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- Nisson, D.M., et al.
(författare)
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Hydrogeochemical and isotopic signatures elucidate deep subsurface hypersaline brine formation through radiolysis driven water-rock interaction
- 2023
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Ingår i: Geochimica et Cosmochimica Acta. - : Elsevier. - 0016-7037 .- 1872-9533. ; 340, s. 65-84
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Tidskriftsartikel (refereegranskat)abstract
- Geochemical and isotopic fluid signatures from a 2.9–3.2 km deep, 45–55 °C temperature, hypersaline brine from Moab Khotsong gold and uranium mine in the Witwatersrand Basin of South Africa were combined with radiolytic and water–rock isotopic exchange models to delineate brine evolution over geologic time, and to explore brine conditions for habitability. The Moab Khotsong brines were hypersaline (Ca-Na-Cl) with 215–246 g/L TDS, and Cl− concentrations up to 4 mol/L suggesting their position as a hypersaline end-member significantly more saline than any previously sampled Witwatersrand Basin fluids. The brines revealed low DIC (∼0.266–∼1.07 mmol/L) with high (∼8.49–∼23.6 mmol/L) DOC pools, and several reduced gaseous species (up to 46 % by volume H2) despite microoxic conditions (Eh = 135–161 mV). Alpha particle radiolysis of water to H2, H2O2, and O2 along with anhydrous-silicate-to-clay alteration reactions predicted 4 mol/L Cl− brine concentration and deuterium enrichment in the fracture waters over a period > 1.00 Ga, consistent with previously reported 40Ar noble gas-derived residence times of 1.20 Ga for this system. In addition, radiolytic production of 7–26 nmol/(L × yr) H2, 3–11 nmol/(L × yr) O2, and 1–8 nmol/(L × yr) H2O2 was predicted for 1–100 g/g 238U dosage scenarios, supporting radiolysis as a significant source of H2 and oxidant species to deep brines over time that are available to a low biomass system (102–103 cells/mL). The host rock lithology was predominately Archaean quartzite, with minerals exposed on fracture surfaces that included calcite, pyrite, and chlorite. Signatures of 18Ocalcite, 13Ccalcite, Δ33Spyrite, 34Spyrite and 87Sr/86Sr obtained from secondary ion mass spectrometry (SIMS) microanalyses suggest several discrete fluid events as the basin cooled from peak greenschist conditions to equilibrium with present-day brine temperatures. The brine physiochemistry, geochemistry, and cellular abundances were significantly different from those of a younger, shallower, low salinity dolomitic fluid in the same mine, and both were different from the mine service water. These results indicate the discovery of one of few long-isolated systems that supports subsurface brine formation via extended water–rock interaction, and an example of a subsurface brine system where abiotic geochemistry may support a low biomass microbial community.
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| 2. |
- Young, E. D., et al.
(författare)
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The relative abundances of resolved (CH2D2)-C-12 and (CH3D)-C-13 and mechanisms controlling isotopic bond ordering in abiotic and biotic methane gases
- 2017
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Ingår i: Geochimica et Cosmochimica Acta. - : Elsevier BV. - 0016-7037 .- 1872-9533. ; 203, s. 235-264
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Tidskriftsartikel (refereegranskat)abstract
- We report measurements of resolved (CH2D2)-C-12 and (CH3D)-C-13 at natural abundances in a variety of methane gases produced naturally and in the laboratory. The ability to resolve (CH2D2)-C-12 from (CH3D)-C-13 provides unprecedented insights into the origin and evolution of CH4. The results identify conditions under which either isotopic bond order disequilibrium or equilibrium are expected. Where equilibrium obtains, concordant Delta (CH2D2)-C-12 and Delta (CH3D)-C-13 temperatures can be used reliably for thermometry. We find that concordant temperatures do not always match previous hypotheses based on indirect estimates of temperature of formation nor temperatures derived from CH4/H-2 D/H exchange, underscoring the importance of reliable thermometry based on the CH4 molecules themselves. Where Delta (CH2D2)-C-12 and Delta (CH3D)-C-13 values are inconsistent with thermodynamic equilibrium, temperatures of formation derived from these species are spurious. In such situations, while formation temperatures are unavailable, disequilibrium isotopologue ratios nonetheless provide novel information about the formation mechanism of the gas and the presence or absence of multiple sources or sinks. In particular, disequilibrium isotopologue ratios may provide the means for differentiating between methane produced by abiotic synthesis vs. biological processes. Deficits in (CH2D2)-C-12 compared with equilibrium values in CH4 gas made by surface-catalyzed abiotic reactions are so large as to point towards a quantum tunneling origin. Tunneling also accounts for the more moderate depletions in (CH3D)-C-13 that accompany the low (CH2D2)-C-12 abundances produced by abiotic reactions. The tunneling signature may prove to be an important tracer of abiotic methane formation, especially where it is preserved by dissolution of gas in cool hydrothermal systems (e.g., Mars). Isotopologue signatures of abiotic methane production can be erased by infiltration of microbial communities, and Delta (CH2D2)-C-12 values are a key tracer of microbial recycling.
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