Magmatic carbon outgassing and uptake of CO2 by alkaline waters

Much of Earth's carbon resides in the “deep” realms of our planet: sediments, crust, mantle, and core. The interaction of these deep reservoirs of carbon with the surface reservoir (atmosphere and oceans) leads to a habitable surface environment, with an equitable atmospheric composition and comfortable range in temperature that together have allowed life to proliferate. The Earth in Five Reactions project (part of the Deep Carbon Observatory program) identified the most important carbon-bearing reactions of our planet, defined as those which perhaps make our planet unique among those in our Solar System, to highlight and review how the deep and surface carbon cycles connect. Here we review the important reactions that control the concentration of carbon dioxide in our atmosphere: outgassing from magmas during volcanic eruptions and during magmatic activity; and uptake of CO2 by alkaline surface waters. We describe the state of our knowledge about these reactions and their controls, the extent to which we understand the mass budgets of carbon that are mediated by these reactions, and finally, the implications of these reactions for understanding present-day climate change that is driven by anthropogenic emission of CO2

Observational constraints on the process and products of Martian serpentinization

The alteration of olivine-rich rocks to serpentine minerals, (hydr)oxides, and H2(aq) through serpentinization is long thought to have influenced the distribution of habitable environments on early Mars and the evolution of the early Martian hydrosphere and atmosphere. Nevertheless, the planetary importance of Martian serpentinization has remained a matter of debate; H2 production rates and mechanisms are poorly understood for serpentinization of Fe-rich Martian olivines, and orbital surveys suggest that serpentines are rarely present in the Martian crust. To constrain the process and products of Martian serpentinization, we acquired petrographic, geochemical, mineralogical, and synchrotron-based spectroscopic data on serpentinized Fe-rich olivines from the 1.1 Ga Duluth Complex (Minnesota, USA). These data indicate that serpentinized Fe-rich olivine would have been accompanied by a five-fold increase in H2 production relative to serpentinized terrestrial mantle peridotites. In contrast to previous expectations of mineral products, a vacancy-coupled Fe3+ substitution for Mg2+ in the serpentine octahedral site yields hisingerite (with minor magnetite) as the dominant Fe serpentine mineral at comparatively low temperature and pH, consistent with meteorite mineralogy and in-situ rover data. The widespread occurrence of Fe3+-phyllosilicates in highly magnetized regions of the Martian crust supports the hypothesis that serpentinization was more pervasive on early Mars than currently estimated. Our results provide the Mars 2020 Perseverance Rover mission with new and specific mineralogical and geochemical signatures of serpentinization and H2 production as it approaches the largest olivine-bearing lithological unit identified on the surface of Mars.Leverhulme Trus

Geochemical evaluation of glauconite carbonation during sedimentary diagenesis

Glauconite is an authigenic, iron-rich clay mineral that is abundant in greensands formations worldwide. Evidence from these formations suggests that glauconite is commonly diagenetically converted to carbonate minerals such as siderite, ankerite, and ferroan dolomite. This process represents a natural CO2 sink that may provide an e ective mechanism for the engineered mineralization of anthropogenic CO2. To evaluate glauconite carbonation reactions and improve our understanding of glauconite diagenesis, we performed a detailed evaluation of the mechanisms through which carbonate minerals naturally replace glauconite during diagenesis of glauconitic sandstones from the Lower Cretaceous Upper Mannville Group in western Alberta, Canada. Using a combination of optical microscopy and scanning electron imaging, electron microprobe and bulk geochemical analyses, and x-ray fluorescence mapping, we show glauconite carbonation in the Mannville group is an reduction-facilitated, coupled glauconite recrystallization and siderite precipitation reaction. X-ray absorption near-edge spectroscopic mapping and spot analyses demonstrate that this reaction is accompanied by a significant shift in the oxidation state of Fe, from dominantly oxidized in glauconite to reduced in carbonate reaction products. Together, these results suggest that geochemical conditions - most importantly, temperature, partial pressure of CO2, and fluid redox state - were thermodynamically favorable for glauconite carbonation during burial diagenesis of Mannville Group sandstones. Results of thermodynamic models illustrate that, although K-feldspar is favored to precipitate during reductive glauconite dissolution and accompanying Fe-carbonate precipitation, its precipitation is likely kinetically limited, and that an Fe-impoverished glauconite is expected to recrystallize instead. Our findings show that glauconite carbonation is likely a common phenomenon in the subsurface, and thus that glauconite is potentially a significant cation source for mineralizing anthropogenic CO2

Observational constraints on the process and products of Martian serpentinization

The alteration of olivine-rich rocks to serpentine minerals, (hydr)oxides, and H2(aq) through serpentinization is long thought to have influenced the distribution of habitable environments on early Mars and the evolution of the early Martian hydrosphere and atmosphere. Nevertheless, the planetary importance of Martian serpentinization has remained a matter of debate; H2 production rates and mechanisms are poorly understood for serpentinization of Fe-rich Martian olivines, and orbital surveys suggest that serpentines are rarely present in the Martian crust. To constrain the process and products of Martian serpentinization, we acquired petrographic, geochemical, mineralogical, and synchrotron-based spectroscopic data on serpentinized Fe-rich olivines from the 1.1 Ga Duluth Complex (Minnesota, USA). These data indicate that serpentinized Fe-rich olivine would have been accompanied by a five-fold increase in H2 production relative to serpentinized terrestrial mantle peridotites. In contrast to previous expectations of mineral products, a vacancy-coupled Fe3+ substitution for Mg2+ in the serpentine octahedral site yields hisingerite (with minor magnetite) as the dominant Fe serpentine mineral at comparatively low temperature and pH, consistent with meteorite mineralogy and in-situ rover data. The widespread occurrence of Fe3+-phyllosilicates in highly magnetized regions of the Martian crust supports the hypothesis that serpentinization was more pervasive on early Mars than currently estimated. Our results provide the Mars 2020 Perseverance Rover mission with new and specific mineralogical and geochemical signatures of serpentinization and H2 production as it approaches the largest olivine-bearing lithological unit identified on the surface of Mars.Leverhulme Trus

Effect of boiler feed water composition on inorganic scaling in once-through steam generators estimated using a Monte Carlo modelling approach

Once-through steam generators (OTSGs) produce steam required to recover hydrocarbons from oil sand deposits. OTSGs generate steam at high pressure and temperature, using boiler feed water (BFW) derived from produced water, recycled condensate boiler blowdown (BBD), and small amounts of make-up water sourced from local groundwater. During the OTSG operation cycle, BFW undergoes significant physical and chemical changes, which can cause varying degrees of mineral (scale) precipitation, depending on the BFW quality. Scaling has negative impacts on OTSG performance and has in the past resulted in OTSG tube leaks. In this study, we performed thermodynamic simulations using a Monte Carlo approach with the objective of determining how the composition of the BFW and the steam quality affect scaling. We used 3 different scenarios, characterized by low, intermediate, and high iron-to-BFW ratios to represent various situations of BFW inter- action with OTSG pipes. Within each scenario, BFW compositions were randomly assigned within industry- relevant variations of variables including steam quality, pH, and concentrations of SiO2(aq), Mg2+, Ca2+, Fe2+, Cl−, HCO3−, K+, Na+, SO4 2− and O2 and were allowed to precipitate scales according to thermodynamically controlled solubilities of minerals as they were heated and boiled. Our results show that inorganic scale in OTSGs is composed mostly of aegirine and various Mg and Mg/Ca silicates. We show that the concentrations of dissolved Si, Mg, and Fe available for interaction with BFW are the main factors controlling the mass and mineralogy of scale, whereas the total dissolved solids (TDS) and Ca concentrations within typical chosen operating limits have negligible impact on the scale mass in OTSGs. The modelling results further indicate that efforts to minimize the concentration of Mg in BFW to very low levels (<0.01 mg/kgBFW) show great promise for minimizing inorganic scale formation in OTSGs. Our equilibrium modelling revealed that steam quality has little impact on the total mass of inorganic scale formed in OTSGs because most of the mineral precipitation occurs at temperatures below 250 ◦C, before boiling starts. However, this finding may not be fully valid if strong kinetic barriers prevent process waters from achieving equilibrium via scale precipitation, especially at lower temperatures. Moreover, because nucleated minerals may be transported through the OTSG without precipitating on the piping walls, increasing steam quality reduces the capacity of BBD to carry over crystallized mineral phases in suspension.Natural Sciences and Engineering Research Council (NSERC)Othe

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