorus is viewed to exist in geological systems almost exclusively in its fully oxidized state as orthophosphate. However, many microorganisms use the partially oxidized forms—phosphite and hypophosphite—as alternative phosphorus sources3, 4, 5, and genomic evidence suggests that this selectivity is ancient6. Elucidating the processes that reduce phosphate is therefore key to understanding the biological cycling of phosphorus. Here we show that cloud-to-ground lightning reduces phosphate in lightning-derived glass compounds, termed fulgurites. We analysed the phosphorus chemistry of ten fulgurites retrieved from North America, Africa and Australia, using microprobes and 31P nuclear magnetic resonance. Half of the fulgurites contained reduced phosphorus, mainly in the form of phosphite. The amount and type of reduced phosphorus was dependent on the composition of the fulgurite section examined: carbon-rich sections contained around 22% reduced phosphorus in the form of iron phosphide, whereas other fulgurites contained between 37 and 68% in the form of phosphite. We suggest that lightning provides some portion of the reduced phosphorus used by microbes, and that phosphate reduction by lightning can be locally important to phosphorus biogeochemistry

Textures, paragenesis and wall-rock alteration of lode-gold deposits in the Charters Towers district, north Queensland: implications for the conditions of ore formation

Ore deposits of the Charters Towers Goldfield (CTGF) are mainly hosted by fault-fill veins. Extensional (∼8% of all veins) and stockwork-like (∼3%) veins are less common and of little economic significance. Crosscutting relationships and published structural and geochronological data indicate a Late Silurian to Early Devonian timing of gold mineralization, coincident with regional shortening (D4) and I-type magmatism. Paragenetic relationships, which are uniform in veins everywhere within the CTGF, suggest that vein formation commenced with the deposition of large volumes of buck quartz (stage I), followed by buck and comb quartz, and significant pyrite and arsenopyrite precipitation (stage II). Gold was introduced during stage III, after earlier sphalerite and coincident with galena and chalcopyrite. Narrow, discontinuous calcite veins of stage IV mark the waning of gold-related hydrothermal activity or a later unrelated episode. Ore zones within the veins are everywhere composed of comb and/or gray quartz, calcite and/or ankerite and bands or clusters of fractured pyrite that are spatially associated with galena, sphalerite or chalcopyrite. Low-grade or barren vein sections, on the other hand, are mainly composed of milky buck quartz with little evidence for modification, overprinting or interaction with later fluids. Gold-related hydrothermal wall-rock alteration is symmetrically zoned, displaying proximal sericite–ankerite and distal epidote–chlorite–hematite assemblages that may be taken to imply wall-rock interaction with near neutral fluids (pH 5–6). Isocon plots assuming immobile Al, P, Ti, Y and Zr consistently indicate As, K, Pb, S and Zn enrichment and Na, Si and Sr depletion in altered wall-rock specimens relative to the least altered rocks. Alteration assemblages, quartz textures, fault rocks and published fluid inclusion and stable isotope data imply that the veins were formed under conditions of episodic fluid overpressuring (∼0.9–3.8 kbar), at a depth of ∼7 km and a temperature of ∼310°C. The published fluid inclusion data also imply that gold precipitation may have been brought about by fluid mixing. However, physi- and chemisorption of gold complexes onto sulfide surfaces may have been important depositional processes and controls on gold enrichment at the millimeter to centimeter scale, given that most gold particles are attached to the surfaces of pyrite crystals of stage II or to etch-pits and fracture surfaces within the earlier pyrite