On the hydrothermal stability of MCM-41. Evidence of capillary tension-induced effects

MCM-41's limited hydrothermal stability has been often related to the hydrolysis of Si-O-Si bonds due to the low degree of condensation, its thin walls or a combination of them. In this work, evidence for an additional factor is provided; a physical effect that occurs during the drying of the hydrothermally treated calcined material due to the intense capillary stress exerted in water. Depending on both physical (i.e. mechanical) and chemical (i.e. hydrolysis) resistances, the structure undergoes differently. Three MCM-41 samples with different degree of condensation were investigated. The most remarkable results are found with un-aged TEOS based material, which gets fully disordered and shrunk for all applied hydrothermal temperatures in water. Comparison between water and a low-surface-tension-solvent drying revealed that capillarity is responsible for the loss of ordering (and shrinkage) at moderate hydrothermal temperatures. The material's structure is hexagonal and shrinkage-free under the low-surface-tension-solvent route. At a high hydrothermal temperature, hydrolysis is extensive and responsible for the loss of ordering. The other remarkable finding regards the aged MCM-41 mesostructure that maintains the hexagonal features at all applied temperatures in water, and it is more stable against capillarity at high temperature. The Na-metasilicate based material is mechanically very stable and gets disordered at high temperature due to hydrolysis.

Effect of Surfactants on the Structure and Morphology of Magnesium Borate Hydroxide Nanowhiskers Synthesized by Hydrothermal Route

Magnesium borate hydroxide (MBH) nanowhiskers were synthesized using a one step hydrothermal process with different surfactants. The effect surfactants have on the structure and morphology of the MBH nanowhiskers has been investigated. The X-ray diffraction profile confirms that the as-synthesized material is of single phase, monoclinic MgBO2(OH). The variations in the size and shape of the different MBH nanowhiskers have been discussed based on the surface morphology analysis. The annealing of MBH nanowhiskers at 500 °C for 4 h has significant effect on the crystal structure and surface morphology. The UV–vis absorption spectra of the MBH nanowhiskers synthesized with and without surfactants show enhanced absorption in the low-wavelength region, and their optical band gaps were estimated from the optical band edge plots. The photoluminescence spectra of the MBH nanowhiskers produced with and without surfactants show broad emission band with the peak maximum at around 400 nm, which confirms the dominant contribution from the surface defect states.

A model of the hydrothermal system at Casa Diablo in Long Valley, California, based on resistivity profiles and soil mercury analyses

A description and model of the near-surface hydrothermal system at Casa Diablo, with its implications for the larger-scale hydrothermal system of Long Valley, California, is presented. The data include resistivity profiles with penetrations to three different depth ranges, and analyses of inorganic mercury concentrations in 144 soil samples taken over a 1.3 by 1.7 km area. Analyses of the data together with the mapping of active surface hydrothermal features (fumaroles, mudpots, etc.), has revealed that the relationship between the hydrothermal system, surface hydrothermal activity, and mercury anomalies is strongly controlled by faults and topography. There are, however, more subtle factors responsible for the location of many active and anomalous zones such as fractures, zones of high permeability, and interactions between hydrothermal and cooler groundwater. In addition, the near-surface location of the upwelling from the deep hydrothermal reservoir, which supplies the geothermal power plants at Casa Diablo and the numerous hot pools in the caldera with hydrothermal water, has been detected. The data indicate that after upwelling the hydrothermal water flows eastward at shallow depth for at least 2 km and probably continues another 10 km to the east, all the way to Lake Crowley.

Role of metalliferous mudstones and graphitic shales in the location, genesis, and paleoenvironment

The Cambrian Tally Pond volcanic belt in central Newfoundland contains numerous volcanogenic massive sulphide (VMS) deposits, prospects, and showings that are locally associated with metalliferous mudstones and/or graphitic shales. Deposits in the belt are bimodal felsic-type VMS that are both base metal- (e.g., Duck Pond, Boundary) and precious metal-enriched (e.g., Lemarchant). At the Lemarchant deposit metalliferous mudstones are genetically and spatially associated with mineralization, whereas the relationship of other mudstones and shales to massive sulphide mineralization is more intricate and remains not fully understood. Metalliferous mudstones represent a hiatus in the volcanic activity where the deposition of hydrothermal products dominated over the abiogenic background sedimentation and/or dilution by volcaniclastic-epiclastic material. Lithogeochemical signatures allow one to distinguish between predominantly hydrothermally or detritally (i.e., non-hydrothermal) derived material. Metalliferous mudstones with a significant hydrothermal component, like those at Lemarchant, have elevated Fe/Al and base-metal contents, compared to detrital shales, and shale-normalized negative Ce and positive Eu anomalies, indicative of deposition from high temperature (>250°C) hydrothermal fluids within an oxygenated water column. Mudstones and shales sampled from other locations in the Tally Pond volcanic belt have more variable signatures ranging from hydrothermal (signatures as above) to non-hydrothermal (no positive Eu-anomalies, flat REE patterns), with some that have mixed (hydrothermal and detrital) signatures. Both S and Pb isotopic compositions indicate that proximal sulphides hosted in mudstones immediately associated with massive sulphide mineralization within the Lemarchant deposit contain a higher proportion of sulphur derived from hydrothermal sources and processes, and have more juvenile lead contributions, when compared to sulphides distal (not associated with massive sulphides) from mineralization. Lead and Nd isotopic compositions of both whole rock and minerals in the Lemarchant mudstones indicate involvement of underlying crustal basement during massive sulphide formation and throughout the evolution of the Tally Pond belt. Metalliferous mudstones precipitated early in the massive sulphide depositional history, but also have undergone syn- and post-ore-forming processes and have a larger lateral extent than the mineralization. Using lithogeochemistry, whole rock and in situ stable and radiogenic isotopes it is possible to distinguish prospective vent proximal (immediately associated with massive sulphide mineralization) from less prospective distal (not associated with massive sulphides) depositional environments and to reconstruct the paleotectonic setting on a deposit- to regional-scale for the Lemarchant deposit and other mudstone-associated prospects in the Tally Pond volcanic belt.

Environmental data from coastal sediments along natural CO2 gradients at a volcanic vent in Papua New Guinea

Natural CO2 venting systems can mimic conditions that resemble intermediate to high pCO2 levels as predicted for our future oceans. They represent ideal sites to investigate potential long-term effects of ocean acidification on marine life. To test whether microbes are affected by prolonged exposure to pCO2 levels, we examined the composition and diversity of microbial communities in oxic sandy sediments along a natural CO2 gradient. Increasing pCO2 was accompanied by higher bacterial richness and by a strong increase in rare members in both bacterial and archaeal communities. Microbial communities from sites with CO2 concentrations close to today's conditions had different structures than those of sites with elevated CO2 levels. We also observed increasing sequence abundance of several organic matter degrading types of Flavobacteriaceae and Rhodobacteraceae, which paralleled concurrent shifts in benthic cover and enhanced primary productivity. With increasing pCO2, sequences related to bacterial nitrifying organisms such as Nitrosococcus and Nitrospirales decreased, and sequences affiliated to the archaeal ammonia-oxidizing Thaumarchaeota Nitrosopumilus maritimus increased. Our study suggests that microbial community structure and diversity, and likely key ecosystem functions, may be altered in coastal sediments by long-term CO2 exposure to levels predicted for the end of the century.