Dissolution Of Primary Minerals Research Articles

Water‐rock interactions drive chemostasis

AbstractThe western U.S. is experiencing shifts in recharge due to climate change, and it is currently unclear how hydrologic shifts will impact geochemical weathering and stream concentration–discharge (C–Q) patterns. Hydrologists often use C–Q analyses to assess feedbacks between stream discharge and geochemistry, given abundant stream discharge and chemistry data. Chemostasis is commonly observed, indicating that geochemical controls, rather than changes in discharge, are shaping stream C–Q patterns. However, few C–Q studies investigate how geochemical reactions evolve along groundwater flowpaths before groundwater contributes to streamflow, resulting in potential omission of important C–Q controls such as coupled mineral dissolution and clay precipitation and subsequent cation exchange. Here, we use field observations—including groundwater age, stream discharge, and stream and groundwater chemistry—to analyse C–Q relations in the Manitou Experimental Forest in the Colorado Front Range, USA, a site where chemostasis is observed. We combine field data with laboratory analyses of whole rock and clay x‐ray diffraction and soil cation‐extraction experiments to investigate the role that clays play in influencing stream chemistry. We use Geochemist's Workbench to identify geochemical reactions driving stream chemistry and subsequently suggest how climate change will impact stream C–Q trends. We show that as groundwater age increases, C–Q slope and stream solute response are not impacted. Instead, primary mineral dissolution and subsequent clay precipitation drive strong chemostasis for silica and aluminium and enable cation exchange that buffers calcium and magnesium concentrations, leading to weak chemostatic behaviour for divalent cations. The influence of clays on stream C–Q highlights the importance of delineating geochemical controls along flowpaths, as upgradient mineral dissolution and clay precipitation enable downgradient cation exchange. Our results suggest that geochemical reactions will not be impacted by future decreasing flows, and thus where chemostasis currently exists, it will continue to persist despite changes in recharge.

Tracing the source and transport of Hg during pedogenesis in strongly weathered tropical soil using Hg isotopes

Soil is one of the largest reservoirs and re-emission sources of mercury (Hg) on Earth’s surface. The accumulation and remobilization of Hg during pedogenesis affect how Hg is transported from terrestrial to aquatic environment and biota, but these processes are poorly understood. Here we present Hg concentration and isotope ratios of soil and bedrock samples from a latosol profile formed through intense weathering of Cenozoic basalts in Zhanjiang, Guangdong Province, China, to trace the sources, transport and transformation processes of Hg during pedogenesis, and to gain insights on the potential impact of tropical soils on global Hg cycling. The entire soil profile shows negative δ202Hg (−2.97‰ ± 0.08‰ to −2.54‰ ± 0.08‰) and negative Δ199Hg (−0.68‰ ± 0.04‰ to −0.43‰ ± 0.04‰), with a gradual downward positive shift of Δ199Hg below 35 cm. An isotopic mixing model based on Δ199Hg suggests a dominant Hg input from atmospheric Hg (HgAtm) and limited contribution (<36%) of geogenic Hg (HgGeo) from the bedrock. The strongly negative Δ199Hg throughout the latosol profile suggests that HgAtm was likely subject to substantial photoreduction on soil surface and migrated downward after incorporation into soils. Moreover, there is a distinct positive shift of δ202Hg alongside a rapid decrease of HgGeo from the bedrock to the weakly weathered basalt, indicating a substantial loss of HgGeo with the preferential release of lighter isotopes during the initial weathering, likely due to the dissolution of primary minerals. In addition, the δ202Hg shows a negative correlation with soil pH at some horizons, attributable to the isotopic fractionation during Hg(II) speciation change in soil solution and the selective complexation/adsorption of different Hg(II) species onto mineral surfaces, which are affected by surface charge properties and thus soil pH. Overall, our results provide direct evidence for the accumulation and downward migration of HgAtm in tropical soils during pedogenesis, as well as the loss of HgGeo during the weathering of bedrock, which may serve as an underappreciated source of Hg in tropical regions and have a potential impact on the Hg isotope signatures in aquatic environments.

Feedbacks between the formation of secondary minerals and the infiltration of fluids into the regolith of granitic rocks in different climatic zones (Chilean Coastal Cordillera)

Abstract. Subsurface fluid pathways and the climate-dependent infiltration of fluids into the subsurface jointly control the intensity and depth of mineral weathering reactions. The products of these weathering reactions (secondary minerals), such as Fe(III) oxyhydroxides and clay minerals, in turn exert a control on the subsurface fluid flow and hence on the development of weathering profiles. We explored the dependence of mineral transformations on climate during the weathering of granitic rocks in two 6 m deep weathering profiles in Mediterranean and humid climate zones along the Chilean Coastal Cordillera. We used geochemical and mineralogical methods such as (micro-) X-ray fluorescence (μ-XRF and XRF), oxalate and dithionite extractions, X-ray diffraction (XRD), and electron microprobe (EMP) mapping to elucidate the transformations involved during weathering. In the profile of the Mediterranean climate zone, we found a low weathering intensity affecting the profile down to 6 m depth. In the profile of the humid climate zone, we found a high weathering intensity. Based on our results, we propose mechanisms that can intensify the progression of weathering to depth. The most important is weathering-induced fracturing (WIF) by Fe(II) oxidation in biotite and precipitation of Fe(III) oxyhydroxides and by the swelling of interstratified smectitic clay minerals that promotes the formation of fluid pathways. We also propose mechanisms that mitigate the development of a deep weathering zone, like the precipitation of secondary minerals (e.g., clay minerals) and amorphous phases that can impede the subsurface fluid flow. We conclude that the depth and intensity of primary mineral weathering in the profile of the Mediterranean climate zone is significantly controlled by WIF. It generates a surface–subsurface connectivity that allows fluid infiltration to great depth and hence promotes a deep weathering zone. Moreover, the water supply to the subsurface is limited in the Mediterranean climate, and thus, most of the weathering profile is generally characterized by a low weathering intensity. The depth and intensity of weathering processes in the profile of the humid climate zone, on the other hand, are controlled by an intense formation of secondary minerals in the upper section of the weathering profile. This intense formation arises from pronounced dissolution of primary minerals due to the high water infiltration (high precipitation rate) into the subsurface. The secondary minerals, in turn, impede the infiltration of fluids to great depth and thus mitigate the intensity of primary mineral weathering at depth. These two settings illustrate that the depth and intensity of primary mineral weathering in the upper regolith are controlled by positive and negative feedbacks between the formation of secondary minerals and the infiltration of fluids.

Pervasive carbonation of peridotite to listvenite (Semail Ophiolite, Sultanate of Oman): clues from iron partitioning and chemical zoning

Abstract. Earth's long-term cycling of carbon is regulated from mid-ocean ridges to convergent plate boundaries by mass transfers involving mantle rocks. Here we examine the conversion of peridotite to listvenite (magnesite + quartz rock) during CO2 metasomatism along the basal thrust of the Semail Ophiolite (Fanja, Sultanate of Oman). At the outcrop scale, this transformation defines reaction zones, from serpentinized peridotites to carbonated serpentinites and listvenites. Based on a detailed petrological and chemical study, we show that carbonation progressed through three main stages involving the development of replacive textures ascribed to early stages, whilst carbonate (± quartz) veining becomes predominant in the last stage. The pervasive replacement of serpentine by magnesite is characterized by the formation of spheroids, among which two types are identified based on the composition of their core regions: Fe-core and Mg-core spheroids. Fe zoning is a type feature of matrix and vein magnesite formed during the onset carbonation (Stage 1). While Fe-rich magnesite is predicted to form at low fluid XCO2 from a poorly to moderately oxidized protolith, our study evidences that the local non-redox destabilization of Fe oxides into Fe-rich magnesite is essential to the development of Fe-core spheroids. The formation of Fe-core spheroids is followed by the pervasive (over-)growth of Mg-rich spheroids and aggregates (Stage 2) at near-equilibrium conditions in response to increasing fluid XCO2. Furthermore, the compositions of carbonates indicate that most siderophile transition elements released by the dissolution of primary minerals are locally trapped in carbonate and oxides during matrix carbonation, while elements with a chalcophile affinity are the most likely to be leached out of reaction zones.

Increased primary mineral dissolution control on a terrestrial silicate lithium isotope record during the middle Miocene Climate Optimum

Lithium isotopes have great potential to fractionate at subaerial environment, so they are promising proxies for tracing chemical weathering history. However, it remains uncertain how to relate lithium isotopic compositions (δ7Li) in sediments to silicate weathering and past climate in terrestrial setting. To tackle this question, we choose the warm and wet middle Miocene climate optimum (MMCO, 17–14 Ma) with large climate variation amplitude and the following cold and dry middle Miocene climate cooling period (MMCC, 14–11 Ma) with damped climatic variation amplitude, as two climate contrasting intervals to study lithium isotopes and content ([Li]) variations of terrestrial mudrocks. Our study site is located at the eastern Qaidam Basin of the northeastern Tibetan Plateau and the precipitation pattern of this part of the basin is similar to the Chinese Loess Plateau over the two studied intervals. The study site is suitable for clarifying link between climate and δ7Li variations because previous studies have demonstrated no provenance shift over the studied interval and short transport distance from source to the study site suggests little chemical weathering over the transportation process. Both δ7Li and [Li] values show larger amplitude over the MMCO (spanning from −1.2 to 3.2 ‰ and from 32.8 to 93.9 ug/g, respectively) than the MMCC interval (−1.8 to 1.2 ‰ and 41.7–80.8 ug/g, respectively), consistent with general feature of global and Chinese Loess Plateau climate. However, δ7Li data are higher over the MMCO in comparison with the MMCC, contrary to expectation of more lithium isotope fractionation at warm interval. We interpret the more positive δ7Li values over the MMCO using increased ratio of primary mineral dissolution over secondary mineral precipitation. Qaidam mudrock and benthic Li records show complementary changes, suggesting their possible link. Furthermore, past research reveals lack of focused uplift of the northeastern Tibetan Plateau over the studied 18–11 Ma. So we conclude that global climate, rather than Tibetan uplift, played an important role in modulating inland Qaidam Basin climate variations over the middle Miocene and that increased chemical weathering over warm climate can lead to a small magnitude of lithium isotope fractionation. Therefore, interpreting chemical weathering history, and hence climate, using lithium isotope data in terrestrial setting requires considering relative importance of primary mineral dissolution versus secondary mineral precipitation.

Geochemical behavior of stable strontium isotopes during continental weathering process: A review

Continental weathering, an important geological process that affects the formation and evolution of the earth, involves the interaction of matter and energy among the lithosphere, atmosphere, hydrosphere, and biosphere. Stable Sr isotope (δ88/86Sr) is a novel non-traditional stable isotope. It has been widely discussed in tracing continental weathering, studying marine Sr cycle, and analyzing biogeochemical behavior in recent years. Its combination with 87Sr/86Sr can indicate the source of Sr and the mass fractionation of geological processes, which has incomparable advantages over other isotopic systems, such as Li, Mg, and Ba. However, owing to the small mass difference (2%) between 86Sr and 88Sr, fractionation is not significant, which makes the measurement of the ratio δ88/86Sr difficult and limits its application to trace continental weathering.In this study, major developments and challenges in using stable Sr isotopes to trace continental weathering are reviewed, when considering high-precision testing methods, characteristics of δ88/86Sr in natural reservoirs, and geochemical behaviors. The high-precision measurement methods currently used for stable Sr isotopes mainly include multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) and thermal ionization mass spectrometry (TIMS), both of which involve chemical purification by a cation exchange column or Sr specific resin, coupled with various methods for quality discrimination correction. The present analytical precision for the determination of δ88/86Sr in geological samples is 0.02‰ ∼ 0.08‰. The δ88/86Sr varies widely in natural reservoirs. In particular, the range of δ88/86Sr values in extraterrestrial reservoirs, the biosphere, the lithosphere, and the hydrosphere are -1.73‰ to +0.66‰, -0.87‰ to +0.85‰, -0.20‰ to +0.53‰ and -0.45‰ to +0.66‰, respectively. Stable Sr isotope fractionation occurs in the processes of differential dissolution of primary minerals (Δ88/86Sr = -0.13‰), formation and adsorption of secondary minerals (Δ88/86Sr = -0.15‰), precipitation of carbonate (Δ88/86Sr = -0.20‰), and biological processes (Δ88/86Sr = -0.15‰), which causes the δ88/86Sr in fluid (solid) phase to δ88/86Sr increases (decrease). Previous research on the fractionation mechanisms and constraint conditions of stable Sr isotopes during continental weathering is insufficient. Thus, promoting a wide application of stable Sr isotopes to trace continental weathering through the combination of field profiles, laboratory experiments and theoretical calculation is urgently warranted.

Concentration-runoff relationships of contrasting small mountainous rivers in the Pacific Northwest, USA: Insights into the weathering of rhenium relative to other weathering products

This study examines dissolved rhenium (Re) concentrations as a function of water runoff using river samples from two contrasting mountainous watersheds, the Eel and Umpqua Rivers in the Pacific Northwest, USA. These watersheds share many key characteristics in terms of size, discharge, climate, and vegetation, but they have a 15-fold difference in sediment yield due to differences in their tectonic setting and uplift and erosion rates. We evaluate concentration-runoff (C-R) relationships and ratios of coefficients of variation (CVC/CVR) for major cations, anions, dissolved inorganic carbon, selected trace elements including Re, and 87Sr/86Sr ratios. Recent research outlines the potential of Re to serve as a tracer for the oxidation of ancient/fossil organic matter because of its close association with petrogenic carbon (OCpetro) in rocks. In both the Eel and Umpqua Rivers, our measurements show that Re behaves similarly to major weathering derived-solutes corrected for atmospheric input, such as Ca2+*, Mg2+*, and Na+* with modest dilution across all tributaries with increasing runoff. Rhenium behaves dissimilarly from other trace elements, such as Mo and U, and is also dissimilar to biologically-cycled nutrients, such as NO3–, PO43−, and K+*, suggesting differences in sources, solute generation mechanisms, and flowpaths. Rhenium behavior is also distinct from that of colloids, which have increasing concentrations with increasing runoff. We find that Re and sulfate corrected for atmospheric input (SO42−*) have distinct C-R relationships, in which SO42−* undergoes greater dilution with increasing runoff. This implies that Re is not dominantly sourced from sulfide weathering, which leaves primary bedrock minerals and OCpetro hosted in bedrock of these watersheds as the likely dominant sources of dissolved Re release. At mean discharge, Re concentration in the Eel river (3.5 pmol L-1) is more than two times greater than Re concentrations in the Umpqua River (1.5 pmol L-1). Furthermore, comparison of two tributary watersheds with similar bedrock but marked differences in erosion rates show higher Re concentrations in Bull Creek (erosion rate of 0.5 mm yr−1) relative to Elder Creek (erosion rate of 0.2 mm yr−1). The results of this study suggest that dissolved Re in the Eel and Umpqua River basins is likely derived from primary mineral dissolution or OCpetro oxidation, and Re fluxes are higher in areas with higher erosion rates, suggesting that tectonic setting is one factor that controls Re release and therefore OCpetro oxidation.

Multiscale physical–chemical analysis of the impact of fracture networks on weathering: Application to nickel redistribution in the formation of Ni-laterite ores, New Caledonia

Supergene processes related to downward water migration and dissolution of primary minerals in the New Caledonian peridotites result in Ni enrichment at the bottom of the lateritic profile near bedrock. However, the combined effects of relief, lateral fluid flow, and complex inherited discontinuity networks filled by serpentine generate a more complex Ni distribution than a simple flat horizon. In surficial environments, fluid flow and mass transfer are not limited to the vertical scale; they can also be related to lateral fluid circulation and local drainage along damage zones in the vicinity of faults. In this study, we present new structural, petrophysical and geochemical data for core samples to shed light on the impact of a fracture network on the alteration and progression of the Ni-enrichment front during weathering. The analysis of element redistribution by XRF mapping coupled with fracture extraction from computed tomography (CT) establishes that the serpentine fracture network comprises sets of sub-orthogonal fractures whose orientations are potentially determined by pre-existing magmatic foliation. The progression of the olivine dissolution front leads to the redistribution and concentration of Ni into the serpentine fracture network as secondary Mg-Ni talc-like phases. The increase in porosity from < 1 % in the bedrock to > 10 % in the saprock is mainly driven by the formation of nanopores. Nanoporosity may control the development of the weathering front and the redistribution of Ni by small-scale diffusion. Structural and geochemical characteristics identified at the sample scale are analogous to those observed on the larger scale of the outcrop and deposit. Scale invariance in the structural organization and geochemical evolution indicates the potential upscaling of the processes involved in the redistribution of Ni.

Weathering intensity and lithium isotopes: A reactive transport perspective

Lithium isotopes have emerged as a powerful tool to probe the response of global weathering to changes in climate. Due to the preferential incorporation of ^6^Li into clay minerals during chemical weathering, the isotope ratio δ^7^Li may be used to interrogate the balance of primary mineral dissolution and clay precipitation. This balance has been linked to relative rates of chemical and physical denudation, such that dissolved δ^7^Li (δ^7^Li~diss~) is highest at moderate weathering intensities when chemical and physical denudation are comparable. However, we argue that current theory linking δ^7^Li to weathering regimes through fluid travel times are unable to explain observations of low δ^7^Li and high Li concentrations in rapidly eroding settings. In this study, we re-examine the relationships between δ^7^Li, Li concentration, and weathering regime by incorporating Li isotopes into simulations of weathering profiles using a reactive transport model (CrunchFlow) that includes advective fluxes of regolith to simulate variable erosion rates in response to uplift. In these simulations, fractionation is implemented through a kinetic fractionation factor during clay precipitation, which allows the δ^7^Li of dissolved and suspended loads in the model to vary as a function of Li/Al ratios in primary and secondary minerals. When the model is run over a range of infiltration and erosion rates, simulations reproduce observed global patterns of δ^7^Li~diss~ and suspended load δ^7^Li as a function of weathering intensity, controlled primarily by water travel times and mineral residence times in weathered bedrock. We find that reduced water travel times at low weathering intensity, however, are inconsistent with observations of high Li concentrations. As an alternative, we demonstrate how the rapid weathering of soluble, Li-rich minerals such as chlorite under low weathering intensities may resolve this apparent discrepancy between data and theory. We also suggest that observed patterns are consistent with geothermal Li sources under low weathering intensities. This work offers a foundation guiding future studies in testing potential mechanisms underlying global riverine δ*^7^*Li~diss~.

Modeling the effect of mineral armoring on the rates of coupled dissolution-precipitation reactions: Implications for chemical weathering

One of the mechanisms influencing weathering rates is mineral armoring, which is the build-up of insoluble coatings on primary mineral phases. Such armoring is often the result of coupled dissolution-precipitation reactions that occur during weathering. While the role of armoring in reducing dissolution rates is widely recognized, a quantitative mechanistic description of the way it impacts mineral weathering rates has not yet been developed. This paper demonstrates how a diffusion boundary layer model can simulate the effect of a porous secondary mineral layer on the rate of primary mineral dissolution under acidic conditions. In the model, the rates are affected by 3 parameters: layer thickness, the ratio of porosity to tortuosity, and the Biot number, which defines the ratio of dissolution to diffusion. Numerical solutions to the equations show that when the porosity/tortuosity ratio is low (~0.01), dissolution rates can be reduced by several orders of magnitude relative to armor-free minerals. Biot numbers greater than 1 were also found to lead to a significant reduction in the dissolution rate. Moreover, comparison with reported experimental data shows that the model can accurately simulate the change in thickness of the secondary mineral coating with time. The dissolution rates of pristine coating-free minerals in laboratory experiments can be orders of magnitude higher than those observed under field conditions, and the results suggest that mineral armoring can account for much of this discrepancy.

Ge/Si Ratio of River Water in the Yarlung Tsangpo: Implications for Hydrothermal Input and Chemical Weathering

Germanium/Silicon (Ge/Si) ratio is a common proxy for primary mineral dissolution and secondary clay formation yet could be affected by hydrothermal and anthropogenic activities. To decipher the main controls of riverine Ge/Si ratios and evaluate the validity of the Ge/Si ratio as a weathering proxy in the Tibetan Plateau, a detailed study was presented on Ge/Si ratios in the Yarlung Tsangpo River, southern Tibetan Plateau. River water and hydrothermal water were collected across different climatic and tectonic zones, with altitudes ranging from 800 m to 5000 m. The correlations between TDS (total dissolved solids) and the Ge/Si ratio and Si and Ge concentrations of river water, combined with the spatial and temporal variations of the Ge/Si ratio, indicate that the contribution of hydrothermal water significantly affects the Ge/Si ratio of the Yarlung Tsangpo River water, especially in the upper and middle reaches. Based on the mass balance calculation, a significant amount of Ge (11–88%) has been lost during its transportation from hydrothermal water to the river system; these could result from the incorporation of Ge on/into clays, iron hydroxide, and sulfate mineral. In comparison, due to the hydrothermal input, the average Ge/Si ratio in the Yarlung Tsangpo River is a magnitude order higher than the majority of rivers over the world. Therefore, evaluation of the contribution of hydrothermal sources should be considered when using the Ge/Si ratio to trace silicate weathering in rivers around the Tibetan Plateau.

Carbonate weathering dominates magnesium isotopes in large rivers: Clues from the Yangtze River

Carbonate weathering regulates the short-term carbon (C) cycle and global climate due to its fast response to hydrological processes. The carbonate weathering flux needs to be well constrained to better understand the climate change at short time scale. Riverine magnesium (Mg) isotopes are sensitive to primary mineral dissolution and so have great potential to trace carbonate weathering. Global large rivers draining continental crust dominate weathering flux to the oceans, but how riverine Mg isotopes respond to carbonate weathering remains unclear. The Yangtze River drainage basin (YRDB) was selected to test the robustness of riverine Mg isotopes (δ26Mg) in tracing continental carbonate weathering because it spans a wide range in lithology, geomorphology and climate. The riverine δ26Mg values within the YRDB show a decreasing trend from the headwater to the mainstream ranging from −1.36‰ to −0.59‰. The dissolved δ26Mg have strong negative correlations with carbonate weathering rate and intensity within the YRDB, indicating a sensitive response of riverine δ26Mg to the carbonate weathering flux. In a compilation of Mg fluxes and δ26Mg in the world's largest rivers, there is similar dominance of carbonate weathering on riverine Mg fluxes and isotopes. Therefore, we propose that riverine δ26Mg in large rivers are a robust tracer of carbonate weathering intensity. Intensifying carbonate weathering under global warming tends to increase riverine Mg and C fluxes to the oceans and thus the atmospheric CO2 sink at the millennial time scale.

Hydrothermal and magmatic contributions to surface waters in the Aso caldera, southern Japan: Implications for weathering processes in volcanic areas

The role of hydrothermal fluids in the dissolution of primary minerals in volcanic areas, hotspots of silicate weathering at the global scale, is not well quantified. This study aims to determine the hydrothermal contribution to the lateral export of solutes from the Aso caldera, southern Japan. A set of indicators for the hydrothermally related contribution is systematically discussed. Spring, groundwater and river water samples were collected along the two main rivers of the caldera, and their major and trace element concentrations, as well as the stable isotopic compositions of water (δ2Η and δ18O), dissolved inorganic carbon (δ13C), and sulphate (δ34S and δ18O) were analysed. Hydrothermal springs in the study area are associated with a substantial sulphate contribution of magmatic origin. In contrast, the hydrochemistry of non-hydrothermal springs reflects surface water-soil interactions. In particular, non-hydrothermal waters have significantly higher selenium to sulphate ratios than hydrothermal waters. The selenium to sulphate ratios allow to distinguish two different sulphur sources in the Aso catchment: hydrothermal waters impacted by the oxidation of sulphides or controlled by disproportionation reactions of SO2, and non-hydrothermal sulphate. Overall, the results show that hydrothermal waters strongly influence the sulphur budget, accounting for 67 to 91% of the total sulphate flux at the caldera outlet. The dissolution of magmatic CO2 and SO2 contribute to >60% of the observed weathering fluxes in this volcanic area. This suggests that magmatic gases and hydrothermal fluids should be considered for the estimation of biogeochemical budgets at the regional and global scales. However, the temporal variation of the magmatic activity and its effect on the chemistry of waters have to be investigated in future work.

The Influence of Hyper-Alkaline Leachate on a Generic Host Rock Composition for a Nuclear Waste Repository: Experimental Assessment and Modelling of Novel Variable Porosity and Surface Area

Deep geological disposal is the preferred solution for long-term storage of radioactive waste in many countries. In a deep repository, cementitious materials are widely used in the structure and buffer/backfill of the repository for the stabilisation of the hazardous materials. The cement acts as a physical barrier and also contributes chemically to waste containment by buffering the groundwater to a high pH, limiting the solubility of many radionuclides. This paper describes an experimental and modelling study which evaluates the geochemical interaction between young cement leachate (YCL, pH = 13) and a generic hard rock (in this case Hollington sandstone, representing a ‘hard’ host rock) during permeation with the leachate, as it drives mineralogical changes in the system. One-dimensional reactive transport was modelled using a mixing cell approach within the PHREEQC geochemical code to identify the essential parameters and understand and scale up the effect of variations in these parameters on the observed geochemical processes. This study also focused on the effects of variable porosity, reactive surface area and pore volume on improving the modelling of rock alteration in the system compared to conventional models that assume constant values for these properties. The numerical results showed that the interaction between the injected hyper-alkaline leachate and the sandstone sample results in a series of mineralogical reactions. The main processes were the dissolution of quartz, kaolinite and k-feldspar which was coupled with the precipitation of calcium silicate hydrate gel and tobermorite-14A (C–S–H), prehnite (hydrated silicate), saponite-Mg (smectite clay) and mesolite (Na–Ca zeolite). The simulation showed that the overall porosity of the system increased as primary minerals dissolve and no stable precipitation of the secondary C–S–H /C–A–S–H phases was predicted. The variable porosity scenario provides a better fitting to experimental data and more detailed trends of chemistry change within the column. The time and the number of moles of precipitated secondary phases were also improved which was related to greater exposure surface area of the minerals in the sandstone sample to the YCL.Article HighlightsThe drop in calcium, aluminium and silicate concentrations is mainly due to the formation of calcium silicate hydrate and zeolite minerals as secondary phases. The simulation showed that the overall porosity of the system increased as primary minerals dissolve and no stable precipitation of the secondary C–S–H /C–A–S–H phases was predicted.The dissolution of primary minerals and the precipitation of secondary C–S–H phases had a minimal effect on the pH values, and this was controlled mainly by the initial fluid chemistry.The variable porosity scenario provides a better fitting to experimental data and more detailed trends of chemistry change within the column.

Pedological trends and implications for forest productivity in a Holocene soil chronosequence, Calvert Island, British Columbia, Canada

Chronosequence studies of soil formation and ecosystem development provide important insights into the pathways and rates of change occurring on centennial and millennial time scales. In cool or temperate humid environments, Podzols are the predominant soil type formed under coniferous forests in coarse-textured parent material and have been a major focus of chronosequence studies. This study examined the rate and mechanisms of Podzol development and related forest productivity in a sand dune chronosequence in a hypermaritime climate in coastal British Columbia (BC). The sequence spans 10 760 ± 864 yr over eight sites and is the first documented chronosequence in coastal BC to span most of the Holocene Epoch. Soil samples from each genetic horizon were analyzed for bulk density, pH and concentrations of total carbon (C), pyrophosphate- and oxalate-extractable aluminum (Al) and iron (Fe), and total elements. Within ∼3500 yr, a mature Podzol had formed, with cemented horizons (ortstein and placic) present. Organo-metallic complexation appeared to be the dominant mechanism involved in podzolization. Despite a mild, moist climate conducive to chemical weathering, all soils had similarly low values for the chemical index of alteration, suggesting that congruent dissolution of primary minerals may be occurring. Ecosystem retrogression is apparent in the latter stages of the chronosequence — a phenomenon not previously documented in coastal BC. Further research is needed to examine the interactions of nutrient limitation, soil physical barriers, and other possible drivers of ecosystem retrogression.

Rate limitations of nano-scale weathering front advance in the slow-eroding Sri Lankan Highlands

In the Sri Lankan Highlands denudation and chemical weathering represent the low-end member in global weathering rates. Here we report on the causes for these low rates in corestones from a highly weathered saprolite profile. By using electron microprobe and transmission electron microscopy (TEM) analyses, we investigated weathering reactions, and derived rates of pyroxene and biotite oxidation. High-resolution TEM analyses on primary minerals showed that the initial weathering products are non-crystalline and that these form the precursors of secondary minerals (kaolinite and smectite). The dissolution of primary minerals is characterised by sharp reaction fronts in the absence of chemical gradients, hence, dissolution can best be described by a dissolution – reprecipitation process. The first observable weathering reaction is the oxidation of structural Fe(II) in pyroxene and biotite. This oxidation is restricted to distinct zones within the minerals without the formation of oxidized layers. While the oxidation is not accompanied by chemical changes, the oxidation of structural Fe(II) in biotite may cause lattice distortion. Pyroxene and biotite oxidation rates were calculated at the corestone-scale by using the gradient of bulk rock Fe(II)/Fetotal ratios, assuming that oxidation is coupled to the weathering front advance rate. At the mineral-scale, oxidation rates were calculated by using gradients of in situ Fe(II)/Fe(III) ratios measured with electron energy-loss spectroscopy (EELS) within the minerals assuming a coupled oxidation-cation diffusion process. The mineral-scale oxidation rates are significantly higher, log Ominin situ = −11 molmin m−2 s−1, than corestone-scale oxidation rates, log Omin = −13 to −15 mol m−2 s−1. We explain the difference to result from the fact that corestone-scale rates average the oxidation over the entire mineral surface. Because at the corestone-scale pyroxene oxidation rates are also similar to dissolution rates, we infer that oxidation preconditions Fe(II)- bearing primary silicate minerals to weathering. However, although oxidation is initiating chemical weathering in this setting and is limited by the supply of O2, overall conversion of bedrock to saprolite is driven by the formation of porosity by fracture formation during this reaction, which allows for fluid transport and subsequent plagioclase weathering. We conclude that in compact bedrock nm- to µm-scale fracture- and porosity generation are the processes that drive weathering in tectonically quiescent regions. They are also the processes at depth that couple the weathering zone with processes at its surface. Finally, the formation of secondary surface layers at the nm-scale is essential in controlling the equilibrium in the local weathering environment and hence mineral dissolution. These layers are likely also those that control isotope fractionation in the weathering zone.

Reaction and Alteration of Mudstone with Ordinary Portland Cement and Low Alkali Cement Pore Fluids

The construction of a repository for the geological disposal of radioactive waste will utilize cement-based materials. Following closure, resaturation will result in the development of a highly alkaline porewater. The alkaline fluid will migrate and react with host rock, producing a chemically disturbed zone (CDZ) around the repository. To understand how these conditions may evolve, a series of batch and flow experiments were conducted with Horonobe mudstone and fluids representative of the alkaline leachates expected from a cementitious repository. Both ordinary Portland cement (OPC) and low alkali cement (LAC) leachates were examined. The impact of the LAC leachates was more limited than the OPC leachates, with experiments using the LAC leachate showing the least reaction and lowest long-term pH of the different leachate types. The reaction was dominated by primary mineral dissolution, and in the case of OPC leachates, precipitation of secondary calcium-silicate-hydrate (C-S-H) phases. Flow experiments revealed that precipitation of the secondary phases was restricted to close to the initial contact zone of the fluids and mudstone. The experimental results demonstrate that a combination of both batch and flow-through experiments can provide the insights required for the understanding of the key geochemical interactions and the impact of transport.

Mineralogy and Geochemistry (HFSE and REE) of the Present-Day Acid-Sulfate Types Alteration from the Active Hydrothermal System of Furnas Volcano, São Miguel Island, The Azores Archipelago

Acid-sulfate alteration is comprised by clays, sulfate, sinter and native sulphur minerals crystallized as neoformation products from dissolution of primary minerals during water-rock interaction. Smectite, kaolinite, halloysite-7 Å and opal-A occur in assemblages with alunite. Smectite represents a mechanical mixture between two (propylitic and acid-sulfate) alteration types. High amounts of high-field strength elements (HFSE) and rare earth elements (REE) were measured in acid-sulfate rocks. The Nb vs. Ta and Zr vs. Hf show a positive trend and a widely scattered relationships, suggesting a large fractionation during acid-sulfate alteration. Higher ∑REE amounts (up to 934.5 ppm) were found in clay-sulfate assemblages and lower ∑REE amounts in sinter (opal-A ± sulfate, 169.05 ppm) than to fresh rocks (up to 751.2 ppm). The acid-sulfate rocks reveal a distinctive gull-wing chondrite-normalized pattern with a negative Eu anomaly and light- and heavy-REE “wings” similar to the gull-wing pattern of fresh rocks. The Eu/Eu* shows a large fractionation of acid sulfate rocks from 0.16 to 0.78 with respect to fresh trachyte products (0.10 to 0.38). Variation of (La/Sm)N and (La/Yb)N ratio show a large fractionation of light-REE and heavy-REE. The Y vs. Dy and Y vs. Ho show a very good positive correlation coefficient and a large Y fractionation in acid-sulfate rocks with respect to fresh rocks.

Features of the Formation of Geochemical Types of Natural Waters in Certain Regions of Central Eurasia

The report presents extensive factual data on the chemical composition of natural waters in different regions of Central Eurasia. The features of the chemical composition of natural waters are revealed for several regions with a humid and arid climate, as well as for tectonomagmatic activation conditions. The abundance of over 50 chemical elements in natural waters is characterized. The geochemical types of waters corresponding to rigorously defined evolution stages of the water–rock system are established for natural waters of all considered regions based on saturation of waters in secondary minerals. The influence of the geochemical conditions on the dissolution of primary minerals and the formation of secondary mineral phases is revealed. The composition of groundwaters is systematized by the features of the origin of their chemical compositions. The role of climatic, geological, and structural factors in the formation of geochemical types of waters in several Central Eurasian regions is shown.

Predicting the potential for mineral scale precipitation in unconventional reservoirs due to fluid-rock and fluid mixing geochemical reactions

Mineral precipitation within hydraulically fractured shale may affect fluid flow pathways and impact long-term hydrocarbon production. The ability to predict geochemical reactions causing problematic mineral precipitation will lead to active reservoir management strategies for improving production. Using the Marcellus Shale as a case study, laboratory experiments and reaction path modeling were applied to determine which reactions occur during hydraulic fracturing, shut-in, flowback, and production timeframes. Experimental results indicate that contact between fracturing fluid and shale will result in dissolution of primary minerals (carbonates, quartz, feldspars, kaolinite, chlorite, pyrite) and secondary mineral precipitation over time periods of less than one week. Precipitation of secondary carbonates, barite, iron oxides, feldspars, amorphous silica and clay is likely to occur within the reservoir during shut in and early flowback due to mixing between fracturing fluid and reservoir brine as based on modeling saturation indices using experimental fluid data. Reaction path modeling corroborates the dissolution and precipitation reactions observed experimentally. Comparison of the results to injected and produced waters from a Marcellus Shale well pad in Greene County, PA, USA, shows that the mineral reactions occur during the hydraulic fracturing, shut in, and early flowback periods. The results presented here demonstrate the value in applying experimental approaches to identify mineral precipitation/dissolution reactions that may significantly impact reservoir performance. The good agreement between geochemical models and experimental results provides confidence that numerical models can be applied to screen the potential fluid-mineral and fluid-mixing reactions in unconventional reservoirs that result in undesired mineral scale precipitation.