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1.
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.  相似文献   

2.
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.  相似文献   

3.
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 molfeldspar m−2 s−1, rates normalised to initial- and final-geometric SSA ranged from 5.74 to 8.88 × 10−10 molfeldspar m−2 s−1 and rates normalised to initial- and final-mass ranged from 0.11 to 1.65 molfeldspar g−1 s−1. For biotite, rates normalised to initial- and final-BET SSA ranged from 1.02 to 2.03 × 10−12 molbiotite m−2 s−1, rates normalised to initial- and final-geometric SSA ranged from 3.26 to 16.21 × 10−12 molbiotite m−2 s−1, rates normalised to initial- and final-geometric edge SSA ranged from 59.46 to 111.32 × 10−12 molbiotite m−2 s−1 and rates normalised to initial- and final-mass ranged from 0.81 to 6.93 × 10−12 molbiotite 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.  相似文献   

4.
The dissolution of chlorite with intermediate Fe-content was studied macroscopically via mixed flow experiments as well as microscopically via atomic force microscopy (AFM). BET surface area normalized steady state dissolution rates at 25 °C for pH 2 to 5 vary between 10−12 and 10−13 mol/m2.s. The order of the dissolution reaction with respect to protons was calculated to be about 0.29. For pH 2 to 4, chlorite was found to dissolve non-stoichiometrically, with a preferred release of the octahedrally coordinated cations. The additional release of octahedrally coordinated cations may be due to the transformation of chlorite to interstratified chlorite/vermiculite from the grain edges inward.In-situ atomic force microscopy performed on the basal surfaces of a chlorite sample, which has been preconditioned at pH 2 for several months, indicated a defect controlled dissolution mechanism. Molecular steps with height differences which correspond to the different subunits of chlorite, e.g. TOT sheet and brucite like layer, originated at surface defects such or compositional inhomogenities or cracks, which may be due to the deformation history of the chlorite sample. In contrast to other sheet silicates, at pH 2 nanoscale etch pits occur on the chlorite basal surfaces within flat terraces terminated by a TOT-sheet as well as within the brucite like layer. The chlorite basal surface dissolves layer by layer, because most of the surface defects are only expressed through single TOT or brucite-like layers. The defect controlled dissolution mechanism favours dissolution of molecular steps on the basal surfaces compared to dissolution of the grain edges. At pH 2 the dissolution of the chlorite basal surface is dominated by the retreat of 14 Å steps, representing one chlorite unit cell.The macroscopic and microscopic chlorite dissolution rates can be linked via the reactive surface area as identified by AFM. The reactive surface area with respect to dissolution consists of only 0.2% of the BET-surface area. A dissolution rate of 2.5 × 10−9 mol/m2s was calculated from macroscopic and microscopic dissolution experiments at pH 2, when normalized to the reactive surface area.  相似文献   

5.
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 δ44/40Ca, δ44/42Ca, and δ26/24Mg 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 δ44/40Ca values and a 0.51‰ range of δ44/42Ca values. Three Mg-bearing minerals display a 1.53‰ range of δ26/24Mg values. These ranges expressed at the mineralogical scale are higher than the ranges thus far reported for bulk igneous rocks. Most of the δ44/40Ca 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 δ44/42Ca values reflects mass-dependent isotope fractionation during igneous differentiation and crystallization. The range of δ26/24Mg values may represent either fractionation during the chloritization of biotite or interaction of the Boulder Creek Granodiorite with Mg-rich metamorphic fluids having low δ26/24Mg 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 δ44/40Ca, δ44/42Ca, and δ26/24Mg values reflect conservative mixing rather than fractionation. Apatite and calcite initially control δ44/40Ca and δ44/42Ca 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 δ26/24Mg 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.  相似文献   

6.
In situ feldspar dissolution rates in an aquifer   总被引：1，自引：0，他引：1  
In situ silicate dissolution rates within the saturated Navajo sandstone, at Black Mesa, Arizona were determined from elemental fluxes in the aquifer. The mass transfer between groundwater and mineral matrix along flow paths was calculated from inverse mass balance modeling. The reaction time is bound by 14C-based travel time. BET surface areas were measured with N2 gas adsorption. Dissolution rates for K-feldspar and plagioclase are 10−19 and 10−16 mol (feldspar) m−2 s−1, respectively, which are ∼105 times slower than laboratory experiment-derived rates under similar pH and temperature but at far from equilibrium conditions. The rates obtained in this study are consistent with the slower field rates found in numerous watershed and soil profile studies. However, these rates are from saturated aquifers, overcoming some concerns on estimated rates from unsaturated systems. The Navajo sandstone is a quartz-sandstone with a relatively simple and well-studied hydrogeology, groundwater geochemistry, and lithology, a large number of groundwater analyses and 14C groundwater ages, groundwater residence times up to ∼37 ky, groundwater pH from ∼8 to 10, and temperature from ∼15 to 35°C.  相似文献   

7.
酸性岩的变质相   总被引：1，自引：0，他引：1       下载免费PDF全文
张翊钧 《地球学报》1988,10(1):105-115
在沸石相变质条件下,花岗岩里浊沸石交代了斜长石和石英,在酸性火山岩里产生明矾石、埃洛石或高岭石。经受绿纤石-葡萄石相变质的花岗岩,其中黑云母变为钙铝榴石、帘石、绿纤石和葡萄石集合体,同时斜长石发生绢云母化。绿片岩相内酸性岩的浅色矿物有石英、微斜长石、钠长石和绿帘石,暗色矿物有绿泥石和黑云母。在角闪岩相变质的酸性岩中,开始出现中、基性斜长石,其中暗色矿物黑云母的镁铁比值要大于角闪石的镁铁比值。经受麻粒岩相变质后,紫苏花岗岩的矿物组成没有变化,但有铀、钍和钾的迁出。  相似文献   

8.
A comparison of published calcite dissolution rates measured far from equilibrium at a pH of ∼ 6 and above shows well over an order of magnitude in variation. Recently published AFM step velocities extend this range further still. In an effort to understand the source of this variation, and to provide additional constraint from a new analytical approach, we have measured dissolution rates by vertical scanning interferometry. In areas of the calcite cleavage surface dominated by etch pits, our measured dissolution rate is 10−10.95 mol/cm2/s (PCO2 10−3.41 atm, pH 8.82), 5 to ∼100 times slower than published rates derived from bulk powder experiments, although similar to rates derived from AFM step velocities. On cleavage surfaces free of local etch pit development, dissolution is limited by a slow, “global” rate (10−11.68 mol/cm2/s). Although these differences confirm the importance of etch pit (defect) distribution as a controlling mechanism in calcite dissolution, they also suggest that “bulk” calcite dissolution rates observed in powder experiments may derive substantial enhancement from grain boundaries having high step and kink density. We also observed significant rate inhibition by introduction of dissolved manganese. At 2.0 μM Mn, the rate diminished to 10−12.4 mol/cm2/s, and the well formed rhombic etch pits that characterized dissolution in pure solution were absent. These results are in good agreement with the pattern of manganese inhibition in published AFM step velocities, assuming a step density on smooth terraces of ∼9 μm−1.  相似文献   

9.
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.  相似文献   

10.
Two distinct series of Variscan granitic rocks have been distinguished in the Gravanho-Gouveia area of Portugal, based on field work, variation diagrams for major and trace elements, rare earth patterns and δ18O versus total FeO diagram of rocks, anorthite content of plagioclase, BaO and P2O5 contents of feldspars and AlVI versus Fe2+ diagram for magmatic muscovite. One series consists of a late-orogenic porphyritic biotite > muscovite granite (G1), less evolved beryl-columbite pegmatites and more evolved beryl-columbite pegmatites showing gradational contacts. The other series consists of post-orogenic porphyritic muscovite > biotite granodiorite to granite (G2), slightly porphyritic muscovite > biotite granite (G3) and lepidolite pegmatites. In each series, pegmatites are derived from the parent granite magma by fractional crystallization of quartz, plagioclase, K-feldspar, biotite and ilmenite. Some metasomatic effects occur like muscovite replacing feldspars, chlorite in pegmatites of the first series and a late muscovite in pegmatites of the second series, probably due to hydrothermal fluids. The lepidolite pegmatites contain cassiterite and two generations of rutile. The first magmatic generation consists of homogeneous crystals and the second generation occurs as heterogeneous zoned crystals derived from hydrothermal fluids. The beryl-columbite pegmatites and lepidolite pegmatites also contain the first magmatic generation and the late hydrothermal generation of zoned columbite-group minerals. More evolved beryl-columbite pegmatites were converted into episyenite by intense hydrothermal alteration and regional circulation of fluids in the granitic rocks.  相似文献   

11.
Bulk dissolution rates for sediment from ODP Site 984A in the North Atlantic are determined using the 234U/238U activity ratios of pore water, bulk sediment, and leachates. Site 984A is one of only several sites where closely spaced pore water samples were obtained from the upper 60 meters of the core; the sedimentation rate is high (11-15 cm/ka), hence the sediments in the upper 60 meters are less than 500 ka old. The sediment is clayey silt and composed mostly of detritus derived from Iceland with a significant component of biogenic carbonate (up to 30%).The pore water 234U/238U activity ratios are higher than seawater values, in the range of 1.2 to 1.6, while the bulk sediment 234U/238U activity ratios are close to 1.0. The 234U/238U of the pore water reflects a balance between the mineral dissolution rate and the supply rate of excess 234U to the pore fluid by α-recoil injection of 234Th. The fraction of 238U decays that result in α-recoil injection of 234U to pore fluid is estimated to be 0.10 to 0.20 based on the 234U/238U of insoluble residue fractions. The calculated bulk dissolution rates, in units of g/g/yr are in the range of 4 × 10−7 to 2 × 10−6 yr−1. There is significant down-hole variability in pore water 234U/238U activity ratios (and hence dissolution rates) on a scale of ca. 10 m. The inferred bulk dissolution rate constants are 100 to 104 times slower than laboratory-determined rates, 100 times faster than rates inferred for older sediments based on Sr isotopes, and similar to weathering rates determined for terrestrial soils of similar age. The results of this study suggest that U isotopes can be used to measure in situ dissolution rates in fine-grained clastic materials.The rate estimates for sediments from ODP Site 984 confirm the strong dependence of reactivity on the age of the solid material: the bulk dissolution rate (Rd) of soils and deep-sea sediments can be approximately described by the expression Rd ≈ 0.1 Age−1 for ages spanning 1000 to 5 × 108 yr. The age of the material, which encompasses the grain size, surface area, and other chemical factors that contribute to the rate of dissolution, appears to be a much stronger determinant of dissolution rate than any single physical or chemical property of the system.  相似文献   

12.
The long-term stability of biogenic uraninite with respect to oxidative dissolution is pivotal to the success of in situ bioreduction strategies for the subsurface remediation of uranium legacies. Batch and flow-through dissolution experiments were conducted along with spectroscopic analyses to compare biogenic uraninite nanoparticles obtained from Shewanella oneidensis MR-1 and chemogenic UO2.00 with respect to their equilibrium solubility, dissolution mechanisms, and dissolution kinetics in water of varied oxygen and carbonate concentrations. Both materials exhibited a similar intrinsic solubility of ∼10−8 M under reducing conditions. The two materials had comparable dissolution rates under anoxic as well as oxidizing conditions, consistent with structural bulk homology of biogenic and stoichiometric uraninite. Carbonate reversibly promoted uraninite dissolution under both moderately oxidizing and reducing conditions, and the biogenic material yielded higher surface area-normalized dissolution rates than the chemogenic. This difference is in accordance with the higher proportion of U(V) detected on the biogenic uraninite surface by means of X-ray photoelectron spectroscopy. Reasonable sources of a stable U(V)-bearing intermediate phase are discussed. The observed increase of the dissolution rates can be explained by carbonate complexation of U(V) facilitating the detachment of U(V) from the uraninite surface. The fraction of surface-associated U(VI) increased with dissolved oxygen concentration. Simultaneously, X-ray absorption spectra showed conversion of the bulk from UO2.0 to UO2+x. In equilibrium with air, combined spectroscopic results support the formation of a near-surface layer of approximate composition UO2.25 (U4O9) coated by an outer layer of U(VI). This result is in accordance with flow-through dissolution experiments that indicate control of the dissolution rate of surface-oxidized uraninite by the solubility of metaschoepite under the tested conditions. Although U(V) has been observed in electrochemical studies on the dissolution of spent nuclear fuel, this is the first investigation that demonstrates the formation of a stable U(V) intermediate phase on the surface of submicron-sized uraninite particles suspended in aqueous solutions.  相似文献   

13.
Pore water chemistry and 234U/238U activity ratios from fine-grained sediment cored by the Ocean Drilling Project at Site 984 in the North Atlantic were used as constraints in modeling in situ rates of plagioclase dissolution with the multicomponent reactive transport code Crunch. The reactive transport model includes a solid-solution formulation to enable the use of the 234U/238U activity ratios in the solid and fluid as a tracer of mineral dissolution. The isotopic profiles are combined with profiles of the major element chemistry (especially alkalinity and calcium) to determine whether the apparent discrepancy between laboratory and field dissolution rates still exists when a mechanistic reactive transport model is used to interpret rates in a natural system. A suite of reactions, including sulfate reduction and methane production, anaerobic methane oxidation, CaCO3 precipitation, dissolution of plagioclase, and precipitation of secondary clay minerals, along with diffusive transport and fluid and solid burial, control the pore fluid chemistry in Site 984 sediments. The surface area of plagioclase in intimate contact with the pore fluid is estimated to be 6.9 m2/g based on both grain geometry and on the depletion of 234U/238U in the sediment via α-recoil loss. Various rate laws for plagioclase dissolution are considered in the modeling, including those based on (1) a linear transition state theory (TST) model, (2) a nonlinear dependence on the undersaturation of the pore water with respect to plagioclase, and (3) the effect of inhibition by dissolved aluminum. The major element and isotopic methods predict similar dissolution rate constants if additional lowering of the pore water 234U/238U activity ratio is attributed to isotopic exchange via recrystallization of marine calcite, which makes up about 10-20% of the Site 984 sediment. The calculated dissolution rate for plagioclase corresponds to a rate constant that is about 102 to 105 times smaller than the laboratory-measured value, with the value depending primarily on the deviation from equilibrium. The reactive transport simulations demonstrate that the degree of undersaturation of the pore fluid with respect to plagioclase depends strongly on the rate of authigenic clay precipitation and the solubility of the clay minerals. The observed discrepancy is greatest for the linear TST model (105), less substantial with the Al-inhibition formulation (103), and decreases further if the clay minerals precipitate more slowly or as highly soluble precursor minerals (102). However, even several orders of magnitude variation in either the clay solubility or clay precipitation rates cannot completely account for the entire discrepancy while still matching pore water aluminum and silica data, indicating that the mineral dissolution rate conundrum must be attributed in large part to the gradual loss of reactive sites on silicate surfaces with time. The results imply that methods of mineral surface characterization that provide direct measurements of the bulk surface reactivity are necessary to accurately predict natural dissolution rates.  相似文献   

14.
Chemical, spectrographic, and isotopic analyses are presentedfor the Franzfontein alkali granite and constituent minerals.This rock has the chemical character of granties produced byliquid crystal equilibrium. Dated at 1, 700?70m.y. by the constituentzircon, its crystallization formed part of a major period (theHuabian episode) of batholithic granite emplacement in northernSouth-West Africa. The occurrence of these crystalline rocksin the core of the Huab anticline defines the maximum possibleage of the overlying Otavi Facies sediments, precluding theircorrelation with the Transvaal System of South Africa. The imprint of the Damara metamorphism (Damaran episode) isreflected in the Sr/Rb age (560?30 m.y.) obtained for the biotite:the inversion of biotite to stilpnomelane and chlorite probablyrepresents the mineralogical effects of that metamorphis. Isotopicdata indicate that changes in the relative concentrations ofRb and Sr differed significantly in plagioclase and microcline;such data from feldspars in metamorphic rocks should, therefore,be interpreted with caution.  相似文献   

15.
The dissolution-precipitation of quartz controls porosity and permeability in many lithologies and may be the best studied mineral-water reaction. However, the rate of quartz-water reaction is relatively well characterized far from equilibrium but relatively unexplored near equilibrium. We present kinetic data for quartz as equilibrium is approached from undersaturation and more limited data on the approach from supersaturated conditions in 0.1 molal NaCl + NaOH + NaSiO(OH)3 solutions with pH 8.2-9.7 at 398, 423, 448, and 473 K. We employed a potentiometric technique that allows precise determination of solution speciation within 2 kJ mol−1 of equilibrium without the need for to perturb the system through physical sampling and chemical analysis. Slightly higher equilibrium solubilities between 423 and 473 K were found than reported in recent compilations. Apparent activation energies of 29 and 37 kJ mol−1 are inferred for rates of dissolution at two surface sites with different values of connectedness: dissolution at Q1 or Q2 silicon sites, respectively. The dissolution mechanism varies with ΔG such that reactions at both sites control dissolution up until a critical free energy value above which only reactions at Q1 sites are important. When our near-equilibrium dissolution rates are extrapolated far from equilibrium, they agree within propagated uncertainty at 398 K with a recently published model by Bickmore et al. (2008). However, our extrapolated rates become progressively slower than model predictions with increasing temperature. Furthermore, we see no dependence of the postulated Q1 reaction rate on pH, and a poorly-constrained pH dependence of the postulated Q2 rate. Our slow extrapolated rates are presumably related to the increasing contribution of dissolution at Q3 sites far from equilibrium. The use of the potentiometric technique for rate measurement will yield both rate data and insights into the mechanisms of dissolution over a range of chemical affinity. Such measurements are needed to model the evolution of many natural systems quantitatively.  相似文献   

16.
Ectomycorrhiza-forming fungi (EMF) alter the nutrient-acquisition capabilities of vascular plants, and may play an important role in mineral weathering and the partitioning of products of weathering in soils under nutrient-limited conditions. In this study, we isolated the weathering function of Suillus tomentosus in liquid-cultures with biotite micas incubated at room temperature. We hypothesized that the fungus would accelerate weathering by hyphal attachment to biotite surfaces and transmission of nutrient cations via direct exchange into the fungal biomass. We combined a mass-balance approach with scanning electron microscopy (SEM) and atomic force microscopy (AFM) to estimate weathering rates and study dissolution features on biotite surfaces. Weathering of biotite flakes was about 2-3 orders of magnitude faster in shaken liquid-cultures with fungus compared to shaken controls without fungus, but with added inorganic acids. Adding fungus in nonshaken cultures caused a higher dissolution rate than in inorganic pH controls without fungus, but it was not significantly faster than organic pH controls without fungus. The K+, Mg2+ and Fe2+ from biotite were preferentially partitioned into fungal biomass in the shaken cultures, while in the nonshaken cultures, K+ and Mg2+ was lost from biomass and Fe2+ bioaccumulated much less. Fungal hyphae attached to biotite surfaces, but no significant surface changes were detected by SEM. When cultures were shaken, the AFM images of basal planes appeared to be rougher and had abundant dissolution channels, but such channel development was minor in nonshaken conditions. Even under shaken conditions the channels only accounted for only 1/100 of the total dissolution rate of 2.7 × 10−10 mol of biotite m−2 s−1. The results suggest that fungal weathering predominantly occurred not by attachment and direct transfer of nutrients via hyphae, but because of the acidification of the bulk liquid by organic acids, fungal respiration (CO2), and complexation of cations which accelerated dissolution of biotite. Results further suggest that both carbohydrate source (abundant here) and a host with which nutrients are exchanged (missing here) may be required for EMF to exert an important weathering effect in soils. Unsaturated conditions and physical dispersal of nutrient-rich minerals in soils may also confer a benefit for hyphal growth and attachment, and promote the attachment-mediated weathering which has been observed elsewhere on soil mineral surfaces.  相似文献   

17.
The Mylliem granitoids of the Meghalaya Plateau, northeastern India, represent one of the disharmonic Neoproterozoic igneous plutons, which are intrusive into low-grade Shillong Group of metasediments. Field studies indicate that the Mylliem granitoids cover an area of about 40 km2 and is characterized by development of variable attitude of primary foliations mostly marked along the margin of the pluton. Xenoliths of both Shillong Group of metasediments and mafic rocks have been found to occur within Mylliem granitoids. Structural study of the primary foliation is suggestive of funnel-shaped intrusion of Mylliem granitoids with no appreciable evidence of shearing. Petrographically, Mylliem granitoids are characterized by pink to white phenocrysts of prismatic microcline/perthite and lath-shaped plagioclase (An20–An29). Groundmass material is characterized by quartz, microcline, plagioclase, muscovite and biotite. Sphene and apatite occur as accessory minerals. Petrographically Mylliem granitoids have been discriminated as granite and granodiorite according to IUGS system of classification.  相似文献   

18.
Biotite dissolution under conditions of high pH and high aluminum, sodium, and nitrate concentrations analogous to those found in tank wastes at the Hanford Site was investigated using continuously stirred flow-through reactors at 22 to 25 °C. Experiments were designed to simulate tank leaks into the Hanford vadose zone where Fe(II) from biotite is the dominant reducing agent available to immobilize certain contaminants. Both non-steady-state and steady-state dissolution kinetics were quantified; interest in non-steady-state kinetics derives from the inherently transitory nature of tank leaks. Biotite was conditioned in pH 8 solutions to simulate the alkaline environment of the Hanford sediment, and then reacted in pH 10-14 solutions, some including 0.055 M Al(NO3)3 and/or 2 M or 6 M NaNO3. Initial dissolution transients (intervals of rapid release rates that decay to slower steady-state rates) showed fast preferential release of K followed by near-stoichiometric release of Si, Al, and Mg, and slower release of Fe. Each increase in pH resulted in a second transient with the greatest amounts of Si, Al, and K released at pH 14, followed by pHs 13, 12, 11, and 10. Fe release also was highest at pH 14, but unchanging at pHs 10-13 within experimental error. Transient releases at high pH are attributed to dissolution of amphoteric secondary phases such as ferrihydrite that are inferred from saturation calculations and solid analyses to form during the conditioning interval. Transient release of Si was inhibited by the presence of 0.055 M Al(NO3)3; the effects of Al(NO3)3 and NaNO3 on the release rates of Al, Fe, Mg, and K were variable and generally outweighed by the effect of pH. Quasi-steady-state release rates were slowest at pH 11-12 (10−12.2 mol biotite m−2 s−1 for Si) and increased in either direction in pH away from this minimum (to 10−11.5 at pHs 8 and 14 for Si). Fe release rates at high pH were sufficient to account for observed Cr(VI) reduction at Hanford. The net release rates of the major framework cations, from which the biotite dissolution rate is inferred, may reflect the precipitation of secondary phases or the alteration of biotite to vermiculite. The most extensive solid-phase alterations were observed in Na-enriched solutions.  相似文献   

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20.
The dissolution rate and mechanism of three different cleavage faces of a dolomite crystal from Navarra (near Pamplona), Spain, were studied in detail by vertical scanning interferometry techniques. A total of 37 different regions (each about 124 × 156 μm in size) on the three sample surfaces were monitored as a function of time during dissolution at 25°C and pH 3. Dissolution produced shallow etch pits with widths reaching 20 μm during 8 h of dissolution. Depth development as a function of time was remarkably similar for all etch pits on a given dolomite surface.On the basis of etch pit distribution and volume as a function of time, the calculated dissolution rate increases from near zero to 4 × 10−11 mol cm−2 s−1 over 5 h. The time variation is different for each of the three cleavage surfaces studied. In addition, the absolute dissolution rates of different parts of the dolomite crystal surface can be computed by using a reference surface. The different surfaces yield an “average” rate of 1.08 × 10−11 mol cm−2 s−1 with a standard deviation of 0.3 × 10−11 mol cm−2 s−1 based on about 60 analyses. The mean absolute rate of the dolomite surface is about 10 times slower than the rate calculated from etch pit dissolution alone. On the other hand, earlier batch rate data that used BET surface areas yield rates that are at least 30 to 60 times faster than our directly measured mean dissolution rate for the same pH and temperature.A conceptual model for mineral dissolution has been inferred from the surface topography obtained by the interferometry investigations. In this model, mineral dissolution is not dominated by etch pit formation itself but rather by extensive dissolution stepwaves that originate at the outskirts of the etch pits. These stepwaves control the overall dissolution as well as the dependence on temperature and saturation state.  相似文献   

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