Reaction kinetics of dolomite rim growth

Reaction rims of dolomite (CaMg[CO₃]₂) were produced by solid-state reactions at the contacts of oriented calcite (CaCO₃) and magnesite (MgCO₃) single crystals at 400 MPa pressure, 750–850 °C temperature, and 3–146 h annealing time to determine the reaction kinetics. The dolomite reaction rims show two different microstructural domains. Elongated palisades of dolomite grew perpendicular into the MgCO₃ interface with length ranging from about 6 to 41 µm. At the same time, a 5–71 µm wide rim of equiaxed granular dolomite grew at the contact with CaCO₃. Platinum markers showed that the original interface is located at the boundary between the granular and palisade-forming dolomite. In addition to dolomite, a 12–80 µm thick magnesio-calcite layer formed between the dolomite reaction rims and the calcite single crystals. All reaction products show at least an axiotactic crystallographic relationship with respect to calcite reactant, while full topotaxy to calcite prevails within the granular dolomite and magnesio-calcite. Dolomite grains frequently exhibit growth twins characterized by a rotation of 180° around one of the $[11\bar{2}0]$ equivalent axis. From mass balance considerations, it is inferred that the reaction rim of dolomite grew by counter diffusion of MgO and CaO. Assuming an Arrhenius-type temperature dependence, activation energies for diffusion of CaO and MgO are E _a (CaO) = 192 ± 54 kJ/mol and E _a (MgO) = 198 ± 44 kJ/mol, respectively.     

Grain growth kinetics of dolomite,magnesite and calcite: a comparative study

The rates of grain growth of stoichiometric dolomite [CaMg(CO₃)₂] and magnesite (MgCO₃) have been measured at temperatures T of 700–800°C at a confining pressure P _c of 300 MPa, and compared with growth rates of calcite (CaCO₃). Dry, fine-grained aggregates of the three carbonates were synthesized from high purity powders by hot isostatic pressing (HIP); initial mean grain sizes of HIP-synthesized carbonates were 1.4, 1.1, and 17 μm, respectively, for CaMg(CO₃)₂, MgCO₃, and CaCO₃, with porosities of 2, 28, and 0.04% by volume. Grain sizes of all carbonates coarsened during subsequent isostatic annealing, with mean values reaching 3.9, 5.1, and 27 μm for CaMg(CO₃)₂, MgCO₃, and CaCO₃, respectively, in 1 week. Grain growth of dolomite is much slower than the growth rates of magnesite or calcite; assuming normal grain growth and n = 3 for all three carbonates, the rate constant K for dolomite (≃5 × 10⁻⁵ μm³/s) at T = 800°C is less than that for magnesite by a factor of ~30 and less than that for calcite by three orders of magnitude. Variations in carbonate grain growth may be affected by differences in cation composition and densities of pores at grain boundaries that decrease grain boundary mobility. However, rates of coarsening correlate best with the extent of solid solution; K is the largest for calcite with extensive Mg substitution for Ca, while K is the smallest for dolomite with negligible solid solution. Secondary phases may nucleate at advancing dolomite grain boundaries, with implications for deformation processes, rheology, and reaction kinetics of carbonates.     

Dissolution kinetics and the weathering of mafic minerals

Fayalite, hypersthene, basalt, and obsidian were dissolved in buffered solutions (25°C; pH 4.5 and 5.5) under air, N₂ or O₂ atmospheres, in order to follow the kinetics of dissolution. Each dissolved more rapidly at lower pH values, dissolving most rapidly in the initial few days, followed by slower dissolution for periods up to six months. Dissolution was more rapid when air was excluded. In oxygen atmospheres an Fe(OH)₃ precipitate armors mineral surfaces, thus inhibiting further dissolution, and further affects the solution by scavenging dissolved silica and cations. Dissolution reactions include initial exchange between cations and H⁺, incongruent dissolution of silicate structures, oxidation of Fe²⁺ in solution, precipitation of Fe(OH)₃, and scavenging of dissolved silica and cations by Fe(OH)₃. Dissolution kinetics may explain weathering of mafic rocks and minerals at the Earth's surface, the formation of Fe-oxide coatings on mineral grains, weathering of submarine mafic rocks and intrastratal solution of mafic minerals in buried sandstones. Early Precambrian weathering would have been more rapid before the appearance of large amounts of oxygen in the atmosphere, and continental denudation rates may have been higher than at present because of this effect and the predominance of mafic igneous rocks at an early stage of continent formation and growth.     

Effects of fluid production on fluid flow during regional and contact metamorphism

Numerical and analytical models of fluid flow that account for fluid production during prograde regional and contact metamorphism show that expulsion of metamorphic fluids dominates the convective flux when crustal permeabilities are less than 0.1–100 μD, depending primarily on the rate of fluid production. When this is the case, fluid circulation is limited or prevented, fluid pressures are elevated above hydrostatic values, and flow throughout most of the model is up and away from the region of maximum fluid production. Fluid circulation is predicted to occur where permeability is high, in dry rocks, or after rates of fluid production decrease as peak temperatures are reached. Large changes in the pattern of flow and influx of externally derived fluids may thus occur in metamorphic terranes when dehydration wanes or ceases and cooling begins. Inclusion of an impermeable horizon in the models further inhibits fluid circulation. Earlier, shallow hydrothermal models and interpretations based on the Rayleigh number may be inappropriate for characterizing fluid flow during prograde metamorphism at depth because they do not account for fluid production.     

Dissolution kinetics of experimentally shocked silicate minerals

The effect of lattice strain on mineral dissolution rates was examined by comparing the dissolution rates of shocked and unshocked minerals. Labradorite, oligoclase and hornblende were explosively shocked at mean pressures ranging from 4 to 22 GPa. The labradorite was examined with transmission electron microscopy to estimate the density of dislocations produced by the shock-loading experiment. Subsamples of the labradorite were then thermally annealed to remove some of the dislocations, and to evaluate the importance of such thermal pre-treatment in preparing mineral surfaces for experiments. The dissolution rates of these minerals were measured in batch experiments at pH-values of 2.7 and 4.0.

Shock-loading did not produce extremely high dislocation densities in the labradorite. The density of dislocations in the unshocked labradorite is ≤ 10¹⁰ m⁻². After shocking, the density increases to 10¹²-10¹³ m⁻². The distribution of dislocations is heterogeneous, and the amount of deformation does not increase substantially with shock pressure. These results are highly atypical of shock-modified minerals, where relatively low shock pressures usually induce high ( 10¹⁵ m⁻²) densities of dislocations. Thermal annealing for 1 hr. at 900°C in a dry furnace removes many dislocations from the shocked labradorite.

The difference in observed dissolution rates between shocked and unshocked minerals appears to have a weak correlation with the increase in the density of dislocations on the mineral surface. The unshocked and shocked oligoclase and hornblende samples exhibit limited dissolution enhancement at pH 4.0. Increasing the density of dislocations by several orders of magnitude with shock-loading causes a relatively small increase in dissolution rates for these silicate minerals. These results suggest that the surface dislocations produced by the shock treatment are not the primary sites for dissolution reactions.     

Dissolution, solution transfer, diffusion versus fluid flow and volume loss during deformation/metamorphism

ABSTRACT Dissolution and solution transfer during deformation/metamorphism are controlled by the partitioning of deformation into progressive shearing and shortening components. Progressive shearing is readily accommodated by slip on the planar crystal structure of phyllosilicates and graphite without accumulating dislocation density gradients across grain boundaries. Progressive shortening is accommodated by the cores of most other minerals (including sulphides). These minerals develop strain, and hence dislocation density gradients, on their rims due to progressive shearing along grain boundaries. These gradients are particularly large when the mineral abuts phyllosilicate or graphite. The resulting chemical potential gradients between the core and rim drive dissolution, causing removal of the highly strained grain margins. Removal of dissolved material by solution transfer is aided by the geometry of shearing of phyllosilicates and graphite around other grains in an active anastomosing foliation. Interlayers and interfaces on boundaries lying at a low angle to the direction of shearing, and oriented relative to the sense of shear such that they can open, gape by small amounts. Water present in these interlayer spaces becomes destructured, considerably enhancing diffusion rates along the foliation. Penetrative volume loss, especially in deforming/metamorphosing pelitic rocks, is large at all metamorphic grades, increasing and becoming more penetrative with depth to at least the transition into granulite and eclogite facies. Transference of material by fluid flow from deep to high levels in the earth's crust is precluded because thousands to tens of thousands of rock volumes of fluid are required, necessitating continual recirculation of fluid from shallow to deep crustal levels in one large or several small sets of cells, unless some extremely large-scale form of fluid channelling is possible. Reassessment of diffusion mechanisms, and hence rates, during deformation and pervasive foliation generation in large volumes of rock where fluid channeling cannot provide enough fluid, indicates that diffusion can proceed with sufficient rapidity that massive recirculation of fluid is no longer required. The amount of fluid can be reduced sufficiently to allow large volume losses by a one-way flow of fluid to the earth's surface, in deforming/metamorphosing environments where the fluid pressure equals or exceeds the hydrostatic pressure. Deformation partitioning-controlled dissolution progressively changes the bulk chemistry of a rock containing phyllosilicates or graphite during deformation/metamorphism because matrix minerals, other than phyllosilicates and graphite, are preferentially removed. The large size of porphyroblasts, if present, tends to preserve them from dissolution. Hence, the bulk chemistry operative during subsequent porphyroblast growth can have changed considerably from that operative when the first porphyroblasts grew, in rocks in which bedding is still well preserved.     

Dissolution study of tremolite and anthophyllite: pH effect on the reaction kinetics

The effect of pH on the kinetics of tremolite and anthophyllite dissolution was investigated at 25 °C in batch reactors over the pH range of 1–13.5, in inorganic buffered solutions. Dissolution rates were obtained based on the release of Si and Mg. Results obtained in this study show different behaviors for both minerals. For tremolite, dissolution rates show a noticeable dependence on pH between 1 and 8, decreasing as pH increases and reaching a minimum around neutral conditions. At basic pH this dependence becomes even stronger, but dissolution takes place together with collateral effects of saturation and carbonation. A preferential release of Ca and Mg is observed in acid media, lowering the Mg/Si ratio to the extent that Mg solubility decreases with pH. For anthophyllite, dissolution rates also show a strong dependence on pH, between 1 and 9.5. At the same pH, anthophyllite dissolves up to 8 times faster than tremolite. For pH > 9.5 this dependence is smooth, and it is probably associated with effects of saturation and carbonation. Dissolution is also non-stoichiometric with a faster release of Mg with respect to Si in acid media. SEM observations show differences in the breakage mechanism of the fibers. The anthophyllite particle breakage during dissolution consists of the splitting of bundle fibers parallel to the fiber longitudinal direction. However, for tremolite, other than fiber splitting, particles shorten induced by coalescence of etch pits developed perpendicular to c axe.     

Dissolution kinetics of probertite in boric acid solution

Probertite (NaCaB₅O₉·5H₂O) and ulexite (NaCaB₅O₉·8H₂O) posses identical chemical formula except for their water content. In this study, the dissolution of probertite in boric acid solution was investigated as a function of temperature and time. As the boric acid concentration increased, the dissolution of probertite also increased. However, the boric acid concentrations above 5 wt.% at 60 °C and 80 °C did not significantly affect the dissolution of probertite. The stirring speed had almost no effect on the dissolution of probertite. The dissolution kinetics of probertite in boric acid solution was controlled by first order pseudo homogeneous reaction. The activation energies for different probertite particle sizes varied from 25.25 kJ/mol K to 28.25 kJ/mol K, indicating that particle size had minor effect on the dissolution of probertite.     

沁水盆地岩性交替井绒囊钻井液实践

为有效解决沁水盆地煤层气井因岩性变化快而引发的漏失、坍塌、掉块等情况,通过室内研究及现场应用,采用绒囊钻井液能够有效解决上述问题。MBS26-11防塌试验井和MBS24-5防漏堵漏试验井钻遇地层多而复杂,邻井坍塌、漏失严重。MBS26-11井二开采用绒囊钻井液,密度为0.95~1.05 g/cm³,黏度为35~38 s,平均机械钻速10.79 m/h,比邻井钻速提高9.2%。钻进过程中无掉块、卡钻现象,顺利完钻。MBS24-5井一开采用膨润土泥浆,漏失严重,漏失速率达6.95 m³/h,采用绒囊钻井液后漏失速率为1.68 m³/h。二开仍采用绒囊钻井液,密度保持0.93~0.98 g/cm³,漏斗黏度在38 s以上,塑性黏度6~14 mPa·s,动切力3.00~6.64 YP/Pa,动塑比保持在0.43~1.66Pa/mPa·s。平均机械钻速5.6 m/h。     

Dissolution kinetics of chrysotile at pH 7 to 10

The rate of chrysotile dissolution over five days was studied in constant-pH, batch suspensions at 25°C. After the first day, release of Mg occurred at a constant rate and exhibited a fractional dependence on pH, [H⁺]^0.24. Interpreted in terms of a site-binding model for adsorption of protons on the surface, this fractional dependence implies that the rate is limited by a chemical reaction involving less than one adsorbed proton per Mg released into solution. The actual magnitude of the rate (10^?15.7 mol cm^?2 s^?1 at pH 8) supports this interpretation. The inorganics NO₃^?, Cl^?, HCO₃^? and SO₄^- and the organics catechol and oxalate affected the rate of Mg release only during the initial 12 to 24 hours of each experiment. Silica release was linear from the outset of each experiment, but showed no definite pH dependence.     

Dissolution kinetics of natural magnesite in lactic acid solutions

In this study, the dissolution of magnesite particles in aqueous lactic acid solutions was investigated in a batch reactor employing the parameters of stirring speed, particle size, temperature and acid concentration. The shrinking core model was evaluated to determine the effect of particle size, temperature and concentration. It was also found that the stirring speed did not change the dissolution. Consequently, it was determined that the dissolution rate is controlled by surface chemical reaction. The activation energy of the process was determined to be 50.3 kJ mol^− 1.     

Dissolution kinetics of natural magnesite in acetic acid solutions

Dissolution of magnesite in acetic acid solutions was investigated. The influence of various parameters such as reaction temperature, particle size and acid concentration was studied in order to elucidate the kinetics of magnesium carbonate. The leaching rate increased with decreasing particle size and with increasing temperature. Initially, the dissolution in terms of acid concentration increased until a definite concentration and then fell with increasing concentration. A kinetic model was researched to describe the dissolution and to analyse the kinetic data, basically. Dissolution curves were evaluated in order to test shrinking core models for fluid–solid systems. Consequently, it was determined that the dissolution of natural magnesite was controlled by chemical reaction, i.e., 1−(1−x)1/3=kt. The apparent activation energy of leaching process was found as 78.40 kJ mol⁻¹.     

Influence of lithology and fluid flow on the temperature distribution in a sedimentary basin: A case study from the Cold Lake area, Alberta, Canada

A detailed study of the groundwater and terrestrial heat flow was carried out over an area of 23,700 km² west of Cold Lake, Alberta, which is part of the western Canada sedimentary basin. The information for the study was provided from data from 3100 wells drilled in the area. The screening and processing of thousands of stratigraphic picks, drillstem test data, bottom hole temperatures and formation water chemistry data was performed mainly using a specially designed software package. As a result, every stratigraphic unit is characterized by appropriate hydraulic and thermal parameters.

A sequence of aquifers, aquitards and aquicludes was differentiated. The groundwater flow in the Paleozoic aquifers is regional in nature and mainly horizontal. The flow in the Cretaceous aquifers is of intermediate type, mainly downward oriented. In general, the permeability of the Cretaceous and Paleozoic strata has such low values that the fluid velocity is less than 1 cm/yr.

The convective heat transport in the hydrostratigraphic sequence is negligible with respect to the conductive heat transfer, as shown by the Peclet number of the fluid and heat flow in porous media. The flow of the terrestrial heat flux from the Precambrian basement of the sedimentary basin to the atmosphere is controlled by the variability in the thermal properties of the formations in the basin.

The geothermal gradients were computed by hydrostratigraphic unit using a linear regression fit to the temperature data. As expected, they show higher values for the less conductive layers, and lower values for the more conductive ones. The weighted average, or the integral geothermal gradient of the whole sedimentary column, was computed by considering the difference between the temperature measured at the Precambrian basement and the annual average temperature at the surface. The areal distribution of the integral geothermal gradient (with an average of 22.0 mK/m) shows a strong correlation with the lithology.

The areal temperature distribution for each hydrostratigraphic unit was analyzed by mapping the deviation of the measured value from the computed geothermal gradient. The lateral heat flow from warmer to colder areas is one order of magnitude smaller than the vertical heat flow. In the more homogeneous units, the lateral heat flow presents a trend that seems to reflect the geometry and lithology.     

Dissolution kinetics of soil clays in sulfuric acid solutions: Ionic strength and temperature effects

Significant amounts of sulfuric acid (H₂SO₄) rich saline water can be produced by the oxidation of sulfide minerals contained in inland acid sulfate soils (IASS). In the absence of carbonate minerals, the dissolution of phyllosilicate minerals is one of very few processes that can provide long-term acid neutralisation. It is therefore important to understand the acid dissolution behavior of naturally occurring clay minerals from IASS under saline–acidic solutions. The objective of this study was to investigate the dissolution of a natural clay-rich sample under saline–acidic conditions (pH 1–4; ionic strengths = 0.01 and 0.25 M; 25 °C) and over a range of temperatures (25–45 °C; pH 1 and pH 4). The clay-rich sample referred to as Bottle Bend clay (BB clay) used was from an IASS (Bottle Bend lagoon) in south-western New South Wales (Australia) and contained smectite (40%), illite (27%), kaolinite (26%) and quartz (6%). Acid dissolution of the BB clay was initially rapid, as indicated by the fast release of cations (Si, Al, K, Fe, Mg). Relatively higher Al (pH 4) and K (pH 2–4) release was obtained from BB clay dissolution in higher ionic strength solutions compared to the lower ionic strength solutions. The steady state dissolution rate (as determined from Si, Al and Fe release rates; R_Si, R_Al, R_Fe) increased with decreasing solution pH and increasing temperature. For example, the highest log R_Si value was obtained at pH 1 and 45 °C (−9.07 mol g⁻¹ s⁻¹), while the lowest log R_Si value was obtained at pH 4 and 25 °C (−11.20 mol g⁻¹ s⁻¹). A comparison of these results with pure mineral dissolution rates from the literature suggests that the BB clay dissolved at a much faster rate compared to the pure mineral samples. Apparent activation energies calculated for the clay sample varied over the range 76.6 kJ mol⁻¹ (pH 1) to 37.7 kJ mol⁻¹ (pH 4) which compare very well with the activation energy values for acidic dissolution of monomineralic samples e.g. montmorillonite from previous studies. The acid neutralisation capacity (ANC) of the clay sample was calculated from the release of all structural cations except Si (i.e. Al, Fe, K, Mg). According to these calculations an ANC of 1.11 kg H₂SO₄/tonne clay/day was provided by clay dissolution at pH 1 (I = 0.25 M, 25 °C) compared to an ANC of 0.21 kg H₂SO₄/tonne clay/day at pH 4 (I = 0.25 M, 25 °C). The highest ANC of 6.91 kg H₂SO₄/tonne clay/day was provided by clay dissolution at pH 1 and at 45 °C (I = 0.25 M), which is more than three times higher than the ANC provided under the similar solution conditions at 25 °C. In wetlands with little solid phase buffering available apart from clay minerals, it is imperative to consider the potential ANC provided by the dissolution of abundantly occurring phyllosilicate minerals in devising rehabilitation schemes.     

泥石流物源区基岩岩性特征探讨

在一定区域内总体均匀的超强降水,并不会导致地形地貌条件大致相同的沟谷流域都发生泥石流,主要原因在于基岩岩性特征的差别。基岩构造总体较均一时,表部松散物的流失是持续渐进的;基岩为软硬相间的岩层,或者受到线性构造破坏,容易出现差异风化,表部物质呈脉动式剥蚀,可以为泥石流启动提供较好的物源条件。     

Dissolution kinetics of magnesite in acidic aqueous solution: a hydrothermal atomic force microscopy study assessing step kinetics and dissolution flux

Magnesite (104) dissolution kinetics were studied in acidic aqueous solutions (2.0 < pH < 4.2) at temperatures between 60 and 90°C by atomic force microscopy (AFM). Comparison of dissolution fluxes obtained by AFM and chemical methods revealed six to seven times larger dissolution fluxes obtained by chemical analysis. Corresponding empirical activation energies were found to be 74 ±22 kJ/mol and 41 ± 4 kJ/mol (at pH 4.2) for the AFM and chemical methods, respectively. The empirical reaction order with respect to proton concentration was 0.36 ± 0.13 and 0.47 ± 0.03 for AFM and chemical methods, respectively. These comparisons suggest that the two experimental measurement methods differ as a result of the different sampling length scales associated with the methods. Negligible changes in step dissolution velocity with changes in bulk pH were found, suggesting that the principal source of increasing dissolution flux with decreasing pH is an increase in step density. However, the observed stable step orientation, which is dependent on pH, suggests that more than one proton adsorption equilibrium should be used to describe the surface chemistry of magnesite in acidic solution.     

Dissolution kinetics of synthetic Na-smectite. An integrated experimental approach

The effect of pH and Gibbs energy on the dissolution rate of a synthetic Na-montmorillonite was investigated by means of flow-through experiments at 25 and 80 °C at pH of 7 and 9. The dissolution reaction took place stoichiometrically at 80 °C, whereas at 25 °C preferential release of Mg over Si and Al was observed. The TEM-EDX analyses (transmission electronic microscopy with quantitative chemical analysis) of the dissolved synthetic phase at 25 °C showed the presence of newly formed Si-rich phases, which accounts for the Si deficit. At low temperature, depletion of Si concentration was attributed to incongruent clay dissolution with the formation of detached Si tetrahedral sheets (i.e., alteration product) whereas the Al behaviour remains uncertain (e.g., possible incorporation into Al-rich phases). Hence, steady-state rates were based on the release of Mg. Ex situ AFM measurements were used to investigate the variations in reactive surface area. Accordingly, steady-state rates were normalized to the initial edge surface area (11.2 m² g⁻¹) and used to propose the dissolution rate law for the dissolution reactions as a function of ΔG_r at 25 °C and pH∼9:

     

Well log data analysis for lithology and fluid identification in Krishna-Godavari Basin,India

Well log analysis provides the information on petrophysical properties of reservoir rock and its fluid content. The present study depicts interpretation of well log responses such as gamma ray, resistivity, density and neutron logs from six wells, namely W-1, W-2, W-9, W-12, W-13 and W-14 under the study area of Krishna-Godavari (K-G) basin. The logs have been used primarily for identification of lithology and hydrocarbon-bearing zones. The gamma ray log trend indicates deposition of cleaning upward sediment. Coarsening upward, clayey-silty-sandy bodies have been evidenced from the gamma ray log. Gas-bearing zones are characterised by low gamma ray, high deep resistivity and crossover between neutron and density logs. Total 14 numbers of hydrocarbon-bearing zones are identified from wells W-9, W-12, W-13 and W-14 using conventional log analysis. Crossplotting techniques are adopted for identification of lithology and fluid type using log responses. Crossplots, namely P-impedance vs. S-impedance, P-impedance vs. ratio of P-wave and S-wave velocities (Vp/Vs) and lambda-mu-rho (LMR), have been analysed to discriminate between lithology and fluid types. Vp/Vs vs. P-impedance crossplot is able to detect gas sand, brine sand and shale whereas P-impedance vs. S-impedance crossplot detects shale and sand trends only. LMR technique, i.e. λρ vs. μρ crossplot is able to discriminate gas sand, brine sand, carbonate and shale. The LMR crossplot improves the detectability and sensitivity of fluid types and carbonate lithology over other crossplotting techniques. Petrophysical parameters like volume of shale, effective porosity and water saturation in the hydrocarbon-bearing zones in these wells range from 5 to 37%, from 11 to 36 and from 10 to 50% respectively. The estimated petrophysical parameters and lithology are validated with limited core samples and cutting samples from five wells under the study area.     

碳酸盐岩溶蚀机制的实验探讨:表面溶蚀与内部溶蚀对比

通过表面溶蚀和内部溶蚀两种实验方式,分别对六种类型碳酸盐岩用0.2%乙酸溶液进行溶蚀实验,对比研究了从表生环境到深埋藏环境下有机酸与不同类型碳酸盐岩的溶蚀作用机制。对比研究表明:(1)在近地表环境下(25℃,1.0 MPa),泥灰岩和含生物碎屑泥晶灰岩的溶解速率大于细晶白云岩,前两者约为后者的2³倍;随着温压的增加,泥灰岩、含生物碎屑泥晶灰岩和细晶白云岩的溶解速率均相应增加,但细晶白云岩的溶解速率增加幅度更大;在深埋藏环境下(180℃,45 MPa到210℃,52.5 MPa),细晶白云岩的溶解速率逐渐与泥灰岩和含生物碎屑泥晶灰岩的溶解速率趋于一致。(2)在60℃,10 MPa时,白云质颗粒灰岩在乙酸溶液中的溶解能力大于粉细晶白云岩和亮晶鲕粒白云岩;随着温压的增加,有机酸溶液对石灰岩与白云岩的溶解能力均相应降低,且石灰岩溶蚀作用下降幅度更大,当温压达到或超过90℃、20 MPa时,粉细晶白云岩和亮晶鲕粒白云岩在乙酸溶液中的溶解能力大于白云质颗粒灰岩。根据实验结果推测:表生和相对浅埋藏的温压条件下,石灰岩的溶解速率和溶解能力大于白云岩,石灰岩的溶蚀作用较白云岩发育;但在深埋藏阶段,由于白云岩的溶解能力大于石灰岩,因此白云岩溶蚀产生的次生孔隙较石灰岩更为发育,这或许是深部的碳酸盐岩储层中多见白云岩储层的重要原因。     

Dissolution kinetics and biodurability of tremolite particles in mimicked lung fluids: Effect of citrate and oxalate

The effect of citrate and oxalate on tremolite dissolution rate was measured at 37 °C in non-stirred flow-through reactors, using modified Gamble’s solutions at pH 4 (macrophages), 7.4 (interstitial fluids) and 5.5 (intermediate check point) containing 0, 0.15, 1.5 and 15 mmol L⁻¹ of citrate or oxalate. The dissolution rates calculated from Si concentration in the output solutions without organic ligands depend on pH, decreasing when the pH increases from −13.00 (pH 4) to −13.35 (pH 7.4) mol g⁻¹ s⁻¹ and following a proton-promoted mechanism. The presence of both ligands enhances dissolution rates at every pH, increasing this effect when the ligand concentration increases. Citrate produces a stronger effect as a catalyst than oxalate, mainly at more acidic pHs and enhances dissolution rates until 20 times for solutions with 15 mmol L⁻¹ citrate. However, at pH 7.4 the effect is lighter and oxalate solutions (15 mmol L⁻¹) only enhances dissolution rates eight times respect to free organic ligand solutions. Dissolution is promoted by the attack to protons and organic ligands to the tremolite surface. Magnesium speciation in oxalate and citrate solutions shows that Mg citrate complexes are more effective than oxalate ones during the alteration of tremolite in magrophages, but this tendency is the opposite for interstitial fluids, being oxalate magnesium complexes stronger. The biodurability estimations show that the destruction of the fibers is faster in acidic conditions (macrophages) than in the neutral solutions (interstitial fluid). At pH 4, both ligands oxalate and citrate reduce the residence time of the fibers with respect to that calculated in absence of ligands. Nevertheless, at pH 7.4 the presence of ligands does not reduce significantly the lifetime of the fibers.