Fluid Chemistry Research Articles

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.

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.

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.

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.

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.

Biotic and abiotic processes in Ediacaran spheroid formation

Organic-rich shales from the uppermost Doushantuo Fm. (South China) record one of the most negative carbonate carbon isotopic excursions in Earth’s history, known as the Shuram excursion, and contain meter to micro-size spheroids. In this study, we use Raman and energy dispersive spectroscopy to identify and describe the most common diagenetic spheroids to refine our understanding of the profound perturbations of the carbon cycle and the evolution of pore fluid chemistry imprinted in the sedimentary Precambrian record, especially in the late Ediacaran. The presence of 13C-depleted carbonate concretions or organic matter (OM) enclosed by lenticular dolomitic structures within the host shale unit suggests OM remineralisation and anaerobic oxidation, resulting in authigenic carbonate precipitation during the earliest stages of sediment diagenesis. Other mineralogical features, however, point to high levels of primary production, such as apatite bands that host spheroidal microfossils with highly fluorescent quartz and OM within abiotic concretions. These observations highlight the importance of considering co-occurring biotic and abiotic processes in explaining the formation of diagenetic spheroids in ancient sedimentary environments. From an astrobiology perspective, the interplay of biotic and abiotic processes reflects the complexity of early life systems and the environments that may exist on other terrestrial planets. Understanding the signatures of biotic and abiotic interactions in the Doushantuo Fm. is crucial for identifying potential biosignatures in extraterrestrial materials, thereby enhancing our understanding of life’s universality and adaptability in diverse and extreme environments.

Variable Iron Mineralogy and Redox Conditions Recorded in Ancient Rocks Measured by In Situ Visible/Near‐Infrared Spectroscopy at Jezero Crater, Mars

AbstractUsing relative reflectance measurements from the Mastcam‐Z and SuperCam instruments on the Mars 2020 Perseverance rover, we assess the variability of Fe mineralogy in Noachian/Hesperian‐aged rocks at Jezero crater. The results reveal diverse Fe3+ and Fe2+ minerals. The igneous crater floor, where small amounts of Fe3+‐phyllosilicates and poorly crystalline Fe3+‐oxyhydroxides have been reported, is spectrally similar to most oxidized basalts observed at Gusev crater. At the base of the western Jezero sedimentary fan, new spectral type points to an Fe‐bearing mineral assemblage likely dominated by Fe2+. By contrast, most strata exposed at the fan front show signatures of Fe3+‐oxides (mostly fine‐grained crystalline hematite), Fe3+‐sulfates (potentially copiapites), strong signatures of hydration, and among the strongest signatures of red hematite observed in situ, consistent with materials having experienced vigorous water‐rock interactions and/or higher degrees of diagenesis under oxidizing conditions. The fan top strata show hydration but little to no signs of Fe oxidation likely implying that some periods of fan construction occurred either during a reduced atmosphere era or during short‐lived aqueous activity of liquid water in contact with an oxidized atmosphere. We also report the discovery of alternating cm‐scale bands of red and gray layers correlated with hydration and oxide variability, which has not yet been observed elsewhere on Mars. This could result from syn‐depositional fluid chemistry variations, possibly as seasonal processes, or diagenetic overprint of oxidized fluids percolating through strata having variable permeability.

Geothermometrical calculations of thermal waters affected by secondary processes: The case of Sierra Elvira (Spain)

Geothermometrical calculations in thermal systems are often limited by the presence of secondary processes that modify the chemistry of the deep reservoir fluid during the ascent to the surface (e.g., mixing, degasification). The effect of secondary processes can be avoided by applying some techniques to reconstruct the chemical equilibrium at depth and the fluid original composition. However, the reconstruction of thermal waters mixed with cold surficial waters is complicated when the dilution factors are unknown. For that case, here, we propose to use an approach consisting of the simulation of a concentration process that removed different amounts of water from the thermal solutions until the equilibrium temperatures of anhydrite and quartz converge for the waters affected by mixing in unknown proportions. Using classical geothermometers and geothermometrical modeling, including the water removal process and CO2 degasification, a temperature range of 78 ± 9 °C at depth has been established for the Sierra Elvira geothermal system whose waters are in chemical equilibrium with respect to calcite, dolomite, anhydrite, quartz, illite, pyrophyllite and beidellite-K. The good agreement in the temperatures obtained for the different thermal fluids of the system suggests a common reservoir for all of them. The methodology used in this study can be applied to other geothermal systems in carbonate rocks affected by mixing.

Characterization of pore water microdynamics and microstructure of clays: The effect of pore fluid chemistry and temperature

It is crucial to figure out the microdynamics of pore water and the microstructure of clays under various thermal and chemical environments when characterizing the physical properties of clays. In this study water microdynamics in clay was investigated via the nuclear magnetic resonance (NMR) technique. The NMR measurements were performed on three clays saturated with distilled water and three salt solutions from 25 to 75°C. The saline and thermal effect on soil-water interaction, water microdynamics and microstructure of clays has been investigated through relaxation times by invoking the DDL theory and the ionic hydration mechanism. Number of jumps (τS/τm) for water molecule is 82 for soils A or C and 520 for soil B when saturated with distilled water, implying the larger surface molecular affinity of soil B. Salt solutions increase the values of τS/τm in the sequence of K+>Ca2+>Na+. Effective activation energy of pore waterΔE= 2.33 kcal/mol, 1.49 kcal/mol and 1.19 kcal/mol for soils A, B and C when saturated with distilled water are obtained. The effect of salt solution on ΔE depends on cation exchange capacity (CEC) and specific surface area (SSA), the larger the CEC and SSA, the smaller the saline effect. In addition, it is found that the pore size distribution of the compacted clay is bimodal, and inter-aggregate pores are greatly influenced by pore fluid chemistry, due to clay aggregation.

The impact of adsorption–desorption reactions on the chemistry of Himalayan rivers and the quantification of silicate weathering rates

Common environmental adsorbents (clay minerals, metal-oxides, metal-oxyhydroxides and organic matter) can significantly impact the chemistry of aqueous fluids via adsorption–desorption reactions. The dissolved chemistry of rivers have routinely been used to quantify silicate mineral dissolution rates, which is a key process for removing carbon dioxide (▪) from the atmosphere over geological timescales. The sensitivity of silicate weathering rates to climate is disproportionately weighted towards regions with high erosion rates. This study quantifies the impact of adsorption-desorption reactions on the chemistry of three large Himalayan rivers over a period of two years, utilising both the adsorbed and dissolved phases. The concentration of riverine adsorbed cations are found to vary principally as a function of the concentration and cation exchange capacity (CEC) of the suspended sediment. Over the study period, the adsorbed phase is responsible for transporting ∼70% of the mobile (adsorbed and dissolved) barium and ∼10% of the mobile calcium and strontium. The relative partitioning of cations between the adsorbed and dissolved phases follows a systematic order in both the monsoon and the dry-season (preferentially adsorbed: Ba > Sr & Ca > Mg & K > Na). Excess mobile sodium (▪=Na-Cl) to silicon (Si) riverine ratios are found to vary systematically during an annual hydrological cycle due to the mixing of low temperature and geothermal waters. The desorption of sodium from uplifted marine sediments is one key process that may increase the Na*/Si ratios. Accounting for the desorption of sodium reduces silicate weathering rate estimates by up to 83% in the catchments. This study highlights that surficial weathering processes alone are unable to explain the chemistry of the rivers studied due to the influence of hydrothermal reactions, which may play an important role in limiting the efficiency of silicate weathering and hence modulating atmospheric ▪ concentrations over geological time.

Polyphased gold enrichment as a key process for high-grade gold formation: Insights from the 10 Moz Jundee-Bogada camp (Yilgarn Craton, Western Australia)

High-grade (> 10 g/t) gold mineralization in orogenic gold deposits is of significant economic importance. Understanding the formation of such enriched ore zones is critical for gold exploration success. The world-class Jundee-Bogada gold camp in the Yilgarn Craton of Western Australia comprises both high-grade (avg. > 10 g/t, Jundee deposit) and low-grade (avg. < 3 g/t, Bogada prospect) lodes, despite shared host stratigraphy. The paragenetic framework established for the Jundee gold deposit suggests that the overall gold endowment developed over three deformation events. An early episode of low-grade gold mineralization is associated with colloform-crustiform veins that formed during extensional deformation (DJB2A). A switch to transtensional deformation (DJB2B) resulted in brecciation of the colloform-crustiform veins and coeval deposition of native gold. Late reverse faults record evidence for a third mineralization stage resulting from a NE-SW-directed shortening (DJB3). Mineralization during this late stage was dominantly low-grade, with local occurrences of ultra-high-grade ore zones (> 100 g/t). Each event records transient changes in fluid chemistry during continued hydrothermal activity that spanned local deformation histories. We argue that at the Jundee gold deposit, protracted gold enrichment during three polyphased mineralization episodes resulted in the formation of high-grade gold ores. Whereas the complete metallogenic history is recorded at the Jundee deposit, gold within the Bogada prospect was introduced solely during the late contractional stage (DJB3), resulting in a bulk low-grade endowment. We hypothesize that gold enrichment in high-grade orogenic gold deposits is a direct consequence of the spatial superimposition of protracted ore-forming events.

A process-based geochemical framework for carbonate sediments during marine diagenesis

A significant proportion of marine calcium carbonate sediments are comprised of metastable minerals that are susceptible to diagenetic alterations during burial. These reactions can reset the geochemical signature of sediments and pore fluids and influence elemental cycling in the ocean. However, the timing and mechanisms by which these reactions take place are poorly constrained. This study uses cores drilled on the slope of the Great Bahama Bank to provide quantitative constraints on important diagenetic reactions; namely respiration-driven dissolution, authigenic carbonate mineral formation, and conversion of aragonite to low Mg calcite (LMC). We perform detailed mineralogical characterization using newly acquired, high resolution X-ray diffraction (XRD) data and over 1000 reanalyzed XRD scans, characterize sediments texturally and elementally using electron microprobe data, calculate pore fluid saturation state with respect to aragonite using a Pitzer ion interaction approach, and use pore fluid chemistry and experimental distribution coefficients to predict authigenic carbonate compositions. These data suggest that aerobic organic matter oxidation, enabled by the advection of oxygenated seawater throughout the upper ∼ 30 m interval of sediment, causes undersaturation and thus dissolution of biogenic high Mg calcite (HMC) and aragonite. Deeper, anaerobic organic matter oxidation takes over and causes supersaturation, promoting authigenic precipitation in the form of HMC, which in turn decreases pore fluid Mg/Ca and promotes aragonite conversion to LMC. One novel aspect of this study is the identification of three types of calcites using the newly acquired XRD and electron microprobe data. Based on their unique crystallographic characteristics and chemical compositions, these types of calcites are interpreted to represent pelagic biogenic LMC, bank-derived biogenic HMC, and authigenic HMC precipitated from pore fluids. Notably, the composition of the authigenic calcite matches that predicted to precipitate from pore fluids using an empirical Mg partition coefficient in calcite. Calcites that form authigenically and from aragonite via replacement are suggested to recrystallize with burial as evidenced by the decrease in Mg content and micro-strain. This process-based geochemical framework assigns diagenetic processes to a specific depth window within the sediment column and paves the way for a mechanistic understanding of carbonate diagenesis, one that is rooted in thermodynamic and kinetic bases.

Extreme shifts in pyrite sulfur isotope compositions reveal the path to bonanza gold

Pyrite is the most common sulfide mineral in hydrothermal ore-forming systems. The ubiquity and abundance of pyrite, combined with its ability to record and preserve a history of fluid evolution in crustal environments, make it an ideal mineral for studying the genesis of hydrothermal ore deposits, including those that host critical metals. However, with the exception of boiling, few studies have been able to directly link changes in pyrite chemistry to the processes responsible for bonanza-style gold mineralization. Here, we report the results of high-resolution secondary-ion mass spectrometry and electron microprobe analyses conducted on pyrite from the Brucejack epithermal gold deposit, British Columbia. Our δ34S and trace element results reveal that the Brucejack hydrothermal system experienced abrupt fluctuations in fluid chemistry, which preceded and ultimately coincided with the onset of ultra-high-grade mineralization. We argue that these fluctuations, which include the occurrence of extraordinarily negative δ34S values (e.g., -36.1‰) in zones of auriferous, arsenian pyrite, followed by sharp increases of δ34S values in syn-electrum zones of nonarsenian pyrite, were caused by vigorous, fault valve-induced episodic boiling (flashing) and subsequent inundation of the hydrothermal system by seawater. We conclude that the influx of seawater was the essential step to forming bonanza-grade electrum mineralization by triggering, through the addition of cationic flocculants and cooling, the aggregation of colloidal gold suspensions. Moreover, our study demonstrates the efficacy of employing high-resolution, in situ analytical techniques to map out individual ore-forming events in a hydrothermal system.