Mineral Redox Buffers and The Stability of Organic Compounds Under Hydrothermal Conditions

1996 ◽  
Vol 432 ◽  
Author(s):  
J. S. Seewald
Keyword(s):  
Organic Compounds ◽  
Active Species ◽  
Hydrothermal Systems ◽  
Hydrothermal Conditions ◽  
Sulfur Species ◽  
Sedimentary Environments ◽  
Mineral Assemblages ◽  
Catalytically Active ◽  
Chemical Conditions ◽  
The Stability

AbstractOrganic compounds play an integral role in numerous geochemical process in subsurface environments. To evaluate factors that regulate the stability of ethane, ethene, propane, and propene in hydrothermal systems a series of experiments were conducted at 300 to 325°C and 350 bars. The experiments contained the mineral assemblages pyrite-pyrrhotite-magnetite, hematite-magnetite-pyrite, and hematite-magnetite to buffer fO2, aH2(aq) and aH2S(aq) at geologically reasonable values.Results of the experiments suggest that under appropriate physical and chemical conditions, metastable redox dependent thermodynamic equilibrium involving liquid water and inorganic iron-bearing mineral assemblages may regulate the relative abundance of short chain alkanes and their corresponding alkenes. In addition, alkenes represent an important intermediary in the conversion of n-alkanes to methane and oxidized species such as carbon dioxide, ketones alcohols, and organic acids.The rates of redox dependent organic reactions during the experiments were strongly influenced by the presence of sulfur. Under relatively oxidizing conditions greater catalytic activity due to the presence of dissolved sulfur species was observed. Fluid speciation calculations suggest that oxidized aquous sulfur compounds represent the catalytically active species.These results suggest that redox conditions and the presence or absence of dissolved sulfur species in natural sedimentary environments may strongly influence the stability of hydrocarbons. Accordingly, models used to predict the stability of oil and the formations of natural gas need to account for chemical processes that involve both organic and inorganic sedimentary components.

Framboid Microcrystal Growth

2021 ◽  
pp. 235-261
Author(s):  
David Rickard
Keyword(s):  
Crystal Growth ◽  
Crystal Surface ◽  
Normal Growth ◽  
Hydrothermal Systems ◽  
Hydrothermal Conditions ◽  
Sedimentary Environments ◽  
Surface Nucleation ◽  
Growth Modes ◽  
Cubic Forms ◽  
Nucleation Growth

Framboid microcrystals grow through surface reaction of S2(-II) or H2S with =FeS moieties at defect sites on the pyrite crystal surface. The surface energies of pyrite vary from the most stable cubic through octahedral to pyritohedral and dodecahedral surfaces. Microcrystals commonly develop as truncated octahedra as the supersaturation decreases during crystal growth in sedimentary environments, although cubic forms may be favored under hydrothermal conditions. Screw dislocation growth followed by surface nucleation growth are the normal growth modes in sediments, whereas surface nucleation growth is likely to dominate in hydrothermal systems. The rate of crystal growth of framboids is unknown but appears to be very fast and normally diffusion-limited. Linear approximations to the diffusion equations show that average 6 μ‎m diameter framboids form in five days in sediments, and formation times increase exponentially from a few hours for ca. 2 μ‎m framboids to three years for the largest 250 μ‎m framboids.

Sewage sludge as a precursor of adsorbents/catalysts for environmental applications

2007 ◽  
Vol 2 (1) ◽  
Author(s):  
A. Ros ◽  
C. Canals-Batlle ◽  
M.A. Lillo-Ródenas ◽  
E. Fuente ◽  
M. A. Montes-Morán ◽  
...  
Keyword(s):  
Sewage Sludge ◽  
Room Temperature ◽  
Waste Water Treatment ◽  
Textural Properties ◽  
Active Species ◽  
Elemental Sulphur ◽  
Gaseous Emissions ◽  
Removal Experiments ◽  
Catalytically Active

This paper focuses on the valorisation of solid residues obtained from the thermal treatment of sewage sludge. In particular, sewage sludge samples were collected from two waste water treatment plants (WWTPs) with different sludge line basic operations. After drying, sludges were heated up to 700 °C in appropriate ovens under diluted air (gasification) and inert (pyrolysis) atmospheres. The solids obtained, as well as the dried (raw) sludges, were characterised to determine their textural properties and chemical composition, including the speciation of their inorganic fraction. All the materials under study were employed as adsorbents/catalysts in H2S removal experiments at room temperature. It was found that, depending on the particular sludge characteristics, outstanding results can be achieved both in terms of retention capacities and selectivity. Some of the solids outperform commercially available sorbents specially designed for gaseous emissions control. In these adsorbents/catalysts, H2S is selectively oxidised to elemental sulphur most likely due to the presence of inorganic, catalytically active species. The role of the carbon-enriched part on these solids is also remarked.

Probing the Catalytically Active Species in POM‐catalysed DNA‐model Hydrolysis

2021 ◽  
Author(s):  
Frederico F Martins ◽  
Ángel Sánchez-González ◽  
Jose Lanuza ◽  
Haralampos N. Miras ◽  
Xabier Lopez ◽  
...  
Keyword(s):  
Active Species ◽  
Catalytically Active

scholarly journals Investigation of Hydrothermally Stressed Silicone Rubber/Silica Micro and Nanocomposite for the Coating High Voltage Insulation Applications

Materials ◽  
2021 ◽  
Vol 14 (13) ◽  
pp. 3567
Author(s):  
Faiza Faiza ◽  
Abraiz Khattak ◽  
Safi Ullah Butt ◽  
Kashif Imran ◽  
Abasin Ulasyar ◽  
...  
Keyword(s):  
Silicone Rubber ◽  
Structural Changes ◽  
Polymer Chains ◽  
Hydrothermal Conditions ◽  
Silica Filler ◽  
Before And After ◽  
Aging Conditions ◽  
The Stability ◽  
Micro Silica ◽  
Applied Stresses

Silicone rubber is a promising insulating material that has been performing well for different insulating and dielectric applications. However, in outdoor applications, environmental stresses cause structural and surface degradations that diminish its insulating properties. This effect of degradation can be reduced with the addition of a suitable filler to the polymer chains. For the investigation of structural changes and hydrophobicity four different systems were fabricated, including neat silicone rubber, a micro composite (with 15% micro-silica filler), and nanocomposites (with 2.5% and 5% nanosilica filler) by subjecting them to various hydrothermal conditions. In general, remarkable results were obtained by the addition of fillers. However, nanocomposites showed the best resistance against the applied stresses. In comparison to neat silicone rubber, the stability of the structure and hydrophobic behavior was better for micro-silica, which was further enhanced in the case of nanocomposites. The inclusion of 5% nanosilica showed the best results before and after applying aging conditions.

scholarly journals Shedding light on the nature of the catalytically active species in photocatalytic reactions using Bi2O3 semiconductor

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Paola Riente ◽  
Mauro Fianchini ◽  
Patricia Llanes ◽  
Miquel A. Pericàs ◽  
Timothy Noël
Keyword(s):  
Experimental Studies ◽  
Heterogeneous Photocatalysis ◽  
Active Species ◽  
Organic Transformations ◽  
Alkyl Bromides ◽  
Catalytically Active ◽  
Visible Light Driven ◽  
Photocatalytic Reactions ◽  
Insight Into ◽  
Photocatalytic Processes

AbstractThe importance of discovering the true catalytically active species involved in photocatalytic systems allows for a better and more general understanding of photocatalytic processes, which eventually may help to improve their efficiency. Bi2O3 has been used as a heterogeneous photocatalyst and is able to catalyze several synthetically important visible-light-driven organic transformations. However, insight into the operative catalyst involved in the photocatalytic process is hitherto missing. Herein, we show through a combination of theoretical and experimental studies that the perceived heterogeneous photocatalysis with Bi2O3 in the presence of alkyl bromides involves a homogeneous BinBrm species, which is the true photocatalyst operative in the reaction. Hence, Bi2O3 can be regarded as a precatalyst which is slowly converted in an active homogeneous photocatalyst. This work can also be of importance to mechanistic studies involving other semiconductor-based photocatalytic processes.

scholarly journals Dual role of CO in the stability of subnano Pt clusters at the Fe3O4(001) surface

2016 ◽  
Vol 113 (32) ◽  
pp. 8921-8926 ◽  
Author(s):  
Roland Bliem ◽  
Jessi E. S. van der Hoeven ◽  
Jan Hulva ◽  
Jiri Pavelec ◽  
Oscar Gamba ◽  
...  
Keyword(s):  
Density Functional ◽  
Elevated Temperatures ◽  
Time Lapse ◽  
Dual Role ◽  
Oxidation Catalyst ◽  
Scanning Tunneling ◽  
Tunneling Microscopy ◽  
Active Metal ◽  
Catalytically Active ◽  
The Stability

Interactions between catalytically active metal particles and reactant gases depend strongly on the particle size, particularly in the subnanometer regime where the addition of just one atom can induce substantial changes in stability, morphology, and reactivity. Here, time-lapse scanning tunneling microscopy (STM) and density functional theory (DFT)-based calculations are used to study how CO exposure affects the stability of Pt adatoms and subnano clusters at the Fe3O4(001) surface, a model CO oxidation catalyst. The results reveal that CO plays a dual role: first, it induces mobility among otherwise stable Pt adatoms through the formation of Pt carbonyls (Pt1–CO), leading to agglomeration into subnano clusters. Second, the presence of the CO stabilizes the smallest clusters against decay at room temperature, significantly modifying the growth kinetics. At elevated temperatures, CO desorption results in a partial redispersion and recovery of the Pt adatom phase.

The Sedimentary Cycle on Early Mars

2019 ◽  
Vol 47 (1) ◽  
pp. 91-118 ◽  
Author(s):  
Scott M. McLennan ◽  
John P. Grotzinger ◽  
Joel A. Hurowitz ◽  
Nicholas J. Tosca
Keyword(s):  
Plate Tectonics ◽  
Sedimentary Rock ◽  
First Order ◽  
Sedimentary Environments ◽  
Source To Sink ◽  
Rock Record ◽  
Mineral Assemblages ◽  
Sedimentary Cycle ◽  
Early Mars ◽  
Over Time

Two decades of intensive research have demonstrated that early Mars ([Formula: see text]2 Gyr) had an active sedimentary cycle, including well-preserved stratigraphic records, understandable within a source-to-sink framework with remarkable fidelity. This early cycle exhibits first-order similarities to (e.g., facies relationships, groundwater diagenesis, recycling) and first-order differences from (e.g., greater aeolian versus subaqueous processes, basaltic versus granitic provenance, absence of plate tectonics) Earth's record. Mars’ sedimentary record preserves evidence for progressive desiccation and oxidation of the surface over time, but simple models for the nature and evolution of paleoenvironments (e.g., acid Mars, early warm and wet versus late cold and dry) have given way to the view that, similar to Earth, different climate regimes on Mars coexisted on regional scales and evolved on variable timescales, and redox chemistry played a pivotal role. A major accomplishment of Mars exploration has been to demonstrate that surface and subsurface sedimentary environments were both habitable and capable of preserving any biological record. ▪ Mars has an ancient sedimentary rock record with many similarities to but also many differences from Earth's sedimentary rock record. ▪ Mars’ ancient sedimentary cycle shows a general evolution toward more desiccated and oxidized surficial conditions. ▪ Climatic regimes of early Mars were relatively clement but with regional variations leading to different sedimentary mineral assemblages. ▪ Surface and subsurface sedimentary environments on early Mars were habitable and capable of preserving any biological record that may have existed.

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