Fluid Chemistry Research Articles

The subseafloor crustal biosphere: Ocean’s hidden biogeochemical reactor

Underlying the thick sediment layer in ocean basins, the flow of seawater through the cracked and porous upper igneous crust supports a previously hidden and largely unexplored active subsurface microbial biome. Subseafloor crustal systems offer an enlarged surface area for microbial habitats and prolonged cell residence times, promoting the evolution of novel microbial lineages in the presence of steep physical and thermochemical gradients. The substantial metabolic potential and dispersal capabilities of microbial communities within these systems underscore their crucial role in biogeochemical cycling. However, the intricate interplay between fluid chemistry, temperature variations, and microbial activity remains poorly understood. These complexities introduce significant challenges in unraveling the factors that regulate microbial distribution and function within these dynamic ecosystems. Using synthesized data from previous studies, this work describes how the ocean crustal biosphere functions as a continuous-flow biogechemical reactor. It simultaneously promotes the breakdown of surface-derived organic carbon and the creation of new, chemosynthetic material, thereby enhancing element recycling and ocean carbon productivity. Insights gained from the qualitative analysis of the extent of biogeochemical microbial activity and diversity across the temperature and chemical gradients that characterize these habitats, as reviewed herein, challenge traditional models of global ocean carbon productivity and provide the development of a new conceptual framework for understanding the quantitative metabolic potential and broad dispersal of the crustal microbial biome.

Modeling saline-fluid flow through subglacial channels

Abstract. Subglacial hydrological systems impact ice dynamics, biological environments, and sediment transport. Previous numerical models of channelized subglacial flow have focused on freshwater in temperate ice without considering variable fluid chemistry and properties. Saline fluids can exist in cold glacier systems where freshwater cannot, making the routing of these fluids critical for understanding their influence on geochemical and physical processes in relevant glacial environments. This study advances previous efforts by modeling saline fluid in cold glacier systems, where variable fluid chemistry significantly influences melt rates and drainage processes. We model the drainage of a hypersaline subglacial lake through an ice-walled channel, highlighting the impact of salinity on channel evolution. The model results show that, in subglacial systems at salinity-dependent melting points, channel walls grow more slowly when fluids have higher salt concentrations, leading to significantly lower discharge rates. At higher salinities, more energy is required to warm the fluid to the new melting point as the brine is diluted, which reduces the energy available for melting the channel walls. We also highlight the impact of increased fluid density on subglacial drainage and the importance of accounting for accurate suspended sediment concentrations when modeling outburst floods. This model provides a framework to assess the impact of fluid chemistry and properties on the spatial and temporal variations of fluid flux.

Fluid-mediated transition from dynamic rupturing to aseismic slip at the base of the seismogenic continental crust

Chemo-mechanical fluid-rock interactions are critical in controlling the frictional-viscous transition in the continental crust and the competition between seismic and aseismic deformation in fault zones. In this study, we provide quantitative constraints on the timing and magnitude of weakening, and associated changes in slip rates, due to fluid-rock interactions at the base of the seismogenic continental crust. Integrating field, microstructural analyses, and micromechanical modelling we constrain the microstructural and mechanical evolution of phyllosilicate-rich, carbonate-bearing brittle-ductile faults/shear zones developed in the Rieserferner granitoid pluton (Eastern Alps). Here, transient overpressure of (H2O + CO2)-rich fluids triggered dynamic rupturing in the strong host rock (>100 MPa), and promoted the development of weak phyllonites through long-term fluid-mediated feldspar-to-mica reactions. These phyllosilicate-rich fault rocks accommodated frictional-viscous aseismic creep at very low differential stresses (<10 MPa) and near-lithostatic fluid pressure conditions. Microscale vein networks overprinting the phyllonite indicate cyclical embrittlement related to increased creep rates (up to 10−7 s−1) that occurred over a timeframe of days to months and potentially related to slow earthquakes (slip rates of 10−8 m/s). These findings offer new constraints on the development and seismogenic potential of phyllosilicate-rich fault zones and on the effect of fluid chemistry on fault zone rheology. Fluid-mediated fault weakening can occur in rather short time (months-to-years) comparable to the interseismic period, progressively promoting long-term, viscous aseismic creep on a previously strong fault zone developed by dynamic rupturing. The combined effect of strain localization, the low permeability of the phyllonitic cores, as well as of fluid chemistry evolution and CO2-enrichment, may lead to the development of brittle-frictional instabilities during transient accelerated-creep events. Therefore, the fluid-mediated microstructural evolution of phyllosilicate-rich fault rocks controls their seismogenic behaviour, potentially leading to accelerated creep, slow earthquakes and slow slip on otherwise aseismically creeping faults.

Evolution of Auriferous Fluids in the Kraaipan-Amalia Greenstone Belts: Evidence from Mineralogical and Isotopic Constraints

The Kraaipan and Amalia greenstone belts in South Africa occur in the western part of the Kaapvaal Craton. The two belts stretch discontinuously in an approximately north–south orientation over a distance of about 250 km from southern Botswana in the north to the Vaal River near Christiana in the south and are separated by a distance of about 90 km. Gold mineralization is hosted in banded iron formation at both the Kalahari Goldridge deposit (Kalgold) in the Kraaipan greenstone belt in the north and the Amalia deposit in the Amalia greenstone belt in the south, with the mineralization associated with quartz–carbonate veins. The footwalls of these deposits are generally composed of mafic volcanic schist and the hanging walls consisting of graywackes, schist and shale units. The Kalgold and Amalia gold deposits show some variation in the redox condition of the mineralizing system and fluid chemistry. The ore mineral assemblage is characterized by magnetite–pyrrhotite–pyrite at Kalgold, which is indicative of reducing conditions, and a magnetite–hematite–pyrite assemblage at Amalia that suggests a relatively oxidizing environment. Average mineralizing temperatures determined from chlorite geothermometry were relatively higher at the Kalahari Goldridge deposit ranging from 350 to 400 °C compared to the slightly cooler range of 330 to 390 °C at Amalia. The composition of the fluids derived from fluid inclusions is indicative of low salinity H2O--CO2±CH4-rich fluids at Kalgold against relatively H2O-CO2-rich fluids at Amalia. Evidence from strontium–carbon–oxygen isotopic ratios from carbonates suggests that differences in redox conditions in the deposits could be attributed to different flow pathways by an evolving fluid from a common source (with minimum 87Sr/86Sr = 0.70354) to the sites of gold deposition, with a significant ore fluid interaction with a thick sequence of carbonaceous meta-pelitic rock units at the Kalahari Goldridge deposit that is absent in the Amalia deposit.

Fluid-rock reaction path modeling of uranium mobility in granite-related mineralization: A case study from the Variscan South Armorican Domain

The mobilization of uranium in granite-related systems presents a complex interplay of chemical and hydrodynamic factors. This is particularly obvious within syn-orogenic detachment zones where per descensum surface-derived fluids interact with per ascensum deeply sourced hydrothermal fluids. In this study, we employ a thermo-hydro-chemical (TH-C) modeling approach to explore the multifaceted processes that govern uranium transport and deposition in such environments. Our findings indicate that uranium mobility is not solely determined by the oxidizing nature of the percolating surface-derived fluids. Actually, the oxidation-reduction potential of these fluids varies as they flow in the crust, ultimately adjusting towards more neutral or mildly reducing conditions conducive to uranium dissolution and precipitation. Even in the presence of magnetite, which enhances the reductive potential of the fluids, uranium continues to dissolve, albeit in much smaller quantities, with U(IV) being the predominant species in the aqueous phase. The study highlights the crucial roles of temperature, pH, and fluid/rock interaction ratios in influencing uranium leaching efficacy. High fluid/rock ratios enhance uranium extraction from source rocks. A fluid/rock ratio around 1 is optimal, maximizing the dissolution of uranium-bearing minerals in the source rock and promoting the precipitation of uranium minerals in different locations along the fluid pathway due to changes in fluid chemistry. The TH-C modeling has the potential to be applied to a variety of other uranium deposits, developed below 300°C.

Tracking hydrothermal particles from the ridge axis to the sediment column along the Endeavour segment of the Juan de Fuca Ridge

Elemental fluxes associated with mid-ocean ridge hydrothermal systems are thought to be important in the ocean budgets of many elements but quantitative models of these fluxes, and how they vary in space and time due to different boundary conditions, are in their infancy. This is especially true for non-conservative elements that can be involved in multiple processes transforming them between the dissolved and particulate phases both in the water column and after sedimentation. To help develop a more robust database for parameterizing the processes operating, we undertook a coupled sediment trap and sediment core study of hydrothermal sediments on the west flank of the Endeavour segment of the Juan de Fuca Ridge. Sediment traps deployed in the Main Endeavour Field (MEF) and 3 and 9 km southwest of this field, along the mean flow direction of the hydrothermal plume, show that the rate of change of the concentration of sulfide-associated elements (Cu, Zn, Cd, Pb, Ag, As, Mo) in sediment settling from the plume differs between elements. We interpret this as indicating both different dissolution rates of phases containing these elements and different rates of scavenging of these elements from seawater. Scavenging is most readily tracked using elements for which the scavenged fraction is large relative to the hydrothermally derived fraction. For such elements, the relative efficiency of scavenging from seawater (REE > Cr > Ni > V > P > U) matches that previously reported from the TAG system on the Mid-Atlantic ridge despite different vent fluid and seawater chemistries that are expected to lead to both differing roles of Fe-sulfide and Fe-oxyhydroxides and different Fe oxidation rates. In the sediment trap samples collected 9 km off-axis, but not in those collected 3 km off-axis, the Mn and Ti concentrations correlate strongly despite these samples having much higher Mn concentrations than background sediment. Since Ti is sourced almost entirely from background terrigenous material such a correlation was not expected. The most reasonable explanation for this is that aggregation of hydrothermally derived particles with terrigenous material settling through the water column controls removal of hydrothermally derived particles from the water column. Changes in sediment composition with depth in the off-axis sediment core, along with differences between the composition of material from the sediment core and the off-axis sediment traps, are interpreted as indicating large post-deposition changes in sediment composition. For example, much or all of the Mn, P, As and Mo carried to the sediments with hydrothermally derived particles is released back into the water column during diagenesis. In contrast, V and REE concentrations in the sediment core are higher than those in the off-axis sediment trap samples, which may be due to continued scavenging in a benthic boundary layer post-deposition. Overall these data are interpreted as indicating that the net loss of many elements from the non-buoyant plume may not be a proxy for loss from the ocean, and a better understanding of post-depositional processes in hydrothermal settings may be important in understanding cycling of the aforementioned elements, and likely others, in seawater.

Hydrothermal mineral replacement of bastnäsite by rhabdophane and monazite: effects of temperature on mineralogy, REE immobilisation, and fractionation

The rare-earth elements (REEs, La–Lu, Y) are essential for the development of renewable technologies. Bastnäsite (REECO3F) is a common REE ore mineral that is often subject to hydrothermal alteration at all crustal levels. Mechanisms of hydrothermal bastnäsite alteration therefore govern the evolution of REE deposits, though these mechanisms remain poorly understood. This experimental work investigates the hydrothermal replacement of bastnäsite by rhabdophane (REEPO4∙xH2O, x = 0–1) and monazite (REEPO4) in phosphatic fluids. Two temperature-dependent alteration pathways were identified; both follow the coupled dissolution-reprecipitation (CDR) mechanism. At 90 °C, bastnäsite was replaced by highly-porous metastable rhabdophane which was then replaced by monazite, forming an inner layer of rhabdophane and an outer layer of monazite. At 220 °C, bastnäsite was replaced directly by monazite. Although replacement initiated more quickly at 220 °C, greater overall replacement occurred at 90 °C (~ 61 wt.% after 500 h, compared to ~ 13 wt.% at 220 °C) due to surface passivation by monazite at 220 °C. Geochemical analyses showed REE fractionation during bastnäsite alteration. At 90 °C, rhabdophane was enriched in heavy REEs (Eu–Lu, Y), likely due to the evolving fluid chemistry, while at 220 °C secondary monazite was enriched in Sm and Ho compared to bastnäsite. These results indicate that: 1) the hydrothermal alteration of bastnäsite by rhabdophane and monazite in ore deposits leads to REE immobilisation, with little net loss of REEs to solution; 2) rhabdophane is metastable relative to monazite at 90 °C, and; 3) variable temperatures can cause different mineral textures and REE fractionation trends during hydrothermal alteration and mineral replacement.

A Theoretical Model for the Hydraulic Permeability of Clayey Sediments Considering the Impact of Pore Fluid Chemistry

The chemistry of the pore fluid within clayey sediments frequently changes in various processes. However, the impacts of pore fluid chemistry have not been well included in the hydraulic permeability model, and the physical bases behind the salinity sensitivity of the hydraulic permeability remains elusive. In this study, a theoretical model for the hydraulic permeability of clayey sediments is proposed, and impacts of the pore fluid chemistry are quantitatively considered by introducing electrokinetic flow theory. Available experimental data were used to verify the theoretical model, and the verified model was further applied as a sensitivity analysis tool to explore more deeply how hydraulic permeability depends on pore fluid chemistry under different conditions. Coupling effects of pore water desalination and the effective stress enhancement on the hydraulic permeability of marine sediments surrounding a depressurization wellbore during hydrate production are discussed. Results and discussion show that the hydraulic permeability reduction is significant only when the electric double layer thickness is comparable to the characteristic pore size, and the reduction becomes more obvious when the ion mobility of the saline solution is smaller and the surface dielectric potential of clay minerals is lower. During gas hydrate production in the ocean, the salinity sensitivity of the hydraulic permeability could become either stronger and weaker, depending on whether the original characteristic pore size of marine sediments is relatively large or small.

Concurrent measurement of strain and chemical reaction rates in a calcite grain pack undergoing pressure solution: Evidence for surface-reaction controlled dissolution

Pressure solution is inferred to be a significant contributor to sediment compaction and lithification, especially in carbonate sediments. For a sediment deforming primarily by pressure solution, the compaction rate should be directly related to the rate of calcite dissolution, transport along grain contacts, and calcite reprecipitation. Previous experimental work has shown that there is evidence that deformation in wet calcite grain packs is consistent with control by pressure solution, but considerable ambiguity remains regarding the rate limiting mechanism. We present the results of laboratory compaction experiments designed to directly measure calcite dissolution and precipitation rates (recrystallization rates) concurrently with strain rate to test whether measured rates are consistent with predicted rates both in absolute magnitude and time evolution. Recrystallization rates are measured using trace element chemistry (Sr/Ca, Mg/Ca) and isotopes (87Sr/86Sr) of fluids flowing slowly through a compacting grain pack as it is being triaxially compressed. Imaging techniques are used to characterize the grain contacts and strain effects in the post-experiment grain pack. Our data show that calcite recrystallization rates calculated from all three geochemical parameters are in approximate agreement and that the rates closely track strain rate. The geochemically inferred rates are close to predicted rates in absolute magnitude. Uncertainty in grain contact dimensions makes distinguishing between surface reaction control and diffusion control difficult. Measured reaction rates decrease faster than predicted from standard pressure solution creep flow laws. This inconsistency may indicate that calcite dissolution rates at grain contacts are more complex, and more time-dependent, than suggested by geometric models designed to predict grain contact stresses.

Conceptual modelling on water-rock reaction and genesis of high pH fluids in a typical granitoid geothermal reservoir: A case from Indus-Tsangpo Suture Zone, India

Two novel thermal springs are investigated along ITSZ of north-west Himalayas in Demchok geothermal belt. The area consists of deep-seated faults in LGB; despite being situated in ITSZ, fluid chemistry of these low-temperature springs differs significantly, specifically in terms of low TDS (161–168 mg/l) and high alkalinity, with neighbouring springs in Puga and Chumathang (∼2100 mg/l). Thermal waters are mixed type (Na–Cl–HCO3–SO4) with elemental composition influenced through silicate rock weathering and partial carbonate dissolution. Variable temperature speciation (25 °C–200 °C) indicates that in reservoir fluid, Na+ precedes over other cations, while sulfate and carbonate complexes being prominent for Mg and Ca, respectively. Aquifer boiling modelling suggests calcite scaling and silica mineral equilibration in reservoir. Environmental stable isotopes (δ18O and δD) suggest high-altitude recharge from Jamlung La (6156 m), with altitude-effect of 0.43 ‰ isotopic depletion per 100 m elevation in altitude. As only silica minerals equilibrate with thermal waters, silica, and gas geothermometers give most conservative estimate of reservoir temperature (125°−135 °C). The steep topography enables extensive lateral flow of hot fluids in outflow zone, leading to high mixing and a high water-rock ratio, which contribute to lower TDS. Conceptual modelling reveals that geothermal system is a low-enthalpic hydrothermal system controlled by joints and permeable fractures, having deep fluid circulation of meteoric waters of ∼1275 m at sub-surface, with anomalous geothermal gradient and steam migration as reservoir heat sources. These fluids closely resemble springs of Guerrero state, Mexico, exhibiting similarities in low-TDS, high-pH, and high concentration of dissolved silica.

Utility of Cerebrospinal Fluid Unstimulated Interferon-Gamma (IRISA-TB) as a Same-Day Test for Tuberculous Meningitis in a Tuberculosis-Endemic, Resource-Poor Setting.

Tuberculous meningitis (TBM) mortality is high and current diagnostics perform suboptimally. We evaluated the diagnostic performance of a DNA-based assay (GeneXpert Ultra) against a new same-day immunodiagnostic assay that detects unstimulated interferon-gamma (IRISA-TB). In a stage 1 evaluation, IRISA-TB was evaluated in biobanked samples from Zambia (n = 82; tuberculosis [TB] and non-TBM), and specificity in a South African biobank (n = 291; non-TBM only). Given encouraging results, a stage 2 evaluation was performed in suspected TBM patients from Zimbabwe and Malawi (n = 668). Patients were classified as having definite, probable or possible TBM, or non-TBM based on their microbiological results, cerebrospinal fluid (CSF) chemistry, and whether they received treatment. In the stage 1 evaluation, sensitivity and specificity of IRISA-TB were 75% and 87% in the Zambian samples, and specificity was 100% in the South African samples. In the stage 2 validation, IRISA-TB sensitivity (95% confidence interval [CI]) was significantly higher than Xpert Ultra (76.2% [55.0%-89.4%] vs 25% [8.9%-53.3%]; P = .0048) when trace readouts were considered negative. Specificity (95% CI) was similar for both assays (91.4% [88.8%-93.4%] vs 86.9% [83.4%-89.8%]). When the Xpert Ultra polymerase chain reaction product was verified by sequencing, the positive predictive value of trace readouts in CSF was 27.8%. Sensitivity of IRISA-TB was higher in human immunodeficiency virus (HIV)-infected versus uninfected participants (85.8% vs 66.7%). As a same-day rule-in test, IRISA-TB had significantly better sensitivity than Xpert Ultra in a TB/HIV-endemic setting. An immunodiagnostic approach to TBM is promising, and further studies are warranted.

Modifying the Effects around the Well can have an Impact on the Drilling Process

Environmental changes around a well can significantly affect the drilling process. This paper examines the effects of flow rate, bottomhole pressure, sheet permeability, viscosity, pressure gradient and well radius on the drilling process. It is shown that the energy-dynamic instability of the sheet’s near-shiva space, a highly active region in the formation, leads to changes in reservoir rock and fluid properties during the drilling process. These changes include physicochemical transformations such as deposition of asphaltenes, paraffins, and resins, as well as swelling of clay particles, which can disrupt reservoir physical properties and affect hydrocarbon flow. In addition, completion and production techniques and the chemistry of drilling and pressure fluids are particularly critical for low-permeability reservoirs. In this paper, the concept of skin effect is also introduced to assess the impact of process fluids on the bottomhole region, and a new assessment model is proposed. The results of the study are important for improving drilling technology and optimising reservoir development.

Effects of fluid salinity and composition on subcritical crack growth in marble

Subcritical fracture growth of rocks in fluid-chemical environments played a crucial role in the weathering process of rocks and the preservation of stone building heritage. Fracture mechanics properties of marble under different fluid compositions and salinity conditions were investigated by carrying out double torsion tests. The subcritical crack growth index (SCI) exhibited different salinity dependencies in two salt solutions. In NaCl solution, the SCI decreased by 1.97 % – 40.50 % with increasing salinity due to the increase in solubility of calcite. The SCI decreased by 4.60 % and 14.01 % respectively as the Na2SO4 salinity increases from 0.01 mol/L to 1 mol/L, and then increased with the increase in salinity, which was related to the relationship between calcite solubility and salinity. Compared to Na2SO4 solution, the weakening effect of NaCl solution on Ka was smaller. In contrast, the fracture toughness (KIC) was insensitive to fluid composition and salinity in the short term, with KIC ranging from 0.65 to 0.79 MPa m1/2 in all salt solutions. The three-dimensional morphology results of the fracture surfaces indicated that the effect of salinity on the roughness of both fracture types was negligible. However, the microstructure of the marble was significantly affected by salinity, and apparent dissolution was observed. The results highlighted the dependence of the subcritical fracture behavior of marble on fluid chemistry, which had implications for the weathering assessment of stone masonry buildings and the permanent protection of stone heritage monuments. In these applications, fluid chemistry could either strengthen or weaken the rock, depending on variations in fluid composition and salinity.

Adsorption pathways of boron on clay and their implications for boron cycling on land and in the ocean

Reversible adsorption and isotope fractionation of boron on the surface of clay minerals is a key process that impacts boron isotope cycling in porewater, rivers and the ocean. However, the differences in boron isotope fractionation factors between various clay minerals and their dependence on fluid chemistry are not well known. We performed two sets of experiments, using solutions of pure water with added boron and seawater, to explore the isotope behavior during adsorption of boron onto kaolinite, smectite and illite. We found that the amount of sorbed boron increases with ionic strength of solutions and is proportional to the cation exchange capacity of a given clay mineral. Maximum adsorption is observed in alkaline seawater, which we attribute to the efficient fixation of magnesium-borate ion pairs onto negatively charged surface sites. Isotopic fractionation is modestly different between clays and demonstrates that clay surfaces preferentially sorb borate, even when the concentration of borate in solution is low. In both pure water and seawater, adsorbed complexes retain the isotopic composition of their dissolved precursors (borate or boric acid) with minimal isotopic fractionation. In other words, isotopic composition of adsorbed boron is set by the ability of clays to adsorb boron from an already fractionated boron pool rather than specific fractionation associated with the complexation reaction. Our experimental results allow us to provide revised constraints on the adsorbed boron being transported in terrestrial fluids and the ocean.

A review of cold seeps in the Western Atlantic, focusing on Colombia and the Caribbean

Areas of the seafloor enriched with seeping fluids host unique chemosynthetic communities, and their interactions not only linked to the presence of oil and gas resources, but directly impact global geochemical cycles. These ecosystems can be found in diverse geological settings, spanning from passive to active continental margins, and encompass environments such as mid-ocean ridges, seamounts, cold brine lakes, mud volcanoes, and carbonate pinnacles. This review aims to examine seep environments in the Western Atlantic, the Caribbean, and Colombia, with a focus on understanding: I) their nature and origin, Itheir associated seabed characteristics, III) the biological communities directly connected to them, and IV) the chemistry and flow of the emitted fluids. The review identifies the close relationship of cold seeps to various geomorphological features, including linear diapir systems, salt diapirs resulting from salt tectonics, regions of mud volcanism, and compact seafloor mounds likely associated with buried mud diapirs. However, existing data on the fauna within these environments predominantly focus on megafauna, such as vestimentiferan tubeworms (Annelida), mussels, and vesicomyid bivalves (Mollusca), overlooking the crucial role of communities of small organisms, including fungi or macrofauna. This review highlights the absence of a consistent consensus among researchers regarding the factors controlling fauna distribution and presence in seep environments. Various authors have put forth divergent factors that influence seep community structures, with some emphasizing water depth, others the geological environment, and some the relationship with geomorphological conditions and fluid emissions. These findings underscore the need for further research into environmental factors and their roles in the observed distribution, presenting a promising avenue for future investigations.

The Preparation Phase of the 2023 Kahramanmaraş (Turkey) Major Earthquakes from a Multidisciplinary and Comparative Perspective

On 6 February 2023, Turkey experienced its most powerful earthquake in over 80 years, with a moment magnitude (Mw) of 7.7. This was then followed by a second earthquake of Mw 7.6 just nine hours later. According to the lithosphere–atmosphere–ionosphere coupling (LAIC) models, such a significant seismic activity is expected to cause anomalies across various observables, from the Earth’s surface to the ionosphere. This multidisciplinary study investigates the preparatory phase of these two major earthquakes by identifying potential precursors across the lithosphere, atmosphere, and ionosphere. Our comprehensive analysis successfully identified and collected various anomalies, revealing that their cumulative occurrence follows an accelerating trend, either exponential or power-law. Most anomalies appeared to progress from the lithosphere upward through the atmosphere to the ionosphere, suggesting a sequential chain of processes across these geospheres. Notably, some anomalies deviated from this overall trend, manifesting as oscillating variations. We propose that these anomalies support a two-way coupling model preceding major earthquakes, highlighting the potential role of fluid chemistry in facilitating these processes.

Calcite recrystallization and its impact on speleothem geochemistry

Speleothems are among the most important archives for past climatic and environmental change. Calcite recrystallization can modify the authigenic structure and geochemical composition of the speleothems and affect the reliability of calcite stalagmites as repositories of authigenic geochemical proxies of past climates and environments. The criteria for distinguishing primary from secondary speleothem calcite, and the conditions (open or semi-closed) of speleothem calcite recrystallization remain poorly understood. Thus, in this study, we investigated the fabric, geochemical composition, and recrystallization dynamics of a partially recrystallized calcite stalagmite (DDH-Z-2) from Didonghe Cave in Shaanxi Province, China, through petrographic observations, fluorescence microscopy, and geochemical analyses (stable isotopes, trace elements, UTh isotopes). We found that: (1) in the DDH-Z-2 stalagmite, open elongated columnar calcite recrystallized into compact elongated columnar calcite. Particulate organic matter and fulvic and humic acids were removed during recrystallization, while aromatic compounds were preserved and became incorporated into the secondary calcite; (2) calcite recrystallization was affected by multiple factors, including external fluid chemistry, primary calcite microstructure, and organic matter; (3) calcite recrystallization occurred under open, fluid-buffered conditions for alteration of the stable isotopes (δ18O and δ13C) and trace elements (Mg, Sr, U). The effect of external fluid composition on trace element (Mg, Sr) composition of secondary calcite varied across the stages of calcite recrystallization. Caution should, therefore, be exercised when using geochemical proxies in stalagmites composed of inclusion-free elongated columnar calcite: such calcite is likely to be recrystallized, and thus record the composition of reactive fluids at the time of recrystallization. Regarding the geochemical system of speleothem diagenesis, the contribution of the parent material and the sources of reactive fluids are key factors to consider.

Evidence of both molecular cloud and fluid chemistry in Ryugu regolith.

The sulfur chemistry of (162173) Ryugu particles can be a powerful tracer of molecular cloud chemistry and small body processes, but it has not been well explored. We report identification of organosulfurs and a sulfate grain in two Ryugu particles, A0070 and A0093. The sulfate grain shows oxygen isotope ratios (δ17O = -11.0 ± 4.3 per mil, δ18O = -7.8 ± 2.3 per mil) that are akin to silicates in Ryugu but exhibit mass-independent sulfur isotopic fractionation (Δ33S = +5 ± 2 per mil). A methionine-like coating on the sulfate grain is isotopically anomalous (δ15N = +62 ± 2 per mil). Both the sulfate and organosulfurs can simultaneously form and survive during aqueous alteration within Ryugu's parent body, under reduced conditions, low temperature, and a pH >7 in the presence of N-rich organic molecules. This work extends the heliocentric zone where anomalous sulfur, formed by selective photodissociation of H2S gas in the molecular cloud, is found.

Experimental constraints on Mg isotope fractionation during the aragonite–calcite transition and implications for seawater δ26Mg reconstruction

The linkage between the variation of the seawater Mg budget and the long-term carbon cycle can be elucidated by seawater Mg isotope composition (δ26Mg). However, obtaining primary seawater δ26Mg signatures from marine archives is challenging due to the widespread alteration of diagenesis. Aragonite, a common primary marine carbonate, can effectively record seawater δ26Mg but is prone to alteration and transformation into calcite during early diagenesis. Therefore, a comprehensive understanding of Mg isotope behavior during the aragonite–calcite transition is essential to enhance the applicability of aragonite δ26Mg. In this study, we investigate the variation of aragonite δ26Mg during diagenesis with a limited supply of Mg by conducting a series of well-controlled aragonite–calcite transition experiments in a closed system. The experimental conditions encompass temperatures of 60 and 90 °C, the presence of Ca and Na in the solution, varying Na concentrations, as well as the presence of calcite seed. Results demonstrate that the significant decrease of bulk carbonate δ26Mg is accompanied by a substantial amount of Mg released into the solution during the aragonite–calcite transition, and the amount of released Mg is controlled by fluid chemistry via altering Mg partitioning in calcite. Furthermore, Mg isotope fractionation during calcite precipitation is influenced by temperature, ionic strength, and the presence of calcite seed, while kinetics played a negligible role in our experiments. Combined with previous experiments, the temperature-dependent Mg isotope fractionation during calcite precipitation in unseeded experiments is Δ26Mgcal-sol = (−0.13 ± 0.06) × 106/T2 – (0.47 ± 0.68). This fractionation is systematically higher than that of seeded experiments by 0.3–0.6 ‰ from 15 to 90 °C and can mainly be attributed to differences in surface free energy between homogeneous and heterogeneous calcite nucleation. These findings offer fundamental understandings of the Mg isotope behavior during the aragonite–calcite transformation, providing useful insights for interpreting the variation of δ26Mg in experimental and natural carbonates and facilitating ancient seawater δ26Mg reconstruction.

CO2-Rock-Brine Interactions in Feldspar-Rich Sandstones That Underwent Intense Heating.

The success of any carbon capture and storage method largely depends on, among other factors, its safety, reliability, and thorough understanding of the interactions among CO2, underground geological formation, and resident brine. Upon injection into the subsurface rock formation, CO2 interacts with the host geological formation and brine, initiating complex geochemical reactions that are often poorly understood and could potentially affect the overall stability and storage capacity of the geological formation, particularly those in close proximity to an intense heat source. For instance, the impact of intense and prolonged heat due to, say, magmatic intrusion on sandstones' framework, authigenic mineralogies, and CO2-storage potentials is still poorly understood. Consequently, in this study, we have investigated the impact of firing on CO2-rock-brine reactions in the Bandera Gray (BG) sandstone. Prior to the CO2 injection using 60 000 ppm brine at 75 °C and 28.7 MPa for 30 days, two samples of the BG sandstone were fired for 6 h in a muffle furnace at 700 and 1100 °C each. The BG samples were then studied for XRD, SEM, and ICP-OES analyses before and after the CO2 injection, mainly to investigate any changes in mineralogical compositions and fluid chemistry. To determine the impact of the CO2-rock-brine interactions on the authigenic and framework mineralogies of the BG sandstones under low pH (∼3) conditions, powdered samples of the pre- and postfired BG sandstones were treated with nitric acid. The findings of the study indicate that there were no observable reactions involving rock-forming minerals and carbonate cement in the unfired and fired (at 700 °C) sandstones after the CO2 injection. However, pervasive feldspar-dissolution porosity was formed in the postfired BG sandstone (1100 °C) after CO2 injection. This was mainly because albite was partly to pervasively transformed into anorthite during firing at 1100 °C, making the feldspar highly susceptible to dissolution under CO2 conditions. This implies that the conversion of albite into chemically unstable anorthite in natural sandstones that underwent intense and prolonged heating could develop significant amounts of secondary dissolution porosity due to CO2 injection, thereby impacting their storage capacities and overall petrophysical properties. This dissolution was separately corroborated using a nitric acid treatment. The findings of the study will provide a better understanding of the CO2-rock-brine reactions involving sandstones that experienced intense heat due to, for instance, magmatic activity over a long geologic time scale, which has largely transformed the chemistry of their feldspars, particularly plagioclase.