Determining mineral weathering rates based on solid and solute weathering gradients and velocities: application to biotite weathering in saprolites

Chemical weathering gradients are defined by the changes in the measured elemental concentrations in solids and pore waters with depth in soils and regoliths. An increase in the mineral weathering rate increases the change in these concentrations with depth while increases in the weathering velocity decrease the change. The solid-state weathering velocity is the rate at which the weathering front propagates through the regolith and the solute weathering velocity is equivalent to the rate of pore water infiltration. These relationships provide a unifying approach to calculating both solid and solute weathering rates from the respective ratios of the weathering velocities and gradients. Contemporary weathering rates based on solute residence times can be directly compared to long-term past weathering based on changes in regolith composition. Both rates incorporate identical parameters describing mineral abundance, stoichiometry, and surface area.

Weathering gradients were used to calculate biotite weathering rates in saprolitic regoliths in the Piedmont of Northern Georgia, USA and in Luquillo Mountains of Puerto Rico. Solid-state weathering gradients for Mg and K at Panola produced reaction rates of 3 to 6×10⁻¹⁷ mol m⁻² s⁻¹ for biotite. Faster weathering rates of 1.8 to 3.6×10⁻¹⁶ mol m⁻² s⁻¹ are calculated based on Mg and K pore water gradients in the Rio Icacos regolith. The relative rates are in agreement with a warmer and wetter tropical climate in Puerto Rico. Both natural rates are three to six orders of magnitude slower than reported experimental rates of biotite weathering.     

Variation in element release rate from different mineral size fractions from the B horizon of a granitic podzol

Far-from-equilibrium batch dissolution experiments were carried out on the 2000–500, 500–250, 250–53 and 53–2 μm size fractions of the mineral component of the B horizon of a granitic iron humus podzol after removal of organic matter and secondary precipitates. The different size fractions were mineralogically and chemically similar, the main minerals present being quartz, alkali and plagioclase feldspar, biotite and chlorite. Specific surface area increased with decreasing grain size. The measured element release rates decreased in the order 53–2>>>2000–500>500–250>250–53 μm. Surface area normalised element release rates from the 2000–500, 500–250 and 250–53 μm size fractions (0.6–77×10⁻¹⁴ mol/m²/s) were intermediate between literature reported surface area normalised dissolution rates for monomineralic powders of feldspar (0.1–0.01×10⁻¹⁴ mol/m²/s) and sheet silicates (100×10⁻¹⁴ mol/m²/s) dissolving under similar conditions. Element release rates from the 53–2 μm fraction (400–3000×10⁻¹⁴ mol/m²/s) were a factor of 4–30 larger than literature reported values for sheet silicates. The large element release rate of the 53–2 μm fraction means that, despite the small mass fraction of 53–2 μm sized particles present in the soil, dissolution of this fraction is the most important for element release into the soil. A theoretical model predicted similar (within a factor of <2) bulk element release rates for all the mineral powders if observed thicknesses of sheet silicate grains were used as input parameters. Decreasing element release rates with decreasing grain size were only predicted if the thickness of sheet silicates in the powders was held constant. A significantly larger release rate for the 53–2 μm fraction relative to the other size fractions was only predicted if either surface roughness was set several orders of magnitude higher for sheet silicates and several orders of magnitude lower for quartz and feldspars in the 53–2 μm fraction compared to the other size fractions or if the sheet silicate thickness input in the 53–2 μm fraction was set unrealistically low. It is therefore hypothesised that the reason for the unpredicted large release rate from the 52–3 μm size fraction is due to one or more of the following reasons: (1) the greater reactivity of the smaller particles due to surface free energy effects, (2) the lack of proportionality between the BET surface area used to normalise the release rates and the actual reactive surface area of the grains and, (3) the presence of traces quantities of reactive minerals which were undetected in the 53–2 μm fraction but were entirely absent in the coarser fractions.     

The dissolution kinetics of a granite and its minerals—Implications for comparison between laboratory and field dissolution rates

The present study compares the dissolution rates of plagioclase, microcline and biotite/chlorite from a bulk granite to the dissolution rates of the same minerals in mineral-rich fractions that were separated from the granite sample. The dissolution rate of plagioclase is enhanced with time as a result of exposure of its surface sites due to the removal of an iron oxide coating. Removal of the iron coating was slower in the experiment with the bulk granite than in the mineral-rich fractions due to a higher Fe concentration from biotite dissolution. As a result, the increase in plagioclase dissolution rate was initially slower in the experiment with the bulk granite. The measured steady state dissolution rates of both plagioclase (6.2 ± 1.2 × 10⁻¹¹ mol g⁻¹ s⁻¹) and microcline (1.6 ± 0.3 × 10⁻¹¹ mol g⁻¹ s⁻¹) were the same in experiments conducted with the plagioclase-rich fraction, the alkali feldspar-rich fraction and the bulk granite.Based on the observed release rates of the major elements, we suggest that the biotite/chlorite-rich fraction dissolved non-congruently under near-equilibrium conditions. In contrast, the biotite and chlorite within the bulk granite sample dissolved congruently under far from equilibrium conditions. These differences result from variations in the degree of saturation of the solutions with respect to both the dissolving biotite/chlorite and to nontronite, which probably was precipitating during dissolution of the biotite and chlorite-rich fraction. Following drying of the bulk granite, the dissolution rate of biotite was significantly enhanced, whereas the dissolution rate of plagioclase decreased.The presence of coatings, wetting and drying cycles and near equilibrium conditions all significantly affect mineral dissolution rates in the field in comparison to the dissolution rate of fully wetted clean minerals under far from equilibrium laboratory conditions. To bridge the gap between the field and the laboratory mineral dissolution rates, these effects on dissolution rate should be further studied.     

Chemistry, reaction mechanisms and micro-structures during retrograde metamorphism of gedrite-biotite-plagioclase bearing rocks from Bergslagen, south-central Sweden

The Proterozoic rhyolitic volcanics constituting the foot-wall rocks in the Stollberg ore-field, Bergslagen, south-central Sweden, locally contain gedrite altered to chlorite and serpentine, biotite altered to chlorite and plagioclase altered to epidote.

The intergrowths between the host gedrite and the chlorite/serpentine inclusions are oriented with the a^* of gedrite parallel to the c^* of serpentine and chlorite. The biotite has been altered to chlorite by brucitization of both the K-interlayer and talc-like layer. In both cases the net change in volume during chloritization is small.

The assumption that Al is conserved during alteration of gedrite and biotite agrees very well with the micro-structures and orientation relations observed by transmission electron microscopy. Normalizing the chlorite to 1.00 mole, the overall chemical change that took place during the retrograde metamorphism of the Stollberg rocks can be written as: 0.84Ged+0.14Bio+0.65Mg+4.76H₂O+0.42H=1.00Chl+0.57Alb+0.72Fe+0.01Na+0.12K+0.01Ti+0.05Mn+0.95H₄SiO₄ The reaction results in ca 9% increase in volume for the solid phases. Thus, a slightly acidic Mg-rich fluid started the reaction and, upon leaving the system, the metasomatic fluid was enriched in Na, Fe, K, and Si.     

In situ determination of long-term basaltic glass dissolution in the unsaturated zone

Maximum in situ weathering rates of basaltic glass measured at the El Malpais National Monument in New Mexico are on the order of 2–5×10⁻¹⁹ mol/cm² s. Rates were calculated from backscattered electron (BSE) imaging of weathered porosity and are equivalent to 1.7–5% of the surface per 1000 years. Weathering is independent of glass composition but appears to increase with flow elevation at El Malpais. Measured rates represent weathering over 3000 years and are substantially lower than glass dissolution rates measured in the laboratory over much shorter time spans. Basaltic glass is a close chemical analogue to glass hosts proposed for encapsulation of high-level nuclear wastes. Radionuclide release rates predicted from the basis of in situ field rates are substantially less than those predicted from short-term laboratory experiments.     

Strontium as a tracer of weathering processes in a silicate catchment polluted by acid atmospheric inputs, Strengbach, France

This paper determines the weathering and atmospheric contributions of Ca in surface water from a small spruce forested silicate catchment (N–E France) receiving acid atmospheric inputs. The bedrock is a granite with K-feldspar and albite as dominant phases. The calcium content in plagioclase is low and the Ca/Na ratio in surface water is high, reflecting other sources of calcium from those expected from the weathering of major mineral phases. The biotite content is low. Only traces of apatite were detected while no calcite was found in spite of a major hydrothermal event having affected the granite. The strontium isotopic ratio ⁸⁷Sr/⁸⁶Sr and Sr content was used as a tracer of weathering and was determined in minerals and bulk bedrock, open field precipitation, throughfall, soil solution, spring and stream water. The Sr isotopic ratio of the reacting weathering end-member was predicted by simulating the alteration of the granite minerals by incorporating strontium into the water–rock interaction kinetic code KINDIS. In the early stages of water–rock interaction, K-feldspar and biotite strongly influence the isotopic composition of the weathering solution whereas, the Na-rich plagioclase appears to be the main long-term reactive weathering end-member. Approximately 50% of dissolved Sr in streamwater are atmospherically derived. The ⁸⁷Sr/⁸⁶Sr ratios of exchangeable Sr in the fine fraction at 1-m depth from a soil profile indicate that the amount of exchangeable Sr seems essentially controlled by atmospheric inputs. The exception is the deep saprolite where weathering processes could supply the Sr (and Ca). Na-Plagioclase weathering obviously control the chemistry and the isotopic composition of surface waters. The weathering of trace mineral plays a secondary role, the exception is for apatite when plagioclase is absent. Our hydrochemical, mineralogical and isotopic investigations show that a major part of the strong Ca losses detected in catchment hydrochemical budgets that result from the neutralization of acid precipitation has an atmospheric origin. Consequently, in the long term, in such areas, the availability of such an exchangeable base cation might be strongly limited and surface waters consequently acidified.     

Changes in mineralogy of loess-paleosol sections across the Chinese Loess Plateau

Quantitative mineralogical analysis of bulk samples and single particles was carried out on three loess sections of different local climate settings on the Chinese Loess Plateau (CLP). Mineralogy, geochemistry, and single-particle petrography of loess and paleosols are relatively uniform over the CLP. However, in detail, there are mineralogical changes related to eolian process and chemical weathering. Particle-size sorting eastward from western sources led to an eastward increase of the total phyllosilicate contents enriched in fine illitic clay minerals. After deposition, detrital minerals susceptible to chemical weathering were sequentially altered in a progressive fashion with increasing precipitation in the order of calcite, dolomite, biotite, illite, chlorite, amphibole, and plagioclase. The weathering of biotite, chlorite, and illite resulted in a significant increase of expandable phyllosilicate contents. The sequential weathering of the minerals is reflected chemically in the decrease of Na and Mg and the increase of iron oxidation. Mineralogy of the Chinese loess at individual sites reflects the effects of size fractionation during eolian transportation and progressive sequential weathering along the climatic gradient, and it is essential to consider both effects when using mineralogical and dependent chemical data in the paleoclimatic reconstruction of the CLP.     

X射线粉晶衍射仪在山东蒙阴金伯利岩蚀变矿物鉴定中的应用

山东蒙阴金伯利岩组成矿物以蚀变矿物为主,X射线粉晶衍射仪鉴定结果显示无矿金伯利岩矿物组分为方解石、白云石、石英、钙锆钛矿,标志性矿物为白云石和钙锆钛矿;贫矿金伯利岩矿物组分为蛇纹石、方解石、钙铝榴石、磁铁矿和金云母,标志性矿物为钙铝榴石;富矿金伯利岩矿物组分为蛇纹石、方解石、绿泥石、磷灰石、磁铁矿和金云母,标志性矿物为绿泥石和磷灰石。采用X射线粉晶衍射仪鉴定金伯利岩蚀变矿物组合,寻找蚀变矿物组分变化与金伯利岩含矿性的关系,利用标志性的蚀变矿物判断金伯利岩无矿、贫矿还是富矿,是非常有意义的。     

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.     

Weathering of the New Albany Shale, Kentucky, USA: I. Weathering zones defined by mineralogy and major-element composition

Comprehensive understanding of chemical and mineralogical changes induced by weathering is valuable information when considering the supply of nutrients and toxic elements from rocks. Here minerals that release and fix major elements during progressive weathering of a bed of Devonian New Albany Shale in eastern Kentucky are documented. Samples were collected from unweathered core (parent shale) and across an outcrop excavated into a hillside 40 year prior to sampling. Quantitative X-ray diffraction mineralogical data record progressive shale alteration across the outcrop. Mineral compositional changes reflect subtle alteration processes such as incongruent dissolution and cation exchange. Altered primary minerals include K-feldspars, plagioclase, calcite, pyrite, and chlorite. Secondary minerals include jarosite, gypsum, goethite, amorphous Fe(III) oxides and Fe(II)-Al sulfate salt (efflorescence). The mineralogy in weathered shale defines four weathered intervals on the outcrop—Zones A–C and soil. Alteration of the weakly weathered shale (Zone A) is attributed to the 40-a exposure of the shale. In this zone, pyrite oxidization produces acid that dissolves calcite and attacks chlorite, forming gypsum, jarosite, and minor efflorescent salt. The pre-excavation, active weathering front (Zone B) is where complete pyrite oxidation and alteration of feldspar and organic matter result in increased permeability. Acidic weathering solutions seep through the permeable shale and evaporate on the surface forming abundant efflorescent salt, jarosite and minor goethite. Intensely weathered shale (Zone C) is depleted in feldspars, chlorite, gypsum, jarosite and efflorescent salts, but has retained much of its primary quartz, illite and illite–smectite. Goethite and amorphous FE(III) oxides increase due to hydrolysis of jarosite. Enhanced permeability in this zone is due to a 14% loss of the original mass in parent shale. Denudation rates suggest that characteristics of Zone C were acquired over 1 Ma. Compositional differences between soil and Zone C are largely attributed to illuvial processes, formation of additional Fe(III) oxides and incorporation of modern organic matter.     

A review and analysis of silicate mineral dissolution experiments in natural silicate melts

We present a database and a graphical analysis of published experimental results for dissolution rates of olivine, quartz plagioclase, clinopyroxene, orthopyroxene, spinel, and garnet in basaltic and andesitic melts covering a range of experimental temperatures (1100–1500°C) and pressures (10⁵ Pa-3.0 GPa). The published datasets of Donaldson (1985, 1990) and Brearly and Scarfe (1986) are the most complete. Experimental dissolution rates from all datasets are recalculated and normalized to a constant oxygen basis to allow for direct comparison of dissolution rates between different minerals. Dissolution rates (ν) range from 5·10⁻¹⁰ oxygen equivalent moles (o.e.m.) cm⁻² s⁻¹ for olivine in a basaltic melt to 1.3·10⁻⁵ o.e.m. cm⁻² s⁻¹ for garnet in a basaltic melt. Values of ln ν are Arthenian for the experiments examined and activation energies range from 118 to 1800 kJ/o.e.m. for quartz and clinopyroxene, respectively.

The relationship between calculated A/RT for the dissolution reactions, where A is the thermodynamic potential affinity, and values of ν is linear for olivine, plagioclase, and quartz. We interpret this as strong evidence in support of using calculated A as a predictor of ν for, at least, superliquidus melt conditions.     

方解石和钾长石在模拟蚯蚓肠液中的初始溶解动力学机理及意义

蚯蚓肠道内小分子有机酸与摄入的土壤矿物相互作用,加速矿物溶解。摄入的土壤在蚯蚓肠道内平均停留时间约为12 h,不足以使土壤矿物产生显著的溶解特征,因此这一过程难以在蚯蚓体内进行评估。本研究通过体外实验控制pH值和有机酸浓度,模拟蚯蚓肠道中有机酸对土壤中常见矿物的溶解反应,探讨了方解石和钾长石在蚯蚓肠道环境中的初始溶解动力学。研究发现,矿物在混合有机酸中的溶解速率比在纯水中高一个数量级,说明有机配体和质子促进了矿物溶解。溶解速率及粒度分析表明,方解石(CaCO₃)溶解速率不受溶解过程中粒度变化的影响,而钾长石(KAlSi₃O₈)粒度在溶解期间未出现显著变化。在此基础上,采用初始速率法模拟了钾长石的初始溶解动力学,计算得出的溶解速率表明钾长石在溶解初期主要为表面K~+的释放。使用缩核模型(shrink core model)和Hixson-Crowell模型对方解石溶解过程进行动力学解析,发现方解石的溶解主要受溶液中反应物内扩散的速率影响。这定量描述了两种矿物在有机酸溶液和纯水中的溶解差异。现有研究表明,有机配体和质子协同促...     

X射线粉晶衍射仪在辽宁瓦房店金伯利岩蚀变矿物鉴定中的应用

瓦房店金伯利岩热液蚀变强烈,原岩矿物组分几乎蚀变殆尽,显微镜下对蚀变矿物鉴定相当困难.利用X射线粉晶衍射技术对蚀变金伯利岩物相进行系统检测,结果显示：42号岩管金伯利岩主要矿物为蛇纹石、金云母和滑石,有少量方解石、锐钛矿、磷灰石、石英、钛铁矿、钙钛矿、榍石、磁铁矿和绿泥石;石灰窑1号无矿金伯利岩岩管主要矿物为蛇纹石、金云母和白云石,有少量方解石、锐钛矿、磷灰石、滑石、磁铁矿和绿泥石;9号无矿金伯利岩岩脉主要矿物为方解石和石英,有少量绿泥石和重晶石;51号贫矿金伯利岩岩管主要矿物为蛇纹石和金云母,方解石化作用不均匀,白云石化作用普遍,有少量锐钛矿、滑石、磁铁矿、绿泥石、磷灰石、钛铁矿、石英;30号贫矿岩管样品风化严重,主要矿物为蒙脱石,有少量方解石、滑石、蛇纹石、榍石、磷灰石.实践证明,采用X射线粉晶衍射仪鉴定金伯利岩蚀变矿物组合是一种非常可行的技术手段.     

Chemical mass balance of calcrete genesis on the Toledo granite (Spain)

The chemical mass balance of calcrete genesis is studied on a typical sequence developed in granite, in the Toledo mountains, Central Spain.

Field evidence and petrographic observations indicate that the texture and the bulk volume of the parent rock are strictly preserved all along the studied calcrete profile.

Microscopic observations indicate that the calcitization process starts within the saprolite, superimposed on the usual mechanisms of granite weathering: the fresh rock is first weathered to secondary clays, mainly smectites, which are then pseudomorphically replaced by calcite. Based on this evidence, chemical mass transfers are calculated, assuming iso-volume transformation from the parent rock to the calcrete.

The mass balance results show the increasing loss of matter due to weathering of the primary phases, from the saprolite towards the calcrete layers higher in the sequence. Zr, Ti or Th, which are classically considered as immobile during weathering, are also depleted along the profile, especially in the calcrete layer. This results from the prevailing highly alkaline conditions, which could account for the simultaneous precipitation of CaCO₃ and silicate dissolution.

The calculated budget suggests that the elements exported from the weathering profile are provided dominantly by the weathering of plagioclase and biotite. We calculate that 8–42% of the original Ca remains in granitic relics, while only 15% of the authigenic Ca released by weathering is reincorporated in the calcite. This suggests that 373 kg/m² of calcium (i.e., three times the original amount) is imported into the calcrete from allochtonous sources, probably due to aeolian transport from distant limestone formations.     

Lead and strontium isotopes as monitors of experimental granitoid mineral dissolution

Flow-through dissolution experiments were carried out on crushed granitoid rock (the Elat Granite) and three mineral separates (plagioclase, perthite, and biotite + chlorite) from this rock at pH 1 and 25°C. Major element concentrations were combined with Pb and Sr isotopic analyses of starting materials and output solutions and together enabled us to elucidate several important mechanisms related to granitoid rock weathering. We observed an initial stage of rock dissolution (<200 hours of reaction) that was characterized by elemental release from traces of calcite and/or apatite and to a lesser extent from the interlayer sites of biotite. Dissolution in the interval of 200 to 400 h was dominated by the release of elements from the interlayer sites of biotite, and at 400 to 1000 h of reaction the chemistry of output solutions was dominated by the release of elements from tetrahedral and octahedral sites of biotite as well as from plagioclase. After 1000 h, the dissolution of plagioclase, and to a lesser extent biotite, dominated the composition of elements released by the rock. We demonstrate that Pb and Sr isotope ratios in the output solutions can be used to identify each of these stages of dissolution. By comparing our experimental results on the release of Pb and Sr isotopes with field measurements of Pb and Sr isotopes in soil chronosequences from the Wind River and the Sierra Nevada Mountains (USA), we are able to show that similar isotopic patterns appear in both the pH 1 experiments and in soils formed under natural conditions at higher pH. By combining these experimental results with previous field studies, we are able to estimate the duration of most of these stages of granitoid weathering under natural conditions in temperate climates. In soils older than a few hundred years and younger than 10,000 yr the release of elements from interlayer sites of biotite controls the weathering flux. Soils between 10,000 and 100,000 yr old are dominated by biotite and plagioclase weathering, with biotite weathering controlling the first part of this period and plagioclase dominating the later part. After more than 100,000 yr, plagioclase, and to a lesser degree biotite, dominate the weathering flux within these granitoid soils.     

An experimental study of calcite dissolution rates at acidic conditions and 25 °C in the presence of NaPO3 and MgCl2

Dissolution rates of single calcite crystals were determined from sample weight loss using free-drift rotating disk techniques. Experiments were performed at 25 °C in aqueous HCl solutions over the bulk solution pH range −1 to 3 and in the presence of trace concentrations of aqueous NaPO₃ and MgCl₂. These salts were chosen for this study because aqueous magnesium and phosphate are known to strongly inhibit calcite dissolution at neutral to basic pH. Reactive solutions were undersaturated with respect to possible secondary phases. Neither an inhibition or enhancement of calcite dissolution rates was observed in the presence of aqueous MgCl₂ at pH 1 and 3. The presence of trace quantities of NaPO₃, which dissociates in solution to Na⁺ and H₂PO₄⁻, decreased the overall calcite dissolution rate at pH≤2. This contrasting behavior could be attributed to the different adsorption behavior of these dissolved species. As calcite surfaces are positively charged in acidic solutions, aqueous Mg²⁺ may not adsorb, whereas aqueous phosphate, present as either the anion H₂PO₄⁻ or the neutral species H₃PO₄⁰, readily adsorbs on calcite surfaces leading to significant dissolution inhibition.     

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.     

Episyenite formation in the Toki granite,central Japan

Episyenite is a quartz-depleted vuggy rock resulting from hydrothermal alteration of granitic rocks. This is the first report of its existence in an island arc, which is identified in a deep drill core of the Toki Cretaceous granite distributed in central Japan. In order to understand the petrographical features of the episyenite, neutron porosity measurement, geochemical analysis, microscopic observation, and X-ray computed tomography scanning were carried out. The results show remarkably high porosity (35.4 %) due to interconnecting vugs and the removal of quartz, plagioclase, and biotite. The Rb–Sr isotopic results and the paragenetic sequence of secondary minerals in the vugs suggest that the hydrothermal alteration process can be divided into an episyenitization stage and a later hydrothermal stage. At the episyenitization stage (70.6 ± 3.1 Ma) ca. 6 million years after the emplacement of the unaltered granite (76.3 ± 1.5 Ma), dissolution of quartz, biotite, and plagioclase occurred and was followed by the precipitation of albite, vermicular chlorite, and platy calcite. The episyenitization is considered as a local alteration of the Toki granite in an isotopically closed system. At the later hydrothermal stage, illite and secondary quartz precipitated from circulating meteoric-derived water in the dissolution vugs. Superimposing alteration at the later hydrothermal stage is limited, which results in the preservation of the episyenite in an almost primitive condition.     

长江干流水化学成因与风化过程CO2消耗通量解析

长江流域面积巨大,岩性多变,加之三峡大坝等重大水利工程的影响,干流河水的水化学成因存在较大争议。此外,以往研究中流域矿物风化过程的碳汇通量估算一般基于阳离子来源分析,但该算法通常涉及多种矿物端元的参数选取,结果具有不确定性。本次研究对长江干流水化学的时空演变进行了整体分析,并基于上游河水样品HCO₃~-含量的校正与计算,提出了一种计算矿物风化过程碳汇通量的新方法。研究结果表明,蒸发盐溶解、循环盐作用、矿物风化及硫酸盐溶解是控制长江干流河水离子组成的主要水文地球化学作用,而人类活动主要影响了离海距离3 000 km以内河水NO₃~-含量;长江上游干流硅酸盐风化消耗CO₂速率为1.16×10~5 mol/(km~2·a),碳酸盐风化消耗CO₂速率为4.75×10~5 mol/(km~2·a)。本研究有助于加深对长江干流主要水文地球化学作用的认识,丰富和完善碳循环研究理论。     

Estimation of reactive mineral surface area during water-rock interaction using fluid chemical data

Mineral dissolution and precipitation reactions actively participate to control fluid chemistry during water-rock interaction. However, it is difficult to estimate and normalize bulk reaction rates if the mineral surface area effectively participating in the reactions is unknown. In this study, we evaluated the changing of the reactive mineral surface area during the interaction between CO₂-rich fluids and albitite rock reacting under flow-through conditions. Our methodology, adopting an inverse modelling approach, is based on the measured chemical fluid composition as raw data. We estimated the rates of dissolution and the reactive surface areas of the different minerals by reconstructing the chemical evolution of the interacting fluids. This was done by a reaction process schema that was defined by a fractional degree of advance of the irreversible mass-transfer process and by attaining the continuum limit during the water-rock interaction. Calculations were carried out for albite, microcline, biotite and calcite assuming that the ion activity of dissolved silica and aluminium ions was limited by the equilibrium with quartz and kaolinite.We found that the absolute dissolution rate of albite, microcline, biotite and calcite remains essentially constant as a function of time, and the calcite dissolution rate is orders of magnitude higher than silicate minerals. On the contrary, the reactive surface area of the parent minerals varied by more than two orders of magnitude during the observed reaction time, especially for albite. We propose that the reactive surface area depends mainly on the stability of the secondary mineral coating that may passivate the effective reactive surface area of the parent minerals.