| 1. |
- 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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| 2. |
- Kminek, G, et al.
(författare)
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COSPAR Sample Safety Assessment Framework (SSAF)
- 2022
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Ingår i: Astrobiology. - : Mary Ann Liebert Inc.. - 1531-1074 .- 1557-8070. ; 22:S1, s. S186-S216
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Tidskriftsartikel (refereegranskat)abstract
- The Committee on Space Research (COSPAR) Sample Safety Assessment Framework (SSAF) has been developed by a COSPAR appointed Working Group. The objective of the sample safety assessment would be to evaluate whether samples returned from Mars could be harmful for Earth's systems (e.g., environment, biosphere, geochemical cycles). During the Working Group's deliberations, it became clear that a comprehensive assessment to predict the effects of introducing life in new environments or ecologies is difficult and practically impossible, even for terrestrial life and certainly more so for unknown extraterrestrial life. To manage expectations, the scope of the SSAF was adjusted to evaluate only whether the presence of martian life can be excluded in samples returned from Mars. If the presence of martian life cannot be excluded, a Hold & Critical Review must be established to evaluate the risk management measures and decide on the next steps. The SSAF starts from a positive hypothesis (there is martian life in the samples), which is complementary to the null-hypothesis (there is no martian life in the samples) typically used for science. Testing the positive hypothesis includes four elements: (1) Bayesian statistics, (2) subsampling strategy, (3) test sequence, and (4) decision criteria. The test sequence capability covers self-replicating and non-self-replicating biology and biologically active molecules. Most of the investigations associated with the SSAF would need to be carried out within biological containment. The SSAF is described in sufficient detail to support planning activities for a Sample Receiving Facility (SRF) and for preparing science announcements, while at the same time acknowledging that further work is required before a detailed Sample Safety Assessment Protocol (SSAP) can be developed. The three major open issues to be addressed to optimize and implement the SSAF are (1) setting a value for the level of assurance to effectively exclude the presence of martian life in the samples, (2) carrying out an analogue test program, and (3) acquiring relevant contamination knowledge from all Mars Sample Return (MSR) flight and ground elements. Although the SSAF was developed specifically for assessing samples from Mars in the context of the currently planned NASA-ESA MSR Campaign, this framework and the basic safety approach are applicable to any other Mars sample return mission concept, with minor adjustments in the execution part related to the specific nature of the samples to be returned. The SSAF is also considered a sound basis for other COSPAR Planetary Protection Category V, restricted Earth return missions beyond Mars. It is anticipated that the SSAF will be subject to future review by the various MSR stakeholders. © Gerhard Kminek et al., 2022;
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| 3. |
- 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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| 4. |
- Onstott, T.C., et al.
(författare)
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Paleo-rock-hosted life on Earth and the search on Mars: a review and strategy for exploration
- 2019
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Ingår i: Astrobiology. - : Mary Ann Liebert Inc, Publishers. - 1531-1074 .- 1557-8070. ; 19:10, s. 1230-1262
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Tidskriftsartikel (refereegranskat)abstract
- Here we review published studies on the abundance and diversity of terrestrial rock-hosted life, the environments it inhabits, the evolution of its metabolisms, and its fossil biomarkers to provide guidance in the search for life on Mars. Key findings are (1) much terrestrial deep subsurface metabolic activity relies on abiotic energy-yielding fluxes and in situ abiotic and biotic recycling of metabolic waste products rather than on buried organic products of photosynthesis; (2) subsurface microbial cell concentrations are highest at interfaces with pronounced chemical redox gradients or permeability variations and do not correlate with bulk host rock organic carbon; (3) metabolic pathways for chemolithoautotrophic microorganisms evolved earlier in Earth's history than those of surface-dwelling phototrophic microorganisms; (4) the emergence of the former occurred at a time when Mars was habitable, whereas the emergence of the latter occurred at a time when the martian surface was not continually habitable; (5) the terrestrial rock record has biomarkers of subsurface life at least back hundreds of millions of years and likely to 3.45 Ga with several examples of excellent preservation in rock types that are quite different from those preserving the photosphere-supported biosphere. These findings suggest that rock-hosted life would have been more likely to emerge and be preserved in a martian context. Consequently, we outline a Mars exploration strategy that targets subsurface life and scales spatially, focusing initially on identifying rocks with evidence for groundwater flow and low-temperature mineralization, then identifying redox and permeability interfaces preserved within rock outcrops, and finally focusing on finding minerals associated with redox reactions and associated traces of carbon and diagnostic chemical and isotopic biosignatures. Using this strategy on Earth yields ancient rock-hosted life, preserved in the fossil record and confirmable via a suite of morphologic, organic, mineralogical, and isotopic fingerprints at micrometer scale. We expect an emphasis on rock-hosted life and this scale-dependent strategy to be crucial in the search for life on Mars.
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