Spatial variations in chemical weathering and CO2 consumption in Nepalese High Himalayan catchments during the monsoon season

The major ion chemistry of the Marsyandi basin and six of its tributaries in the Nepalese Himalaya have been investigated during the monsoon months of 2002. Weekly water samples taken at 10 river monitoring stations in the Annapurna watershed over the course of 4 months provide chemical weathering data for the region at an unprecedented temporal and spatial resolution. The river chemistry of all but one basin is heavily dominated by carbonate weathering which, compared to silicate weathering, contributes 80 to 97% of the total solute load. This prevalence is due to a combination of (a) intrinsically faster dissolution kinetics of carbonates, (b) relatively high runoff and (c) glacial meltwater and low temperatures at high altitudes resulting in enhanced carbonate solubilities. Monitoring stations with headwaters in the Tethyan Sedimentary Series (TSS) are particularly carbonate-rich and slightly supersaturated with respect to calcite through half of the monsoon season. Silicate weathering in the TSS is driven largely by sulfuric acid and therefore does not contribute significantly to the drawdown of atmospheric CO₂. With respect to the tributaries in the Greater Himalayan Sequence (GHS), carbonate weathering is practically as predominant as for the TSS, in spite of the largely felsic lithology of the GHS. Relative to the TSS, the primary proton source in the GHS has shifted, with at least 80% of the protons derived from carbonic acid. Averaged over the whole field area, the CO₂ fluxes, based on silicate-derived Ca and Mg, are considerably lower than the global average. Assuming that this study area is representative of the entire range, we conclude that in situ weathering of the High Himalayas does not represent a significant sink of atmospheric carbon dioxide, despite the presence of a watershed south of the GHS that is characterized by a four times higher CO₂ consumption rate than the global average. Silicate weathering rates of all basins appear to be climate controlled, displaying a tight correlation with runoff and temperature. Given the extremely low chemical weathering under transport-limited conditions in high-altitude crystalline terrains outside of the monsoon season, this would result in virtually no chemical exhumation for 2/3 of the year in such a cold and arid climate, north of the rain shadow cast by the High Himalayas.     

Stream geochemistry, chemical weathering and CO2 consumption potential of andesitic terrains, Dominica, Lesser Antilles

Recent studies of chemical weathering of andesitic-dacitic material on high-standing islands (HSIs) have shown these terrains have some of the highest observed rates of chemical weathering and associated CO₂ consumption yet reported. However, the paucity of stream gauge data in many of these terrains has limited determination of chemical weathering product fluxes. In July 2006 and March 2008, stream water samples were collected and manual stream gauging was performed in watersheds throughout the volcanic island of Dominica in the Lesser Antilles. Distinct wet and dry season solute concentrations reveal the importance of seasonal variations on the weathering signal. A cluster analysis of the stream geochemical data shows the importance of parent material age on the overall delivery of solutes. Observed Ca:Na, HCO₃:Na and Mg:Na ratios suggest crystallinity of the parent material may also play an important role in determining weathering fluxes. From total dissolved solids concentrations and mean annual discharge calculations we calculate chemical weathering yields of (6-106 t km⁻² a⁻¹), which are similar to those previously determined for basalt terrains. Silicate fluxes (3.1-55.4 t km⁻² a⁻¹) and associated CO₂ consumption (190-1575 × 10³ mol km⁻² a⁻¹) determined from our study are among the highest determined to date. The calculated chemical fluxes from our study confirm the weathering potential of andesitic-dacitic terrains and that additional studies of these terrains are warranted.     

Mitigation of asphaltics deposition during CO2 flood by enhancing CO2 solvency with chemical modifiers

CO₂ injected in the reservoir of McElroy Field, TX, for a CO₂ flood was in the supercritical state. Supercritical CO₂ fluid is capable of extracting light and intermediate hydrocarbons from rocks but is unable to extract heavy hydrocarbons and asphaltics. Therefore, plugging of asphaltics in reservoir rocks and a consequent reduction in injectivity and recovery may result when CO₂ only is used in enhanced oil recovery. By adding common solvents as chemical modifiers, the flooding fluid shows marked improvement in solvency for heavy components of crudes due to its increased density and polarity. Numerous supercritical CO₂ fluid extractions of dolomite rock from the Grayburg Formation containing known amount of spiked McElroy crude oil have been carried out to evaluate extraction efficiencies of CO₂ and CO₂ with chemical modifiers at various temperatures and pressures. All experiments show that extraction efficiency increases with increasing CO₂ pressure but decreases with increasing temperature. Addition of chemical modifiers to CO₂ also shows improved extraction efficiency and reduced asphaltic deposits. Under the pressure and temperature similar to McElroy reservoir conditions; chemically modified CO₂ yielded almost 3 times as much oil extracts as those in extractions with CO₂ only. It also reduced the asphaltics content in extracted rocks to nearly one half; indicating its potential for mitigating asphaltics plugging of formation rocks     

鄱阳湖流域岩石化学风化特征及CO2消耗量估算

岩石风化过程中所产生的碳汇是全球碳循环的重要组成部分,该领域受到研究全球变化科学家们的普遍关注。文中通过对鄱阳湖流域河水系统的样品采集和化学成分分析,研究了河水化学成分来源及流域岩石风化所产生的碳汇效应。以大气降水、蒸发岩、硅酸岩和碳酸盐岩为4个端员,计算出它们对河水中溶解质的贡献率分别为10．4％、21．9％、30．...     

青藏高原东部长江流域盆地地表化学剥蚀通量剥蚀速率大气CO2净消耗率研究

2000~2002年期间,笔者对青藏高原东部长江流域溶质载荷分别进行了取样分析并对流域盆地化学剥蚀通量、剥蚀速率和大气CO₂净消耗率进行了计算。结果表明,流域盆地化学剥蚀速率以河源区楚玛尔河最高为2.34×10⁶mol/a/km²,沱沱河最低为1.40×10⁶mol/a/km²,四大支流雅砻江为1.69×10⁶mol/a/km²,金沙江为1.74×10⁶mol/a/km²,大渡河为1.57×10⁶mol/a/km²,岷江为1.88×10⁶mol/a/km²;流域盆地ФCO₂估算结果以大渡河最高为101.81×10³mol/a/km²,楚玛尔河最低为7.55×10³mol/a/km²,金沙江为44.38×10³mol/a/km²,雅砻江为69.64×10³mol/a/km²,岷江为81.90×10³mol/a/km²,沱沱河为21.90×10³mol/a/km²。并对长江流域地表化学剥蚀速率主要控制因素进行了讨论。     

Seasonality of bedrock weathering chemistry and CO2 consumption in a small watershed, the White River, Vermont

The draw down of CO₂ from the atmosphere during mineral weathering plays a major role in the global budget of this greenhouse gas. Silicate minerals remove twice the CO₂ of carbonate minerals per mole of calcium in runoff during weathering. Bedrock weathering chemistry was investigated in the White River watershed of northeastern USA to investigate whether there are seasonal differences in carbonate and silicate weathering chemistry. Geographic Information Systems analyses of bedrock geology were combined with major element concentrations in river waters to gain an understanding of the consistency of mineral weathering during three seasons. The percent of carbonate mineralogy comprising the bedrock in tributaries of the White River varied from less than 5% to 45% by area. A mass balance calculation using major element concentrations in waters was applied to estimate the seasonal relationships between bedrock geology and bicarbonate flux. In all tributaries and the main stem of the White River the highest calculated percent of bicarbonate from carbonate mineral weathering was measured in the late fall. The results suggest that carbonate and silicate bedrock weathering processes are seasonally controlled. Thus single season sampling could not accurately represent an entire year's geochemical budget. In the White River, water samples obtained solely during the summer would consistently underestimate the total yearly source of bicarbonate from carbonate bedrock weathering. The same sample set would also provide data that would lead to an underestimation of the yearly atmospheric CO₂ draw down by bedrock weathering in the watershed. For example at four of the seven locations studied there was an almost two-fold difference between summer and spring calculated atmospheric CO₂ consumption rates.     

CO2 and sulfuric acid controls of weathering and river water composition

Reactions of CO₂ with carbonate and silicate minerals in continental sediments and upper part of the crystalline crust produce HCO₃⁻ in river and ground waters. H₂SO₄ formed by the oxidation of pyrite and reacting with carbonates may produce CO₂ or HCO₃⁻. The ratio, ψ, of atmospheric or soil CO₂ consumed in weathering to HCO₃⁻ produced depends on the mix of CO₂ and H₂SO₄, and the proportions of the carbonates and silicates in the source rock. An average sediment has a CO₂ uptake potential of ψ = 0.61. The potential increases by inclusion of the crystalline crust in the weathering source rock. A mineral dissolution model for an average river gives ψ = 0.68 to 0.72 that is within the range of ψ = 0.63 to 0.75, reported by other investigators using other methods. These results translate into the CO₂ weathering flux of 20 to 24 × 10¹²mol/yr.     

Climatic and lithologic controls on the temporal and spatial variability of CO2 consumption via chemical weathering: An example from the Australian Victorian Alps

A detailed geochemical study on river waters of the Australian Victorian Alps was carried out to determine: (i) the relative significance of silicate, carbonate, evaporite and sulfide weathering in controlling the major ion composition and; (ii) the factors regulating seasonal and spatial variations of CO₂ consumption via silicate weathering in the catchments. Major ion chemistry implies that solutes are largely derived from evaporation of precipitation and chemical weathering of carbonate and silicate lithologies. The input of solutes from rock weathering was determined by calculating the contribution of halite dissolution and atmospheric inputs using local rain and snow samples. Despite the lack of carbonate outcrops in the study area and waters being undersaturated with respect to calcite, the dissolution of vein calcite accounts for up to 67% of the total dissolved cations, generating up to 90% of dissolved Ca and 97% of Mg. Dissolved sulfate has δ³⁴S values of 16 to 20‰_CDT, indicating that it is derived predominantly from atmospheric deposition and minor gypsum weathering and not from bacterial reduction of FeS₂. This militates against sulphuric acid weathering in Victorian rivers. Ratios of Si vs. the atmospheric corrected Na and K concentrations range from ~ 1.1 to ~ 4.3, suggesting incongruent weathering from plagioclase to smectite, kaolinite and gibbsite.Estimated long-term average CO₂ fluxes from silicate weathering range from ~ 0.012 × 10⁶ to 0.039 × 10⁶ mol/km²/yr with the highest values in rivers draining the basement outcrops rather than sedimentary rocks. This is about one order of magnitude below the global average which is due to low relief, and the arid climate in that region. Time series measurements show that exposure to lithology, high physical erosion and long water–rock contact times dominate CO₂ consumption fluxes via silicate weathering, while variations in water temperature are not overriding parameters controlling chemical weathering. Because the atmospheric corrected concentrations of Na, K and Mg act non-conservative in Victorian rivers the parameterizations of weathering processes, and net CO₂ consumption rates in particular, based on major ion abundances, should be treated with skepticism.     

Increasing shallow groundwater CO2 and limestone weathering, Konza Prairie, USA

In a mid-continental North American grassland, solute concentrations in shallow, limestone-hosted groundwater and adjacent surface water cycle annually and have increased steadily over the 15-year study period, 1991-2005, inclusive. Modeled groundwater CO₂, verified by measurements of recent samples, increased from 10^−2.05 atm to 10^−1.94 atm, about a 20% increase, from 1991 to 2005. The measured groundwater alkalinity and alkaline-earth element concentrations also increased over that time period. We propose that carbonate minerals dissolve in response to lowered pH that occurs during an annual carbonate-mineral saturation cycle. The cycle starts with low saturation during late summer and autumn when dissolved CO₂ is high. As dissolved CO₂ decreases in the spring and early summer, carbonates become oversaturated, but oversaturation does not exceed the threshold for precipitation. We propose that groundwater is a CO₂ sink through weathering of limestone: soil-generated CO₂ is transformed to alkalinity through dissolution of calcite or dolomite. The annual cycle and long-term increase in shallow groundwater CO₂ is similar to, but greater than, atmospheric CO₂.     

Oxygen isotope exchange between H2O and CO2 at elevated CO2 pressures: Implications for monitoring of geological CO2 storage

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on δ¹³C values of CO₂ to trace the migration of injected CO₂ in the subsurface. More recently the use of δ¹⁸O values of both CO₂ and reservoir fluids has been proposed as a method for quantifying in situ CO₂ reservoir saturations due to O isotope exchange between CO₂ and H₂O and subsequent changes in δ¹⁸O_H2O values in the presence of high concentrations of CO₂. To verify that O isotope exchange between CO₂ and H₂O reaches equilibrium within days, and that δ¹⁸O_H2O values indeed change predictably due to the presence of CO₂, a laboratory study was conducted during which the isotope composition of H₂O, CO₂, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50 °C and up to 19 MPa) and varying CO₂ pressures. Conditions typical for the Pembina Cardium CO₂ Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that δ¹⁸O values of CO₂ were on average 36.4 ± 2.2‰ (1σ, n = 15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5‰ for the experimental temperatures of 50 °C. By using ¹⁸O enriched water for the experiments it was demonstrated that changes in the δ¹⁸O values of water were predictably related to the fraction of O in the system sourced from CO₂ in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO₂ is related to the total volumetric saturation of CO₂ and water as a fraction of the total volume of the system, it is concluded that changes in δ¹⁸O values of reservoir fluids can be used to calculate reservoir saturations of CO₂ in CCS settings given that the δ¹⁸O values of CO₂ and water are sufficiently distinct.     

Selection of coals of different maturities for CO2 Storage by modelling of CH4 and CO2 adsorption isotherms

CO₂ injection in unmineable coal seams could be one interesting option for both storage and methane recovery processes. The objective of this study is to compare and model pure gas sorption isotherms (CO₂ and CH₄) for well-characterised coals of different maturities to determine the most suitable coal for CO₂ storage. Carbon dioxide and methane adsorption on several coals have been investigated using a gravimetric adsorption method. The experiments were carried out using both CO₂ and CH₄ pure gases at 25 °C from 0.1 to 5 MPa (1 to 50 bar). The experimental results were fitted using Temkin's approach but also with the corrected Langmuir's and the corrected Tóth's equations. The two last approaches are more accurate from a thermodynamical point of view, and have the advantage of taking into account the fact that experimental data (isotherms) correspond to excess adsorption capacities. These approaches allow better quantification of the adsorbed gas. Determined CO₂ adsorption capacities are from 0.5 to 2 mmol/g of dry coal. Modelling provides also the affinity parameters of the two gases for the different coals. We have shown these parameters determined with adsorption models could be used for classification and first selection of coals for CO₂ storage. The affinity ratio ranges from a value close to 1 for immature coals to 41 for high rank coals like anthracites. This ratio allows selecting coals having high CO₂ adsorption capacities. In our case, the modelling study of a significant number of coals from various ranks shows that anthracites seem to have the highest CO₂ storage capacities. Our study provides high quality affinity parameters and values of CO₂ and CH₄ adsorption capacities on various coals for the future modelling of CO₂ injection in coal seams.     

火山岩吸附CO2气的成藏潜力及实例分析

火山岩的脱气实验和对昌德东CO2气藏气源的分析结果表明加热火山岩到250℃时,脱出挥发分总量为0.0299～0.0790mL/g,其中CO2脱出量为0.0218～0.0706mL/g(0.429～1.387wt%);挥发组分以CO2为主,还含有H2、CO、CH4等还原性气体,以及少量低碳烷烃,CO2含量和总烃呈现反比关系;基性岩的CO2脱出量、脱出率高于中、酸性岩;CO2脱出量与岩石碱质含量正相关.松辽盆地北部昌德东CO2气藏成藏模式为"自生自储",成藏CO2气主要来自深部被火山岩吸附的气.随岩浆上升,在岩浆冷凝成火山岩的过程中被吸附于火山岩的节理、劈理和晶体位错之中的CO2气,连同火山岩包体中的残留气,成为高纯CO2气藏的主要补给源,并非地幔气体沿大断裂上来直接充注成藏.     

The CO2 system in rivers of the Australian Victorian Alps: CO2 evasion in relation to system metabolism and rock weathering on multi-annual time scales

The patterns of dissolved inorganic C (DIC) and aqueous CO₂ in rivers and estuaries sampled during summer and winter in the Australian Victorian Alps were examined. Together with historical (1978–1990) geochemical data, this study provides, for the first time, a multi-annual coverage of the linkage between CO₂ release via wetland evasion and CO₂ consumption via combined carbonate and aluminosilicate weathering. δ¹³C values imply that carbonate weathering contributes ∼36% of the DIC in the rivers although carbonates comprise less than 5% of the study area. Baseflow/interflow flushing of respired C3 plant detritus accounts for ∼50% and atmospheric precipitation accounts for ∼14% of the DIC. The influence of in river respiration and photosynthesis on the DIC concentrations is negligible. River waters are supersaturated with CO₂ and evade ∼27.7 × 10⁶ mol/km²/a to ∼70.9 × 10⁶ mol/km²/a CO₂ to the atmosphere with the highest values in the low runoff rivers. This is slightly higher than the global average reflecting higher gas transfer velocities due to high wind speeds. Evaded CO₂ is not balanced by CO₂ consumption via combined carbonate and aluminosilicate weathering which implies that chemical weathering does not significantly neutralize respiration derived H₂CO₃. The results of this study have implications for global assessments of chemical weathering yields in river systems draining passive margin terrains as high respiration derived DIC concentrations are not directly connected to high carbonate and aluminosilicate weathering rates.     

Geochemistry of the headwaters of the Yangtze River, Tongtian He and Jinsha Jiang: Silicate weathering and CO2 consumption

Water and sediment samples were collected from the headwaters of the Yangtze River, Tongtian He and Jinsha Jiang (upstream of the Yangtze River which flows on the eastern Qinghai-Tibet Plateau). A detailed geochemical study of the river system was carried out to determine: (i) temporal and spatial variations of the major ions and their implications; (ii) contribution of carbonate, silicate and evaporite to the river dissolved load and (iii) CO₂ consumption via silicate weathering. Results show that cations derived from evaporite dissolution account for 44.7–82.8% of the total cations in the headwaters of the Yangtze River and increasing from SE to NW of the drainage basin. The contribution from silicate weathering gradually increases from the headwaters due to exposure of intrusive rocks and volcanic rocks in the Jinsha Jiang suture belt. Proportion of cations derived from silicate weathering to the total cations in river waters reaches a maximum at Panzhihua City, which is consistent with the abundant exposure of Cenozoic granitoids and Precambrian high-grade metamorphic rocks around Panzhihua. The Jinsha Jiang basin has higher silicate weathering rates but lower carbonate weathering rates than the middle and lower reaches of the Yangtze River. The calculated enrichment factors of potentially harmful metals in the river sediments are within the range of 0.33–2.59, indicative of level 1 or 2 contamination. The highest enrichment factor for Co, Cr and V is found in Panzhihua City, indicating that it has been influenced by anthropogenic sources.     

卫星遥感探测大气CO2浓度研究最新进展

大气CO₂是一种重要的长寿命温室气体,卫星遥感探测大气CO₂浓度,可以连续地获得其全球时空分布变化情况,进而提高对大气CO₂源汇分布及区域和全球碳循环的认识,进一步增强对全球气候变化的研究和预测。卫星遥感探测大气CO₂浓度已经开始成为一个新的研究领域,文章综合论述了利用卫星平台遥感探测大气CO₂浓度分布的最新研究状况。首先简单地叙述了现阶段对大气CO₂浓度时空分布和变化情况的直接仪器观测结果,在此基础上比较全面地综述了卫星遥感测量大气CO₂浓度的主要方法及获得的结果,包括利用近红外反射太阳光谱或地气热红外发射辐射光谱及两者的组合进行得模拟和卫星实测反演研究,最后简单地进行了总结和展望。     

CO2 solubility in dacitic melts equilibrated with H2O-CO2 fluids: Implications for modeling the solubility of CO2 in silicic melts

The solubility of CO₂ in dacitic melts equilibrated with H₂O-CO₂ fluids was experimentally investigated at 1250°C and 100 to 500 MPa. CO₂ is dissolved in dacitic glasses as molecular CO₂ and carbonate. The quantification of total CO₂ in the glasses by mid-infrared (MIR) spectroscopy is difficult because the weak carbonate bands at 1430 and 1530 cm⁻¹ can not be reliably separated from background features in the spectra. Furthermore, the ratio of CO_2,mol/carbonate in the quenched glasses strongly decreases with increasing water content. Due to the difficulties in quantifying CO₂ species concentrations from the MIR spectra we have measured total CO₂ contents of dacitic glasses by secondary ion mass spectrometry (SIMS).At all pressures, the dependence of CO₂ solubility in dacitic melts on x^fluid_CO2,total shows a strong positive deviation from linearity with almost constant CO₂ solubility at x_CO2fluid > 0.8 (maximum CO₂ solubility of 795 ± 41, 1376 ± 73 and 2949 ± 166 ppm at 100, 200 and 500 MPa, respectively), indicating that dissolved water strongly enhances the solubility of CO₂. A similar nonlinear variation of CO₂ solubility with x_CO2fluid has been observed for rhyolitic melts in which carbon dioxide is incorporated exclusively as molecular CO₂ (Tamic et al., 2001). We infer that water species in the melt do not only stabilize carbonate groups as has been suggested earlier but also CO₂ molecules.A thermodynamic model describing the dependence of the CO₂ solubility in hydrous rhyolitic and dacitic melts on T, P, f_CO2 and the mol fraction of water in the melt (x_water) has been developed. An exponential variation of the equilibrium constant K₁ with x_water is proposed to account for the nonlinear dependence of x_CO2,totalmelt on x_CO2fluid. The model reproduces the CO₂ solubility data for dacitic melts within ±14% relative and the data for rhyolitic melts within 10% relative in the pressure range 100-500 MPa (except for six outliers at low x_CO2fluid). Data obtained for rhyolitic melts at 75 MPa and 850°C show a stronger deviation from the model, suggesting a change in the solubility behavior of CO₂ at low pressures (a Henrian behavior of the CO₂ solubility is observed at low pressure and low H₂O concentrations in the melt). We recommend to use our model only in the pressure range 100-500 MPa and in the x_CO2fluid range 0.1-0.95. The thermodynamic modeling indicates that the partial molar volume of total CO₂ is much lower in rhyolitic melts (31.7 cm³/mol) than in dacitic melts (46.6 cm³/mol). The dissolution enthalpy for CO₂ in hydrous rhyolitic melts was found to be negligible. This result suggests that temperature is of minor importance for CO₂ solubility in silicic melts.     

Changes in Atlantic Thermohaline Circulation under Different Atmospheric CO2 Scenarios in a Climate Model

INTRODUCTIONThermohaline circulation(THC)is normally de-fined as the density-driven global-scale oceanic circu-lation,which flows northwardin the upper layer andsouthward in the deeper layer in the Atlantic.Itplays ani mportant role in the global meridional heatand the freshwater transports(Marotzke,2000).Thus,changes in the THC alter the global oceanheat transport and affect the global cli mate(Broeck-er,1991).The increase in the concentration of greenhousegases will reduce the effici…     

Iron weathering products in a CO2 + (H2O or H2O2) atmosphere: Implications for weathering processes on the surface of Mars

Various iron-bearing primary phases and rocks have been weathered experimentally to simulate possible present and past weathering processes occurring on Mars. We used magnetite, monoclinic and hexagonal pyrrhotites, and metallic iron as it is suggested that meteoritic input to the martian surface may account for an important source of reduced iron. The phases were weathered in two different atmospheres: one composed of CO₂ + H₂O, to model the present and primary martian atmosphere, and a CO₂ + H₂O + H₂O₂ atmosphere to simulate the effect of strong oxidizing agents. Experiments were conducted at room temperature and a pressure of 0.75 atm. Magnetite is the only stable phase in the experiments and is thus likely to be released on the surface of Mars from primary rocks during weathering processes. Siderite, elemental sulfur, ferrous sulfates and ferric (oxy)hydroxides (goethite and lepidocrocite) are the main products in a water-bearing atmosphere, depending on the substrate. In the peroxide atmosphere, weathering products are dominated by ferric sulfates and goethite. A kinetic model was then developed for iron weathering in a water atmosphere, using the shrinking core model (SCM). This model includes competition between chemical reaction and diffusion of reactants through porous layers of secondary products. The results indicate that for short time scales, the mechanism is dominated by a chemical reaction with second order kinetics (k = 7.75 × 10⁻⁵ g⁻¹/h), whereas for longer time scales, the mechanism is diffusion-controlled (De_A = 2.71 × 10⁻¹⁰ m²/h). The results indicate that a primary CO₂- and H₂O-rich atmosphere should favour sulfur, ferrous phases such as siderite or Fe²⁺-sulfates, associated with ferric (oxy)hydroxides (goethite and lepidocrocite). Further evolution to more oxidizing conditions may have forced these precursors to evolve into ferric sulfates and goethite/hematite.     

The role of sulfur in chemical weathering and atmospheric CO2 fluxes: Evidence from major ions, δCDIC, and δSSO4 in rivers of the Canadian Cordillera

Water samples from the Fraser, Skeena and Nass River basins of the Canadian Cordillera were analyzed for dissolved major element concentrations (HCO₃⁻, SO₄²⁻, Cl⁻, Ca²⁺, Mg²⁺, K⁺, Na⁺), δ¹³C of dissolved inorganic carbon (δ¹³C_DIC), and δ³⁴S of dissolved sulfate (δ³⁴S_SO4) to quantify chemical weathering rates and exchanges of CO₂ between the atmosphere, hydrosphere, and lithosphere. Weathering rates of silicates and carbonates were determined from major element mass balance. Combining the major element mass balance with δ³⁴S_SO4 (−8.9 to 14.1‰_CDT) indicates sulfide oxidation (sulfuric acid production) and subsequent weathering of carbonate and to a lesser degree silicate minerals are important processes in the study area. We determine that on average, 81% of the riverine sulfate can be attributed to sulfide oxidation in the Cordilleran rivers, and that 25% of the total weathering cation flux can be attributed to carbonate and silicate dissolution by sulfuric acid. This result is validated by δ¹³C_DIC values (−9.8 to −3.7‰ _VPDB) which represents a mixture of DIC produced by the following weathering pathways: (i) carbonate dissolution by carbonic acid (−8.25‰) > (ii) silicate dissolution by carbonic acid (−17‰) ≈ (iii) carbonate dissolution by sulfuric acid derived from the oxidation of sulfides (coupled sulfide-carbonate weathering) (+0.5‰).δ³⁴S_SO4 is negatively correlated with δ¹³C_DIC in the Cordilleran rivers, which further supports the hypothesis that sulfuric acid produced by sulfide oxidation is primarily neutralized by carbonates, and that sulfide-carbonate weathering impacts the δ¹³C_DIC of rivers. The negative correlation between δ³⁴S_SO4 and δ¹³C_DIC is not observed in the Ottawa and St. Lawrence River basins. This suggests other factors such as landscape age (governed by tectonic uplift) and bedrock geology are important controls on regional sulfide oxidation rates, and therefore also on the magnitude of sulfide-carbonate weathering—i.e., it is more significant in tectonically active areas.Calculated DIC fluxes due to Ca and Mg silicate weathering by carbonic acid (38.3 × 10³ mol C · km⁻² · yr⁻¹) are similar in magnitude to DIC fluxes due to sulfide-carbonate weathering (18.5 × 10³ mol C · km⁻² · yr⁻¹). While Ca and Mg silicate weathering facilitates a transfer of atmospheric CO₂ to carbonate rocks, sulfide-carbonate weathering can liberate CO₂ from carbonate rocks to the atmosphere when sulfide oxidation exceeds sulfide deposition. This implies that in the Canadian Cordillera, sulfide-carbonate weathering can offset up to 48% of the current CO₂ drawdown by silicate weathering in the region.