Highly enriched carbon and oxygen isotopes in carbonate-derived CO₂ at Gale crater, Mars

One objective of the Curiosity rover is to search for habitable conditions, past and present, on the surface of Mars. Carbonate minerals can record diagnostic signatures of their formation environment. This paper focuses on carbon and oxygen isotope measurements of carbonate minerals detected within the Gale crater. Notably, these carbonates are extremely enriched in 13C and 18O, more so than other Martian materials. We highlight two processes (evaporation-driven Rayleigh distillation and cryogenic precipitation) that could explain these isotopic enrichments and explore whether those processes are consistent with our current understanding of Mars. These isotopic values offer a poignant example of how the Martian carbon cycle differs from that on Earth without the influences of a biosphere

Weathering-driven porosity generation in altered oceanic peridotites

Tomographic study of pore networks in serpentinized peridotite, where pore structures are characterized from the nanometer to the micrometer scale. Pores are localized at grain boundaries of olivine with no secondary mineralization, which we suggest formed formed due to olivine dissolution during low-temperature seafloor weathering. The resulting elemental fluxes are exported from the subseafloor to seawater.Ultramafic rocks exposed at slow and ultra-slow spreading mid-ocean ridges represent a significant and extremely reactive portion of the oceanic lithosphere. Thus, mechanistic understanding of the processes by which seawater infiltrates into and reacts with these rocks is essential for constraining their contribution to the chemistry of the oceans and the coupled carbonate-silicate cycle. Recent observations indicate that nanoscale processes contribute to seawater-driven alteration of ultramafic rocks, but conventional petrographic and tomographic observations of the associated physical features are challenging to link to these nanoscale features. Moreover, multiple generations and varying conditions of fluid infiltration often obscure the relative roles of higher-temperature serpentinization, where reactions are mostly isochemical, and lower-temperature weathering reactions, where observations suggest the release of massive amounts of magnesium. Here we bridge these scales and investigate the specific role of weathering processes in dissolution-driven porosity generation by integrating focused ion beam scanning electron microscopy nanotomography and micro-computed X-ray tomography imaging of the pore structures preserved in drill cores of serpentinized oceanic peridotites. Relict olivine crystals in all imaged samples contain abundant etch pits, and those in the higher-resolution FIB-SEM imagery show the presence of channel-like dissolution structures. The pore channels preferentially affect olivine along grain boundaries and show anisotropic distribution likely controlled by crystallographic features. The pores formed via olivine dissolution are interpreted to result from dissolution of serpentinized peridotite at conditions where serpentine and carbonate precipitation are kinetically inhibited, i.e., at weathering conditions. Importantly, the calculated connectivity of the imaged pore structures increases as the scale of investigation increases, suggesting that weathering-driven olivine dissolution facilitates further seawater infiltration and olivine dissolution, a positive feedback that can sustain continued magnesium extraction until the rocks are ultimately cut off from seawater circulation via sedimentation. Thus, while much attention has been directed towards constraining geochemical fluxes from the higher-temperature alteration of ultramafic rocks, our results support literature studies suggesting that mineral dissolution, and hence elemental fluxes, are significant at the lower temperatures of seafloor weathering. Our data thus provide mechanistic evidence of the physical process contributing to the observed elemental loss from weathered oceanic peridotites.Natural Sciences and Engineering Research Council (NSERC

Weathering-driven porosity generation in altered oceanic peridotites

Ultramafic rocks exposed at slow and ultra-slow spreading mid-ocean ridges represent a significant and extremely reactive portion of the oceanic lithosphere. Thus, mechanistic understanding of the processes by which seawater infiltrates into and reacts with these rocks is essential for constraining their contribution to the chemistry of the oceans and the coupled carbonate-silicate cycle. Recent observations indicate that nanoscale processes contribute to seawater-driven alteration of ultramafic rocks, but conventional petrographic and tomographic observations of the associated physical features are challenging to link to these nanoscale features. Moreover, multiple generations and varying conditions of fluid infiltration often obscure the relative roles of higher-temperature serpentinization, where reactions are mostly isochemical, and lower-temperature weathering reactions, where observations suggest the release of massive amounts of magnesium. Here we bridge these scales and investigate the specific role of weathering processes in dissolution-driven porosity generation by integrating focused ion beam scanning electron microscopy nanotomography and micro-computed X-ray tomography imaging of the pore structures preserved in drill cores of serpentinized oceanic peridotites. Relict olivine crystals in all imaged samples contain abundant etch pits, and those in the higher-resolution FIB-SEM imagery show the presence of channel-like dissolution structures. The pore channels preferentially affect olivine along grain boundaries and show anisotropic distribution likely controlled by crystallographic features. The pores formed via olivine dissolution are interpreted to result from dissolution of serpentinized peridotite at conditions where serpentine and carbonate precipitation are kinetically inhibited, i.e., at weathering conditions. Importantly, the calculated connectivity of the imaged pore structures increases as the scale of investigation increases, suggesting that weathering-driven olivine dissolution facilitates further seawater infiltration and olivine dissolution, a positive feedback that can sustain continued magnesium extraction until the rocks are ultimately cut off from seawater circulation via sedimentation. Thus, while much attention has been directed towards constraining geochemical fluxes from the higher-temperature alteration of ultramafic rocks, our results support literature studies suggesting that mineral dissolution, and hence elemental fluxes, are significant at the lower temperatures of seafloor weathering. Our data thus provide mechanistic evidence of the physical process contributing to the observed elemental loss from weathered oceanic peridotites

Alkalinity Generation Constraints on Basalt Carbonation for Carbon Dioxide Removal at the Gigaton-per-Year Scale

The world adds about 51 Gt of greenhouse gases to the atmosphere each year, which will yield dire global consequences without aggressive action in the form of carbon dioxide removal (CDR) and other technologies. A suggested guideline requires that proposed CDR technologies be capable of removing at least 1% of current annual emissions, about half a gigaton, from the atmosphere each year once fully implemented for them to be worthy of pursuit. Basalt carbonation coupled to direct air capture (DAC) can exceed this baseline, but it is likely that implementation at the gigaton-per-year scale will require increasing per-well CO2 injection rates to a point where CO2 forms a persistent, free-phase CO2 plume in the basaltic subsurface. Here, we use a series of thermodynamic calculations and basalt dissolution simulations to show that the development of a persistent plume will reduce carbonation efficiency (i.e., the amount of CO2 mineralized per kilogram of basalt dissolved) relative to existing field projects and experimental studies. We show that variations in carbonation efficiency are directly related to carbonate mineral solubility, which is a function of solution alkalinity and pH/CO2 fugacity. The simulations demonstrate the sensitivity of carbonation efficiency to solution alkalinity and caution against directly extrapolating carbonation efficiencies inferred from laboratory studies and small-injection-rate field studies conducted under elevated alkalinity and/or pH conditions to gigaton-per-year scale basalt carbonation. Nevertheless, all simulations demonstrate significant carbonate mineralization and thus imply that significant mineral carbonation can be expected even at the gigaton-per-year scale if basalts are given time to react

Serpentine–Hisingerite Solid Solution in Altered Ferroan Peridotite and Olivine Gabbro

We present microanalyses of secondary phyllosilicates in altered ferroan metaperidotite, containing approximately equal amounts of end-members serpentine ((Mg,Fe2+)3Si2O5(OH)4) and hisingerite (□Fe3+2Si2O5(OH)4·nH2O). These analyses suggest that all intermediate compositions can exist stably, a proposal that was heretofore impossible because phyllosilicate with the compositions reported here have not been previously observed. In samples from the Duluth Complex (Minnesota, USA) containing igneous olivine Fa36–44, a continuous range in phyllosilicate compositions is associated with hydrothermal Mg extraction from the system and consequent relative enrichments in Fe2+, Fe3+ (hisingerite), Si, and Mn. Altered ferroan–olivine-bearing samples from the Laramie Complex (Wyoming, USA) show a compositional variability of secondary FeMg–phyllosilicate (e.g., Mg–hisingerite) that is discontinuous and likely the result of differing igneous olivine compositions and local equilibration during alteration. Together, these examples demonstrate that the products of serpentinization of ferroan peridotite include phyllosilicate with iron contents proportionally larger than the reactant olivine, in contrast to the common observation of Mg-enriched serpentine in “traditional” alpine and seafloor serpentinites. To augment and contextualize our analyses, we additionally compiled greenalite and hisingerite analyses from the literature. These data show that greenalite in metamorphosed banded iron formation contains progressively more octahedral-site vacancies (larger apfu of Si) in higher XFe samples, a consequence of both increased hisingerite substitution and structure modulation (sheet inversions). Some high-Si greenalite remains ferroan and seems to be a structural analogue of the highly modulated sheet silicate caryopilite. Using a thermodynamic model of hydrothermal alteration in the Fe–silicate system, we show that the formation of secondary hydrothermal olivine and serpentine–hisingerite solid solutions after primary olivine may be attributed to appropriate values of thermodynamic parameters such as elevated a S i O 2 ( a q ) and decreased a H 2 ( a q ) at low temperatures (~200 °C). Importantly, recent observations of Martian rocks have indicated that they are evolved magmatically like the ferroan peridotites analyzed here, which, in turn, suggests that the processes and phyllosilicate assemblages recorded here are more directly relevant to those occurring on Mars than are traditional terrestrial serpentinites

The contribution of aqueous catechol-silica complexes to silicification during carbonate diagenesis

Pore-filling and carbonate-replacing silica is exceedingly common in carbonates, but the fundamental geochemical mechanisms that drive these silicification reactions during diagenesis remain poorly understood. An existing mode has proposed that carbonate silicification proceeds through an interface-coupled dissolution-precipitation reaction, but it lacks a mechanism that enables pore fluids to reach the requisite level of supersaturation with respect to silica to allow nucleation and growth. Here, we present a sequence of batch experiments ranging in duration from 7 to 49 days designed to test the hypothesis that these reactions are facilitated by the formation and destruction of organo-silica complexes during diagenesis. Our results illustrate that the stability of organo-silica complexes is dependent upon the concentration of organic molecules in solution, as well as pH, 16 salinity, and solution redox state. Together, these results allow us to present the following scheme for organo-silica complex mediation of silicification reactions: Firstly, the breakdown of organic matter in the presence of siliceous material creates organo-silica complexes, leading to silica-enriched pore fluids, a process which is enhanced by the anoxic conditions accompanying sediment burial. Then, as environmental conditions evolve (fO2, salinity, light, fCO2, pH...), the stability of the organo-silica complexes diminishes, and the organo-silica complexes break down. Simultaneously, the pore fluids become intensely silica-supersaturated in direct proportion to the amount of organic material remaining in solution. The resulting supersaturation drives carbonate silicification via the precipitation of silica minerals, a process which is aided by the presence of silica “nuclei” (such as sponge spicules). This study contributes new data and a conceptual model that will aid in the ongoing quest to understand carbonate silicification reactions and their potential applications in hydrocarbon exploitation and geologic CO2 storage. Moreover, it helps to explain the common association between silica precipitates and organic mineral in the sedimentary rock record