Weathering of the Rio Blanco quartz diorite, Luquillo Mountains, Puerto Rico: Coupling oxidation, dissolution, and fracturing

In the mountainous Rio Icacos watershed in northeastern Puerto Rico, quartz diorite bedrock weathers spheroidally, producing a 0.2-2 m thick zone of partially weathered rock layers (∼2.5 cm thickness each) called rindlets, which form concentric layers around corestones. Spheroidal fracturing has been modeled to occur when a weathering reaction with a positive ΔV of reaction builds up elastic strain energy. The rates of spheroidal fracturing and saprolite formation are therefore controlled by the rate of the weathering reaction.Chemical, petrographic, and spectroscopic evidence demonstrates that biotite oxidation is the most likely fracture-inducing reaction. This reaction occurs with an expansion in d (0 0 1) from 10.0 to 10.5 Å, forming “altered biotite”. Progressive biotite oxidation across the rindlet zone was inferred from thin sections and gradients in K and Fe(II). Using the gradient in Fe(II) and constraints based on cosmogenic age dates, we calculated a biotite oxidation reaction rate of 8.2 × 10⁻¹⁴ mol biotite m⁻² s⁻¹. Biotite oxidation was documented within the bedrock corestone by synchrotron X-ray microprobe fluorescence imaging and XANES. X-ray microprobe images of Fe(II) and Fe(III) at 2 μm resolution revealed that oxidized zones within individual biotite crystals are the first evidence of alteration of the otherwise unaltered corestone.Fluids entering along fractures lead to the dissolution of plagioclase within the rindlet zone. Within 7 cm surrounding the rindlet-saprolite interface, hornblende dissolves to completion at a rate of 6.3 × 10⁻¹³ mol hornblende m⁻² s⁻¹: the fastest reported rate of hornblende weathering in the field. This rate is consistent with laboratory-derived hornblende dissolution rates. By revealing the coupling of these mineral weathering reactions to fracturing and porosity formation we are able to describe the process by which the quartz diorite bedrock disaggregates and forms saprolite. In the corestone, biotite oxidation induces spheroidal fracturing, facilitating the influx of fluids that react with other minerals, dissolving plagioclase and chlorite, creating additional porosity, and eventually dissolving hornblende and precipitating secondary minerals. The thickness of the resultant saprolite is maintained at steady state by a positive feedback between the denudation rate and the weathering advance rate driven by the concentration of pore water O₂ at the bedrock-saprolite interface.     

Kinetics of biotite dissolution and Fe behavior under low O2 conditions and their implications for Precambrian weathering

Biotite dissolution experiments were carried out to better understand the dissolution kinetics and Fe behavior under low O₂ conditions, and to give an insight into the Precambrian weathering. Mineral dissolution with a continuous flow-through reactor was employed at 25 °C for up to 65 days varying partial pressure of atmospheric oxygen (PO₂), pH (6.86 and 3.01) and Fe content in mineral (1.06 and 0.11 mol of Fe per O₁₀(OH,F)₂ for biotite and phlogopite, respectively) independently for the examination of their effects on biotite dissolution. Low PO₂ conditions were achieved in a newly developed glove box (PO₂ ? 6 × 10⁻⁴ atm; referred to as anoxic conditions), which was compared to the present, ambient air conditions (0.2 atm of PO₂; oxic conditions). The biotite dissolution rate was slightly faster under anoxic conditions at pH 6.86 while it was not affected by PO₂ at pH 3.01. There was no direct effect of Fe content on dissolution rate at pH 6.86 while there was a small difference in dissolution rate between biotite and phlogopite at pH 3.01. The 1.5 order-of-magnitude faster release rate of Fe under anoxic conditions for biotite dissolution at pH 6.86 resulted from the difference in ratio of Fe³⁺ precipitates remaining in the reactor to Fe dissolved (about 60% and 100% under anoxic and oxic conditions, respectively), which is caused mainly by the difference in PO₂. The results infer that the Fe²⁺ and Fe³⁺ contents in the Paleoproterozoic paleosols, fossil weathering profiles, are reflected by atmospheric oxygen levels at the time of weathering.     

Does reactive surface area depend on grain size? Results from pH 3, 25 °C far-from-equilibrium flow-through dissolution experiments on anorthite and biotite

Laboratory determined mineral weathering rates need to be normalised to allow their extrapolation to natural systems. The principle normalisation terms used in the literature are mass, and geometric- and BET specific surface area (SSA). The purpose of this study was to determine how dissolution rates normalised to these terms vary with grain size. Different size fractions of anorthite and biotite ranging from 180-150 to 20-10 μm were dissolved in pH 3, HCl at 25 °C in flow through reactors under far from equilibrium conditions. Steady state dissolution rates after 5376 h (anorthite) and 4992 h (biotite) were calculated from Si concentrations and were normalised to initial- and final- mass and geometric-, geometric edge- (biotite), and BET SSA. For anorthite, rates normalised to initial- and final-BET SSA ranged from 0.33 to 2.77 × 10⁻¹⁰ mol_feldspar m⁻² s⁻¹, rates normalised to initial- and final-geometric SSA ranged from 5.74 to 8.88 × 10⁻¹⁰ mol_feldspar m⁻² s⁻¹ and rates normalised to initial- and final-mass ranged from 0.11 to 1.65 mol_feldspar g⁻¹ s⁻¹. For biotite, rates normalised to initial- and final-BET SSA ranged from 1.02 to 2.03 × 10⁻¹² mol_biotite m⁻² s⁻¹, rates normalised to initial- and final-geometric SSA ranged from 3.26 to 16.21 × 10⁻¹² mol_biotite m⁻² s⁻¹, rates normalised to initial- and final-geometric edge SSA ranged from 59.46 to 111.32 × 10⁻¹² mol_biotite m⁻² s⁻¹ and rates normalised to initial- and final-mass ranged from 0.81 to 6.93 × 10⁻¹² mol_biotite g⁻¹ s⁻¹. For all normalising terms rates varied significantly (p ? 0.05) with grain size. The normalising terms which gave least variation in dissolution rate between grain sizes for anorthite were initial BET SSA and initial- and final-geometric SSA. This is consistent with: (1) dissolution being dominated by the slower dissolving but area dominant non-etched surfaces of the grains and, (2) the walls of etch pits and other dissolution features being relatively unreactive. These steady state normalised dissolution rates are likely to be constant with time. Normalisation to final BET SSA did not give constant ratios across grain size due to a non-uniform distribution of dissolution features. After dissolution coarser grains had a greater density of dissolution features with BET-measurable but unreactive wall surface area than the finer grains. The normalising term which gave the least variation in dissolution rates between grain sizes for biotite was initial BET SSA. Initial- and final-geometric edge SSA and final BET SSA gave the next least varied rates. The basal surfaces dissolved sufficiently rapidly to influence bulk dissolution rate and prevent geometric edge SSA normalised dissolution rates showing the least variation. Simple modelling indicated that biotite grain edges dissolved 71-132 times faster than basal surfaces. In this experiment, initial BET SSA best integrated the different areas and reactivities of the edge and basal surfaces of biotite. Steady state dissolution rates are likely to vary with time as dissolution alters the ratio of edge to basal surface area. Therefore they would be more properly termed pseudo-steady state rates, only appearing constant because the time period over which they were measured (1512 h) was less than the time period over which they would change significantly.     

An atomic force microscopy study of calcite dissolution in saline solutions: The role of magnesium ions

In situ Atomic Force Microscopy, AFM, experiments have been carried out using calcite cleavage surfaces in contact with solutions of MgSO₄, MgCl₂, Na₂SO₄ and NaCl in order to attempt to understand the role of Mg²⁺ during calcite dissolution. Although previous work has indicated that magnesium inhibits calcite dissolution, quantitative AFM analyses show that despite the fact that Mg²⁺ inhibits etch pit spreading, it increases the density and depth of etch pits nucleated on calcite surfaces and, subsequently, the overall dissolution rates: i.e., from 10^−11.75 mol cm⁻² s⁻¹ (in deionized water) up to 10^−10.54 mol cm⁻² s⁻¹ (in 2.8 M MgSO₄). Such an effect is concentration-dependent and it is most evident in concentrated solutions ([Mg²⁺] >> 50 mM). These results show that common soluble salts (especially Mg sulfates) may play a critical role in the chemical weathering of carbonate rocks in nature as well as in the decay of carbonate stone in buildings and statuary.     

Iron isotope fractionation during proton- and ligand-promoted dissolution of primary phyllosilicates

We studied stable iron isotope fractionation during dissolution of a biotite and chlorite enriched mineral fraction from granite by HCl and 5 mM oxalic acid in a pH range of 4-5.9. Batch experiments covered a time period from 2 h to 100 days and were performed at initial potassium concentrations of 0, 0.5, and 5 mM to induce different levels of biotite exfoliation. All experiments were kept anoxic to investigate solely the dissolution step without the influence of oxidation and precipitation of secondary Fe oxyhydroxides. Oxalic acid increased the release of Fe by a factor of ∼15 compared with the HCl experiments. Addition of 0.5 mM K to initial solutions in proton-promoted dissolution decreased the release of Fe by 30-65% depending on the dissolution stage. In ligand-controlled dissolution, K reduced the Fe release only to a minor extent. All solutions of the early dissolution stages were enriched in light Fe isotopes by up to −1.4‰ in δ⁵⁶Fe compared with the isotopic composition of biotite and chlorite mineral separates, which we explained by a kinetic isotope effect. In proton-promoted dissolution, early released fractions of K-enriched experiments were significantly lighter (−0.7‰ to −0.9‰) than in the initially K-free experiments. The evolution of Fe isotope ratios in solution was modeled by a linear combination of kinetic isotope effects during two independent dissolution processes attacking different crystallographic sites. In ligand-controlled dissolution, K did not influence the kinetic isotope effect and the Fe isotope composition in solution in the late dissolution stages remained slightly lighter than the bulk composition of the biotite/chlorite enriched mineral fraction. This study demonstrates that the initial Fe weathering flux should be enriched in light Fe isotopes and that Fe isotope data in combination with dissolution kinetics and stoichiometry provide new insights into dissolution mechanisms.     

Silicate weathering in anoxic marine sediments

Two sediment cores retrieved at the northern slope of Sakhalin Island, Sea of Okhotsk, were analyzed for biogenic opal, organic carbon, carbonate, sulfur, major element concentrations, mineral contents, and dissolved substances including nutrients, sulfate, methane, major cations, humic substances, and total alkalinity. Down-core trends in mineral abundance suggest that plagioclase feldspars and other reactive silicate phases (olivine, pyroxene, volcanic ash) are transformed into smectite in the methanogenic sediment sections. The element ratios Na/Al, Mg/Al, and Ca/Al in the solid phase decrease with sediment depth indicating a loss of mobile cations with depth and producing a significant down-core increase in the chemical index of alteration. Pore waters separated from the sediment cores are highly enriched in dissolved magnesium, total alkalinity, humic substances, and boron. The high contents of dissolved organic carbon in the deeper methanogenic sediment sections (50-150 mg dm⁻³) may promote the dissolution of silicate phases through complexation of Al³⁺ and other structure-building cations. A non-steady state transport-reaction model was developed and applied to evaluate the down-core trends observed in the solid and dissolved phases. Dissolved Mg and total alkalinity were used to track the in-situ rates of marine silicate weathering since thermodynamic equilibrium calculations showed that these tracers are not affected by ion exchange processes with sediment surfaces. The modeling showed that silicate weathering is limited to the deeper methanogenic sediment section whereas reverse weathering was the dominant process in the overlying surface sediments. Depth-integrated rates of marine silicate weathering in methanogenic sediments derived from the model (81.4-99.2 mmol CO₂ m⁻² year⁻¹) are lower than the marine weathering rates calculated from the solid phase data (198-245 mmol CO₂ m⁻² year⁻¹) suggesting a decrease in marine weathering over time. The production of CO₂ through reverse weathering in surface sediments (4.22-15.0 mmol CO₂ m⁻² year⁻¹) is about one order of magnitude smaller than the weathering-induced CO₂ consumption in the underlying sediments. The evaluation of pore water data from other continental margin sites shows that silicate weathering is a common process in methanogenic sediments. The global rate of CO₂ consumption through marine silicate weathering estimated here as 5-20 Tmol CO₂ year⁻¹ is as high as the global rate of continental silicate weathering.     

Weathering and the mobility of phosphorus in the catchments and forefields of the Rhône and Oberaar glaciers, central Switzerland: Implications for the global phosphorus cycle on glacial-interglacial timescales

In this study we evaluate the dynamics of the biophile element phosphorus (P) in the catchment and proglacial areas of the Rhône and Oberaar glaciers (central Switzerland). We analysed erosion and dissolution rates of P-containing minerals in the subglacial environment by sampling water and suspended sediment in glacier outlets during three ablation and two accumulation seasons. We also quantified biogeochemical weathering rates of detrital P in proglacial sedimentary deposits using two chronosequences of samples of fresh, suspended, material obtained from the Oberaar and Rhône water outlets, Little-Ice-Age (LIA) moraines and Younger Dryas (YD) tills in each catchment. Subglacial P weathering is mainly a physical process and detrital P represents more than 99% of the precipitation-corrected total P denudation flux (234 and 540 kg km⁻² yr⁻¹ for the Rhône and Oberaar catchments, respectively). The calculated detrital P flux rates are three to almost five times higher than the world average flux. The precipitation-corrected soluble reactive P (SRP) flux corresponds to 1.88-1.99 kg km⁻² yr⁻¹ (Rhône) and 2.12-2.44 kg km⁻² yr⁻¹ (Oberaar), respectively. These fluxes are comparable to those of tropical rivers draining transport-limited, tectonically inactive weathering areas.In order to evaluate the efficiency of detrital P weathering in the Rhône and Oberaar proglacial areas, we systematically graded apatite grains extracted from the chronosequence in each catchment relative to weathering-induced changes in their surface morphologies (grades 1-4). Fresh apatite grains are heavily indented and dissolution rounded (grade 1). LIA grains from two 0-10 cm deep moraine samples show extensive dissolution etching, similar to surface grains from the YD profile (mean grades 2.7, 3.5 and 3.5, respectively). In these proglacial deposits, the weathering front deepens progressively as a function of time due to biocorrosion in the evolving acidic pedosphere, with mechanical indentations on grains acting as sites of preferential dissolution. We also measured iron-bound, organic and detrital P concentrations in the chronosequence and show that organic and iron-bound P has almost completely replaced detrital P in the top layers of the YD profiles. Detrital P weathering rates are calculated as 310 and 280 kg km⁻² yr⁻¹ for LIA moraines and 10 kg km⁻² yr⁻¹ for YD tills. During the first 300 years of glacial sediment exposure P dissolution rates are shown to be approximately 70 times higher than the mean global dissolved P flux from ice-free continents. After 11.6 kyr the flux is 2.5 times the global mean. These data strengthen the argument for substantial changes in the global dissolved P flux on glacial-interglacial timescales. A crude extrapolation from the data described here suggests that the global dissolved P flux may increase by 40-45% during the first few hundred years of a deglaciation phase.     

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.     

Major ion chemistry of the Yarlung Tsangpo-Brahmaputra river: Chemical weathering, erosion, and CO2 consumption in the southern Tibetan plateau and eastern syntaxis of the Himalaya

The Yarlung Tsangpo-Brahmaputra river drains a large portion of the Himalaya and southern Tibetan plateau, including the eastern Himalayan syntaxis, one of the most tectonically active regions on the globe. We measured the solute chemistry of 161 streams and major tributaries of the Tsangpo-Brahmaputra to examine the effect of tectonic, climatic, and geologic factors on chemical weathering rates. Specifically, we quantify chemical weathering fluxes and CO₂ consumption by silicate weathering in southern Tibet and the eastern syntaxis of the Himalaya, examine the major chemical weathering reactions in the tributaries of the Tsangpo-Brahmaputra, and determine the total weathering flux from carbonate and silicate weathering processes in this region. We show that high precipitation, rapid tectonic uplift, steep channel slopes, and high stream power generate high rates of chemical weathering in the eastern syntaxis. The total dissolved solids (TDS) flux from the this area is greater than 520 tons km⁻² yr⁻¹ and the silicate cation flux more than 34 tons km⁻² yr⁻¹. In total, chemical weathering in this area consumes 15.2 × 10⁵ mol CO₂ km⁻² yr⁻¹, which is twice the Brahmaputra average. These data show that 15-20% of the total CO₂ consumption by silicate weathering in the Brahmaputra catchment is derived from only 4% of the total land area of the basin. Hot springs and evaporite weathering provide significant contributions to dissolved Na⁺ and Cl⁻ fluxes throughout southern Tibet, comprising more than 50% of all Na⁺ in some stream systems. Carbonate weathering generates 80-90% of all dissolved Ca²⁺ and Mg²⁺ cations in much of the Yarlung Tsangpo catchment.     

Tree-mycorrhiza symbiosis accelerate mineral weathering: Evidences from nanometer-scale elemental fluxes at the hypha-mineral interface

In soils, mycorrhiza (microscopic fungal hypha) living in symbiosis with plant roots are the biological interface by which plants obtain, from rocks and organic matter, the nutrients necessary for their growth and maintenance. Despite their central role in soils, the mechanism and kinetics of mineral alteration by mycorrhiza are poorly constrained quantitatively. Here, we report in situ quantification of weathering rates from a mineral substrate, (0 0 1) basal plane of biotite, by a surface-bound hypha of Paxillus involutus, grown in association with the root system of a Scots pine, Pinus sylvestris. Four thin-sections were extracted by focused ion beam (FIB) milling along a single hypha grown over the biotite surface. Depth-profile of Si, O, K, Mg, Fe and Al concentrations were performed at the hypha-biotite interface by scanning transmission electron microscopy-energy dispersive X-ray spectroscopy (STEM-EDX). Large removals of K (50-65%), Mg (55-75%), Fe (80-85%) and Al (75-85%) were observed in the topmost 40 nm of biotite underneath the hypha while Si and O are preserved throughout the depth-profile. A quantitative model of alteration at the hypha-scale was developed based on solid-state diffusion fluxes of elements into the hypha and the break-down/mineralogical re-arrangement of biotite. A strong acidification was also observed with hypha bound to the biotite surface reaching pH < 4.6. When consistently compared with the abiotic biotite dissolution, we conclude that the surface-bound mycorrhiza accelerate the biotite alteration kinetics between pH 3.5 and 5.8 to ∼0.04 μmol biotite m⁻² h⁻¹. Our current work reaffirms that fungal mineral alteration is a process that combines our previously documented bio-mechanical forcing with the μm-scale acidification mediated by surface-bound hypha and a subsequent chemical element removal due to the fungal action. As such, our study presents a first kinetic framework for mycorrhizal alteration at the hypha-scale under close-to-natural experimental conditions.     

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.     

In situ investigation of dissolution of heavy metal containing mineral particles in an acidic forest soil

We report the application of an in situ method to obtain field dissolution rates of fine mineral particles in soils. Samples with different metal-containing mineral and slag particles (lead oxide, copper concentrate and copper slag) from the mining and smelting industry were buried in the topsoil of an acidic forest soil for up to 18 months. In addition we studied the dissolution of these particles in samples of the same soil, in a sand matrix and in acid solution under constant temperature and moisture conditions in the laboratory. Under field conditions the PbO particles dissolved quite rapidly (2.4 ± 0.7 × 10⁻¹⁰ mol Pb m⁻² s⁻¹), whereas the copper concentrate (<1 × 10⁻¹¹ mol Cu m⁻² s⁻¹) and the copper slag particles (4.3 ± 0.8 × 10⁻¹¹ mol Cu m⁻² s⁻¹) proved to be more resistant to weathering. In addition to qualitative information on dissolution features (SEM), the method yielded quantitative data on in situ dissolution rates. The dissolution rates followed the order: sand with acid percolation (pH 3.5; lab) < soil (lab) < soil (field) < acid solution (pH 3.5; lab). Dissolution rates in soil were found to be lower under laboratory than under field conditions. The faster field rates may in part be attributed to the higher biological activity in the field soil compared to the same soil in the laboratory.     

The major ion, δCa, δCa, and δMg geochemistry of granite weathering at pH = 1 and T = 25 °C: power-law processes and the relative reactivity of minerals

We dissolved Boulder Creek Granodiorite in a plug flow reactor for 5794 h at pH = 1 and T = 25 °C. The primary purpose of the experiment was to identify controls on dissolved δ^44/40Ca, δ^44/42Ca, and δ^26/24Mg values during granite weathering. Herein, we also examine the origin of Ca and Mg isotopic variability among minerals composing the Boulder Creek Granodiorite, and we constrain fundamental characteristics of granite weathering important for quantifying the elemental and isotopic geochemistry of the reactor output. Nine Ca-bearing minerals display an 8.80‰ range of δ^44/40Ca values and a 0.51‰ range of δ^44/42Ca values. Three Mg-bearing minerals display a 1.53‰ range of δ^26/24Mg values. These ranges expressed at the mineralogical scale are higher than the ranges thus far reported for bulk igneous rocks. Most of the δ^44/40Ca variability reflects ⁴⁰Ca enrichment in K-feldspar, and to a lesser extent, biotite, due to the radioactive decay of ⁴⁰K over the 1.7 Ga age of the rock, whereas the entire range of δ^44/42Ca values reflects mass-dependent isotope fractionation during igneous differentiation and crystallization. The range of δ^26/24Mg values may represent either fractionation during the chloritization of biotite or interaction of the Boulder Creek Granodiorite with Mg-rich metamorphic fluids having low δ^26/24Mg values.The elemental and isotopic composition of the reactor output varied substantially during the experiment. We synthesize the mineralogical and fluid data using coupled mass-conservation equations solved at non-steady-state. Model calculations reveal an intricate balance between increasing specific surface area and decreasing mineral concentrations. While surface area normalized dissolution rate constants were time-invariant, specific surface area increased as a power-law function of time through positive feedbacks between mechanical disaggregation, chemical dissolution, and mineral depletion. Variations in dissolved δ^44/40Ca, δ^44/42Ca, and δ^26/24Mg values reflect conservative mixing rather than fractionation. Apatite and calcite initially control δ^44/40Ca and δ^44/42Ca values, followed by biotite, titanite, epidote, hornblende, and plagioclase. The release of radiogenic ⁴⁰Ca clearly defines the period where biotite dissolution dominates. The brucite layer of chlorite initially controls δ^26/24Mg values, followed by biotite, the TOT layer of chlorite, and hornblende. Through direct isotopic tracking, these results demonstrate that trace minerals, such as apatite and calcite in the case of Ca and brucite in the case of Mg, dominate elemental release during the incipient stages of granite weathering. The results further show that biotite dissolution dominates the middle stages of granite weathering and that plagioclase dissolution only becomes important during relatively late stages. The Ca and Mg isotope variations associated with these stages are distinct and potentially resolvable in soil mineral weathering studies.     

Atmospheric CO2 consumption by chemical weathering in North America

CO₂ consumption by chemical weathering is an integral part of the boundless carbon cycle, whose spatial patterns and controlling factors on continental scale are still not fully understood. A dataset of 338 river catchments throughout North America was used to empirically identify predictors of bicarbonate fluxes by chemical weathering and interpret the underlying controlling factors. Detailed analysis of major ion ratios enables distinction of the contributions of silicate and carbonate weathering and thus quantifying CO₂ consumption. Extrapolation of the identified empirical model equations to North America allows the analysis of the spatial patterns of the CO₂ consumption by chemical weathering.Runoff, lithology and land cover were identified as the major predictors of the riverine bicarbonate fluxes and the associated CO₂ consumption. Other influence factors, e.g. temperature, could not be established in the models. Of the distinguished land cover classes, artificial surfaces, dominated by urban areas, increase bicarbonate fluxes most, followed by shrubs, grasslands, managed lands, and forests. The extrapolation results in an average specific bicarbonate flux of 0.3 Mmol km⁻² a⁻¹ by chemical weathering in North America, of which 64% originates from atmospheric CO₂, and 36% from carbonate mineral dissolution. Chemical weathering in North America thus consumes 50 Mt atmospheric CO₂-C per year. About half of that originates from 10% of the area of North America.The estimated strength of individual predictors differs from previous studies. This highlights the need for a globally representative set of regionally calibrated models of CO₂ consumption by chemical weathering, which apply very detailed spatial data to resolve the heterogeneity of earth surface processes.     

Iron isotope fractionation during leaching of granite and basalt by hydrochloric and oxalic acids

Transport of iron (Fe) within hydrothermal and soil environments involves the transferral into aqueous solutions by leaching of complex, polyminerallic rocks. Understanding the isotope fractionation mechanisms during this process is key for any application of the Fe-isotope system to biogeochemical studies. Here, we reacted biotite granite and tholeiite-basalt with 0.5 M hydrochloric acid and 5 mM oxalic acid solutions at ambient temperature. Solution aliquots were recovered over a seven-day period and analysed for major and trace element concentrations and Fe isotopic compositions. In all experiments, Fe initially released into solution was isotopically lighter, with Δ⁵⁶Fe_{solution-rock} as low as −1.80‰ in the granite-hydrochloric acid system. The oxalic acid experiments showed similar patterns but smaller fractionation. In all experiments, the Δ⁵⁶Fe_{solution-rock} reduced over time, which would be in line with the formation of a leached layer as proposed before [Brantley S. L., Liermann L. J., Guynn R. L., Anbar A., Icopini G. A., and Barling J. (2004) Fe isotopic fractionation during mineral dissolution with and without bacteria. Geochim. Cosmochim. Acta68(15), 3189-3204]. Granite and basalts reacting with hydrochloric acid reached apparent steady-state values of −0.60 ± 0.15‰ and −0.40 ± 0.20‰, respectively, whilst experimental values with oxalic acid were −1.0 ± 0.15‰ and −0.50 ± 0.15‰. During the granite experiments, alteration of biotite to chlorite, followed by dissolution of chlorite, were likely the dominant processes, whilst in the basalt experiments, dissolution of pigeonite was likely the principal source of Fe. Variations in pH during the hydrochloric acid experiments were minimal, remaining below 0.5 at all times. In oxalic acid solutions, the pH increased to over 4, leading likely to precipitation of secondary minerals and adsorption/co-precipitation of Fe onto mineral surfaces. These processes could contribute to the greater fractionation observed in the final stages of the oxalic acid experiments. Our results highlight the importance of mineralogy and fluid composition on the Fe-isotope systematics during weathering. The fractionation processes identified for granites and basalts are in line with those inferred from field observations in soils, sediments, groundwater and hydrothermal deposits and from laboratory studies of single-mineral leaching.     

Regolith mass balance inferred from combined mineralogical, geochemical and geophysical studies: Mule Hole gneissic watershed, South India

The aim of this study is to propose a method to assess the long-term chemical weathering mass balance for a regolith developed on a heterogeneous silicate substratum at the small experimental watershed scale by adopting a combined approach of geophysics, geochemistry and mineralogy. We initiated in 2003 a study of the steep climatic gradient and associated geomorphologic features of the edge of the rifted continental passive margin of the Karnataka Plateau, Peninsular India. In the transition sub-humid zone of this climatic gradient we have studied the pristine forested small watershed of Mule Hole (4.3 km²) mainly developed on gneissic substratum. Mineralogical, geochemical and geophysical investigations were carried out (i) in characteristic red soil profiles and (ii) in boreholes up to 60 m deep in order to take into account the effect of the weathering mantle roots. In addition, 12 Electrical Resistivity Tomography profiles (ERT), with an investigation depth of 30 m, were generated at the watershed scale to spatially characterize the information gathered in boreholes and soil profiles. The location of the ERT profiles is based on a previous electromagnetic survey, with an investigation depth of about 6 m. The soil cover thickness was inferred from the electromagnetic survey combined with a geological/pedological survey.Taking into account the parent rock heterogeneity, the degree of weathering of each of the regolith samples has been defined using both the mineralogical composition and the geochemical indices (Loss on Ignition, Weathering Index of Parker, Chemical Index of Alteration). Comparing these indices with electrical resistivity logs, it has been found that a value of 400 Ohm m delineates clearly the parent rocks and the weathered materials. Then the 12 inverted ERT profiles were constrained with this value after verifying the uncertainty due to the inversion procedure. Synthetic models based on the field data were used for this purpose. The estimated average regolith thickness at the watershed scale is 17.2 m, including 15.2 m of saprolite and 2 m of soil cover.Finally, using these estimations of the thicknesses, the long-term mass balance is calculated for the average gneiss-derived saprolite and red soil. In the saprolite, the open-system mass-transport function τ indicates that all the major elements except Ca are depleted. The chlorite and biotite crystals, the chief sources for Mg (95%), Fe (84%), Mn (86%) and K (57%, biotite only), are the first to undergo weathering and the oligoclase crystals are relatively intact within the saprolite with a loss of only 18%. The Ca accumulation can be attributed to the precipitation of CaCO₃ from the percolating solution due to the current and/or the paleoclimatic conditions. Overall, the most important losses occur for Si, Mg and Na with −286 × 10⁶ mol/ha (62% of the total mass loss), −67 × 10⁶ mol/ha (15% of the total mass loss) and −39 × 10⁶ mol/ha (9% of the total mass loss), respectively. Al, Fe and K account for 7%, 4% and 3% of the total mass loss, respectively. In the red soil profiles, the open-system mass-transport functions point out that all major elements except Mn are depleted. Most of the oligoclase crystals have broken down with a loss of 90%. The most important losses occur for Si, Na and Mg with −55 × 10⁶ mol/ha (47% of the total mass loss), −22 × 10⁶ mol/ha (19% of the total mass loss) and −16 × 10⁶ mol/ha (14% of the total mass loss), respectively. Ca, Al, K and Fe account for 8%, 6%, 4% and 2% of the total mass loss, respectively.Overall these findings confirm the immaturity of the saprolite at the watershed scale. The soil profiles are more evolved than saprolite but still contain primary minerals that can further undergo weathering and hence consume atmospheric CO₂.     

Mineral weathering and elemental transport during hillslope evolution at the Susquehanna/Shale Hills Critical Zone Observatory

Located in the uplands of the Valley and Ridge physiographic province of Pennsylvania, the Susquehanna/Shale Hills Critical Zone Observatory (SSHO) is a tectonically quiescent, first-order catchment developed on shales of the Silurian Rose Hill Formation. We used soil cores augered at the highest point of the watershed and along a subsurface water flowline on a planar hillslope to investigate mineral transformations and physical/chemical weathering fluxes. About 25 m of bedrock was also drilled to estimate parent composition. Depletion of carbonate at tens of meters of depth in bedrock may delineate a deep carbonate-weathering front. Overlying this, extending from ∼6 m below the bedrock-soil interface up into the soil, is the feldspar dissolution front. In the soils, depletion profiles for K, Mg, Si, Fe, and Al relative to the bedrock define the illite and chlorite reaction fronts. When combined with a cosmogenic nuclide-derived erosion rate on watershed sediments, these depletion profiles are consistent with dissolution rates that are several orders of magnitudes slower for chlorite (1-5 × 10⁻¹⁷ mol m⁻² s⁻¹) and illite (2-9 × 10⁻¹⁷ mol m⁻² s⁻¹) than observed in the laboratory. Mineral reactions result in formation of vermiculite, hydroxy-interlayered vermiculite, and minor kaolinite. During weathering, exchangeable divalent cations are replaced by Al as soil pH decreases.The losses of Mg and K in the soils occur largely as solute fluxes; in contrast, losses of Al and Fe are mostly as downslope transport of fine particles. Physical erosion of bulk soils also occurs: results from a steady-state model demonstrate that physical erosion accounts for about half of the total denudation at the ridgetop and midslope positions. Chemical weathering losses of Mg, Na, and K are higher in the upslope positions likely because of the higher degree of chemical undersaturation in porewaters. Chemical weathering slows down in the valley floor and Al and Si even show net accumulation. The simplest model for the hillslope that is consistent with all observations is a steady-state, clay weathering-limited system where soil production rates decrease with increasing soil thickness.     

Geochemical fluxes and weathering of volcanic terrains on high standing islands: Taranaki and Manawatu-Wanganui regions of New Zealand

Sediment fluxes from high standing oceanic islands (HSIs) such as New Zealand are some of the highest known [Milliman J. D. and Syvitski J. P. M. (1992) Geomorphic/tectonic control of sediment discharge to the ocean: the importance of small mountainous rivers. J. Geol.100, 525-544]. Recent geochemical work has suggested that along with their extremely high physical weathering yields, many New Zealand watersheds also have very high chemical weathering yields. In New Zealand, the magnitude of both the physical and chemical weathering yields is related to the lithology of the watershed. Most of the previous work on this topic has been undertaken in Southern Alps watersheds of schist and greywacke and in East Cape watersheds of semi-consolidated marine sediments and greywacke. We recently sampled North Island watersheds in the Taranaki and Manawatu-Wanganui regions which have been subjected to volcanism since the Miocene. We sampled watersheds that contain both volcanic and sedimentary rocks. A series of water and sediment samples was collected and analyzed for major, minor and trace elements. This was done to quantify the weathering intensities in the watersheds and to establish the relationship between physical and chemical weathering yields in volcanic lithologies. Our results reveal distinct chemical signatures for the different regions. Waters draining the Taranaki region volcanics are significantly enriched in K⁺, and depleted in Ca²⁺ and Sr²⁺ compared to waters draining the Manawatu-Wanganui region volcanics, which also traverse expanses of sedimentary siltstones and mudstones. The Ca²⁺ and Sr²⁺ depletions may reflect the relative absence of CaCO₃ in the Taranaki region watersheds. In addition, sediment samples from the Taranaki region show significant enrichment in Ti, Al, Ca, Fe, Mn, Mg, Ca, and P and depletion in Si and Rb compared to those of the Manawatu-Wanganui region. From total dissolved solids concentrations and mean annual water discharge, we calculate chemical weathering yields of 60-240 tons km⁻² a⁻¹. These weathering yields fall within the middle to upper range of those previously documented for the Southern Alps (93-480 tons km⁻² a⁻¹) and East Cape (62-400 tons km⁻² a⁻¹). Calculated silicate weathering yields of 12-33.6 tons km⁻² a⁻¹ and CO₂ consumption of 852-2390 × 10³ mol km⁻² a⁻¹ for the rivers draining the Taranaki volcanic region are higher than those previously reported for watersheds hosted in sedimentary and metamorphosed rock terrains on HSIs. CO₂ consumption is found to be within the range previously measured for the basaltic terrains of the Deccan Traps (580-2450 × 10³ mol km⁻² a⁻¹) and Réunion Island(1300-4400 × 10³ mol km⁻² a⁻¹). Our calculated chemical weathering yields demonstrate the importance of HSIs, particularly those with volcanic terrains, when considering global geochemical fluxes.     

Hydration of rhyolitic glass during weathering as characterized by IR microspectroscopy

The mechanism and rate of hydration of rhyolitic glass during weathering were studied. Doubly polished thin sections of two rhyolites with different duration of weathering (Ohsawa lava: 26,000 yr, Awanomikoto lava: 52,000 yr) were prepared. Optical microscope observation showed that altered layers had developed along the glass surfaces. IR spectral line profile analysis was conducted on the glass sections from the surface to the interior for a length of 250 μm and the contents of molecular H₂O (H₂O_m), OH species (OH) and total water (H₂O_t) were determined. The diffusion profile of H₂O_m in Ohsawa lava extends beyond the layer observed by optical microscope. The content of H₂O_m in the hydrated region is much higher than that of OH species. Thus, the reaction from H₂O_m to OH appears to be little and H₂O_m is the dominant water species moving into the glass during weathering. Based on the concentration profiles, the diffusion coefficients of H₂O_m(D_H2Om) and H₂O_t(D_H2Ot) were determined to be 2.8 × 10⁻¹⁰ and 3.4 × 10⁻¹⁰ μm² s⁻¹ for Ohsawa lava, and 5.2 × 10⁻¹¹ and 4.1 × 10⁻¹¹ μm² s⁻¹ for Awanomikoto lava, respectively. The obtained D_H2Om during weathering are more than 2-3 orders of magnitude larger than the diffusion coefficient at ∼20 °C that is extrapolated from the diffusivity data for >400 °C. This might suggest that the mechanism of water transport is different at weathering conditions and >400 °C.     

Chemical weathering in the Three Rivers region of Eastern Tibet

Three large rivers - the Chang Jiang (Yangtze), Mekong (Lancang Jiang) and Salween (Nu Jiang) - originate in eastern Tibet and run in close parallel over 300 km near the eastern Himalayan syntaxis. Seventy-four river water samples were collected mostly during the summer season from 1999 to 2004. Their major element compositions vary widely, with total dissolved solids (TDS) ranging from 31 to 3037 mg/l, reflecting the complex geologic makeup of the vast drainage basins. The major ion distribution of the main channel samples primarily reflects the weathering of carbonates. Evaporite dissolution prevails in the headwater samples of the Chang Jiang in the Tibetan Plateau interior, as evidenced by the high TDS (928 and 3037 mg/l) and the Na-Cl dominant major element composition. Local tributary samples of the Mekong and Salween, draining the Lincang Batholith and the Tengchong Volcano, show distinctive silicate weathering signatures. We used five reservoirs - rain, halite, sulfate, carbonate, and silicate - in a forward model to calculate the contribution from silicate weathering to the total dissolved load and to estimate the consumption rate of atmospheric CO₂ by silicate weathering. Carbonate weathering accounts for about 50% of the total cationic charge (TZ⁺) in the samples of the Mekong and the Salween exiting the Tibetan Plateau. In the “exit” sample of the Chang Jiang, 45% of TZ⁺ is from halite dissolution inherited from the extreme headwater tributaries in the interior of the plateau, and carbonates contribute only 26% to the TZ⁺. The net rate of CO₂ consumption by silicate weathering is (103-121) × 10³ mol km⁻² year⁻¹, lower than the rivers draining the Himalayan front. GIS-based analyses indicate that runoff and relief can explain 52% of the spread in the rate of atmospheric CO₂ drawdown by silicate weathering, but other climatic (temperature, precipitation, potential evapotranspiration) and geomorphic (elevation, slope) factors also show collinearity. Only qualitative conclusions can be drawn for the significance of lithology due to lack of digitized lithologic information. The effect of the peculiar drainage pattern due to tectonic forcing is not readily apparent in the major element composition or in increased chemical weathering rates. The ⁸⁷Sr/⁸⁶Sr ratios and the silicate weathering rates are in general lower in the Three Rivers than in the rivers draining the Himalayan front.