Evolution of crystal sizes in the series of dissolution and precipitation events in open magma systems

We propose a model that describes the evolution of crystal sizes and crystal size distributions (CSD) of igneous phenocrysts in a sequence of dissolution and crystallization events. This model is based on the assumption that crystal dissolution is rate-limited by diffusion in melt while crystal growth is controlled by the slower kinetic of new nucleation and growth. As a result, the dissolution rate is inversely proportional to crystal size coming into effect through the curvature of the crystal's surface, but the growth rate does not depend on the crystal size. Closed-form analytical solution of equation for CSD is obtained. We apply results of modeling to quartz and zircon, two prime minerals in silicic igneous systems that are widely used in geochemical and isotopic investigations. The time-series of multiple solution–reprecipitation episodes generate concave-downward CSDs and this result fits well with experimental and natural observations on the abundant concave-down CSD in silicic igneous rocks. We suggest that maturation of crystal populations with sizes above several micrometers can not be caused by a size effect on the solubility of the crystals (Ostwald ripening), but is rather driven by thermal oscillations in experiments and in nature. The model predicts that mean crystal size increases with time proportionally to ∼ t^0.20, which is very close to the published experimental results for quartz maturation with the exponent of 0.19–0.22. Our proposed model gives an opportunity to use natural CSDs for interpretation of pre-eruptive magma history, when solubilities and diffusion data are available for constituent elements of the dissolving mineral. In particular, we present time estimates for maturing zircon populations in large volume ignimbrites and estimate that it takes 100–1000 yrs to mature an initially exponential CSD to a lognormal CSD.     

Compaction of a Rock Fracture Moderated by Competing Roles of Stress Corrosion and Pressure Solution

Unusually rapid closure of stressed fractures, observed in the initial stages of loading and at low temperatures, is examined using models for subcritical crack growth and pressure solution. The model for stress corrosion examines tensile stress concentrations induced at the Hertzian contact of propping fracture asperities, and mediates fracture growth according to a kinetic rate law. Conversely, pressure solution is described by the rate-limiting process of dissolution, resulting from the elevated stresses realized at the propping asperity contact. Both models are capable of following the observed compaction of fractures in novaculite. However, closure rates predicted for stress corrosion cracking are orders of magnitudes faster than those predicted for pressure dissolution. For consistent kinetic parameters, predictions from stress corrosion better replicate experimental observations, especially in the short-term and at low temperature when mechanical effects are anticipated to dominate. Rates and magnitudes of both stress corrosion and pressure solution are dependent on stresses exerted over propping asperities. Rates of closure due to stress corrosion cracking are shown to be always higher than for pressure solution, except where stress corrosion ceases as contact areas grow, and local stresses drop below an activation threshold. A simple rate law is apparent for the progress of fracture closure, defined in terms of a constant and an exponent applied to the test duration. For current experimental observations, this rate law is shown to replicate early progress data, and shows promise to define the evolution of transport properties of fractures over extended durations.     

Mechanism of accelerated dissolution of mineral crystals by cavitation erosion

Cavitation,a phenomenon produced by a moving fluid,is ubiquitous in the water environment of the Earth's surface and its related mechanical action in the process of cavitation leads to the widespread erosion of rock in nature.Although the mechanical action of flowing water body that accelerates the rock mass loss and fragmentation of rock(abrasion,erosion,and etching)and other phenomena have been much studied,its acceleration of mineral crystal dissolution is rarely reported.The physical mechanism of effect is not yet clear.The cavitation bubble produced in the cavitation process is at the micron level,and its related mechanical action leading to the accumulation of rock mineral dissolution is manifested in time and space in the process of the chemical element's migration between water and rock minerals.Cavitation erosion may be one of the important driving forces for the migration of geochemical elements within the lithosphere and hydrosphere.In this paper,based on the crystal dissolution stepwave dynamic theory and the theoretical derivation and calculation of Gibbs free energy change of the mineral crystals plastic deformation which caused by the mechanical action of cavitation erosion,we give the possible mechanism of accelerating the transient dissolution of mineral crystals by cavitation erosion—the cavitation bubbles on the surface of the near crystal release the high speed micro-jet and shock wave perpendicular to the surface during the collapsing,in which the water hammer pressure produced by micro-jet at the solid–liquid interface causes instantaneous plastic deformation on the crystal surface under the condition that it is larger than the yield stress of the crystal.Under the influence of the thermal effect of the plastic deformation process and the change of Gibbs free energy(the dislocation elastic strain energy of plastic deformation on the crystal surface may be included),the local instantaneous dissolution rate of the mineral surface is accelerated.The continuous cavitation erosion eventually causes fracture and breaking of the mineral crystal,meanwhile,the Gibbs–Thomson effect may enhance the dissolution of mineral crystals more prominently.At the same time,the correctness of the mechanism is verified qualitatively by the acoustic cavitation experiment with the same erosion mechanism.     

Salt weathering: influence of evaporation rate,supersaturation and crystallization pattern

Micro- and macroscale experiments which document the dynamics of salt damage to porous stone have yielded data which expose weaknesses in earlier interpretations. Previously unexplained differences are found in crystal morphology, crystallization patterns, kinetics and substrate damage when comparing the growth of mirabilite (Na₂SO₄. 10H₂O) and thenardite (Na₂SO₄) versus halite (NaCl). The crystallization pattern of sodium sulphate was strongly affected by relative humidity (RH), while a lesser RH effect was observed for sodium chloride. Macroscale experiments confirmed that mirabilite (crystallizing at RH > 50 per cent) and thenardite (crystallizing at RH < 50 per cent) tend to form subflorescence in highly localized areas under conditions of constant RH and temperature. This crystallization pattern was more damaging than that of halite, since halite tended to grow as efflorescence or by filling the smallest pores of the stone in a homogeneous fashion, a result which contradicts Wellman and Wilson's theoretical model of salt damage. Low RH promoted rapid evaporation of saline solutions and higher supersaturation levels, resulting in the greatest damage to the stone in the case of both sodium sulphate and sodium chloride crystallization. At any particular crystallization condition, sodium chloride tended to reach lower supersaturation levels (resulting in the crystallization of isometric crystals) and created negligible damage, while sodium sulphate reached higher supersaturation ratios (resulting in non-equilibrium crystal shapes), resulting in significant damage. ESEM showed no damage from sodium sulphate due to hydration. Instead, after water condensation on thenardite crystals, rapid dissolution followed by precipitation of mirabilite took place, resulting in stone damage by means of crystallization pressure generation. It is concluded that salt damage due to crystallization pressure appears to be largely a function of solution supersaturation ratio and location of crystallization. These key factors are related to solution properties and evaporation rates, which are constrained by solution composition, environmental conditions, substrate properties, and salt crystallization growth patterns. When combined with a critical review of salt damage literature, these experiments allow the development of a model which explains variations in damage related to combinations of different salts, substrates and environmental conditions. Copyright © 1999 John Wiley & Sons, Ltd.     

Modelling the Kinetics of Calcium Hydroxide Dissolution in Water

In water treatment calcium hydroxide is used in softening and decarbonization techniques as well as in stabilization processes. Due to its slight solubility calcium hydroxide is applied as suspension. The dissolution kinetics plays a major role in these processes. For the characterization of calcium hydroxide dissolution empirical methods exist. These methods allow relative comparison of different calcium hydroxide products. Thus in this study a dissolution rate model is presented that is based on the chemical reactions determining the dissolution. This model allows to predict the dissolution with respect to particle diameter and temperature. However, the most important factor is the particle diameter i.e. the total surface of particles in solution. Furthermore an effect of the dosed amount of calcium hydroxide particles on the solubility was found.     

Recycling and “re-hydration” of degassed magma inducing transient dissolution/crystallization events at Stromboli (Italy)

Intrusive degassing and recycling of degassed and dense magma at depth have been proposed for a long time at Stromboli. The brief explosive event that occurred at the summit craters on 9 January 2005 threw out bombs and lapilli that could be good candidates to illustrate recycling of shallow degassed magma at depth. We present an extensive data set on both the textures and the mineral, bulk rock and glassy matrix chemistry of the “9 Jan” products. The latter have the common shoshonitic–basaltic bulk composition of lavas and scoriae issued from typical strombolian activity. In contrast they differ by the heterogeneous chemistry of their matrix glasses and their crystal textures that testify to crystal dissolution event(s) just prior magma crystallization upon ascent and eruption. Comparison between mineral paragenesis of the natural products and experimental phase equilibria suggest water-induced magma re-equilibration. We propose that mineral dissolution is related to water enrichment of the recycled degassed magma, via differential gas bubble transfer and to some extents its physical mixing with volatile-rich magma blobs. However, all these features illustrate transient processes. Even though evidence of mineral dissolution is ubiquitous at Stromboli, its effect on the bulk magma chemistry is minor because of the subtle interplay between mineral dissolution and crystallization in magmas having comparable bulk chemistry.     

Effect of Iron and Manganese Ions on the Crystal Growth of Calcium Carbonate

The present study describes examinations of growth rate of calcium carbonate using seed crystals of different sizes in the range of 10 to 50 μm at concentrations in the range of 5 to 50 g·L^?1. The rate constant related to the crystal surface per volume was found to be independend of the crystal size. The effect of temperature on the rate constant was described using the Arrhenius equation. The use of suspension of lime as precipitating agent leads to decrease of the rate constant compared to lime water. This effect can be explained by the dissolution of suspended calcium hydroxide particles. Using the presented conditions (SI₀ = 2.8), no impact of iron and manganese ions was observed.     

Modelling the fate of oxidisable organic contaminants in groundwater

Subsurface contamination by organic chemicals is a pervasive environmental problem, susceptible to remediation by natural or enhanced attenuation approaches or more highly engineered methods such as pump-and-treat, amongst others. Such remediation approaches, along with risk assessment or the pressing need to address complex scientific questions, have driven the development of integrated modelling tools that incorporate physical, biological and geochemical processes.We provide a comprehensive modelling framework, including geochemical reactions and interphase mass transfer processes such as sorption/desorption, non-aqueous phase liquid dissolution and mineral precipitatation/dissolution, all of which can be in equilibrium or kinetically controlled. This framework is used to simulate microbially mediated transformation/degradation processes and the attendant microbial population growth and decay. Solution algorithms, particularly the split-operator (SO) approach, are described, along with a brief résumé of numerical solution methods. Some of the available numerical models are described, mainly those constructed using available flow, transport and geochemical reaction packages. The general modelling framework is illustrated by pertinent examples, showing the degradation of dissolved organics by microbial activity limited by the availability of nutrients or electron acceptors (i.e., changing redox states), as well as concomitant secondary reactions. Two field-scale modelling examples are discussed, the Vejen landfill (Denmark) and an example where metal contamination is remediated by redox changes wrought by injection of a dissolved organic compound. A summary is provided of current and likely future challenges to modelling of oxidisable organics in the subsurface.     

多尺度CT成像技术识别超低渗透砂岩储层纳米级孔喉

以鄂尔多斯盆地X地区长6储层为研究对象,利用多尺度CT成像技术、聚焦离子束扫描电镜技术,结合Avizo软件的强大数据处理和数值模拟功能,对研究区目的层岩石样品进行不同尺度孔喉分维数重构,建立三维超低渗透砂岩储层纳米级孔隙结构模型.研究表明,微米尺度下,超低渗透砂岩储层孔喉形态呈点状、球状和条带状及管状.储集空间类型以溶蚀微孔为主且多孤立分布,局部孔隙为片状,连通性较差.纳米尺度下,超低渗透砂岩储层孔喉系统整体较发育,孔喉形态呈球状、短管状.远离裂隙处多为孤立状,连通性较差,仅具有储集能力.微裂缝、粒间缝发育部位多为短管状,有一定连通性,相当于喉道.微观非均质性较强,岩样整体较致密,局部相互连通,溶蚀孔及裂隙对储集能力、渗滤能力具有控制作用.数值计算求得目的层A、Y、C三个样品的孔隙度分别为6.95%、5.55%、4.44%,渗透率分别为0.828×10^-3μm^2、0.115×10^-3μm^2、0.00065×10^-3μm^2.聚焦离子束扫描电镜与多尺度CT成像技术相结合能够定量表征超低渗透砂岩储层微、纳米级孔隙结构.     

Methods to Estimate Source Zone Depletion of Fuel Releases by Groundwater Flow

We compare two methods for estimating the natural source zone depletion (NSZD) rate at fuel release sites that occurs by groundwater flow through the source zone due to dissolution and transport of biodegradation products. Dissolution is addressed identically in both methods. The “mass budget method”, previously proposed and applied by others, estimates the petroleum hydrocarbon biodegradation rate based on dissolved electron acceptor delivery and dissolved biodegradation product removal by groundwater flow. The mass budget method relies on assumed stoichiometry for the degradation reactions and differences in concentrations of dissolved species (oxygen, nitrate, sulfate, reduced iron, reduced manganese, nonvolatile dissolved organic carbon, methane) at monitoring locations upgradient and downgradient of the source zone. We illustrate a refinement to account for degradation reactions associated with loss of reduced iron from solution. The “carbon budget method,” a simplification of approaches applied by others, addresses carbon‐containing species in solution or lost from solution (precipitated) and does not require assumptions about stoichiometry or information about electron acceptors. We apply both methods to a fuel release site with unusually detailed monitoring data and discuss applicability to more typical and less thoroughly monitored sites. The methods, as would typically be applied, yield similar results but have different constraints and uncertainties. Overall, we conclude that the carbon budget method has greater practical utility as it is simpler, requires fewer assumptions, accounts for most iron‐reducing reactions, and does not include CO₂ that escapes from the saturated to the unsaturated zone.     

Rates of dissolution of aluminosilicates in seawater

Dissolution of eight clay minerals, four zeolites, and quartz in seawater has been monitored for81/2 years. For most of the minerals, dissolution can be described as a first-order reaction in which dissolved silica approaches from undersaturation steady concentration values with time. Characteristic reaction rate constants (k₁) are of the order of 10^?7 sec^?1. One of the zeolites, clinoptilolite, shows a different dissolution behavior: SiO₂ concentration in solution reaches a high value within one year, followed by a decline to a lower value, suggestive of precipitation of another silicate phase (possibly sepiolite).A mathematical solution is given for a kinetic equation combining the parabolic-rate and first-order rate processes. It is shown that in a wide range of silicate dissolution reactions taking place over long periods of time, the presence of the parabolic-rate dissolution processes cannot be detected, thereby making its inclusion in the kinetic equations unnecessary. The experimental rates of dissolution are comparable to the SiO₂^? dissolution rates in oceanic sediments near the sediment/water interface. But deeper in the sediment, the calculated dissolution rates are significantly lower than the near-interface and experimental values.     

Weathering of quartz as an Archean climatic indicator

Chert and other hard monomineralic quartz grains weather mostly by mechanical processes in modern environments. Their clasts are overrepresented in conglomerates and sands relative to their sources regions. Conversely, macroscopic dissolution features, including quartzite karst, are rare but not nonexistent. The similar rarity of quartz dissolution in Archean deposits provides a paleothermometer for climate on the early Earth. For example, chert is overrepresented in conglomerates and sands of the ∼3.2 Ga Moodies Group (South Africa) relative to the source region. Features related to the far-from-equilibrium dissolution rate are particularly diagnostic as it increases an order of magnitude over 25 °C, much more than solubility. Extrapolating from observed dissolution rates in modern environments that weather at ∼25 °C, we expect obvious dissolution features in ancient climates above ∼50 °C. Polycrystalline quartz and chert would readily disaggregate by solution along grain boundaries, yielding silt and clay. Quartz grains within slowly weathering granite would become friable, yielding silt and clay, rather than sand. At still higher temperatures, Al₂O₃-rich clays from weathered granite would stand above solution-weathered chert on low-relief surfaces. The observed lack of these features is evidence that the Archean climate was not especially hot.     

Compositions of spinels from cumulative anorthites of the Mutnovskii,Ksudach, Golovnina,and Malyi Semyachik Volcanoes,in Kamchatka

Microprobe studies of unzoned plagioclases (An_92–96) from crystal tuff of Mutnovskii Volcano and allivalite nodules of rocks from the Ksudach, Malyi Semyachik, and Golovnina Volcanoes revealed small inclusions of a dark-colored mineral that was later identified as spinel. Microprobe analyses showed that the grains are unzoned and spinel inclusions of different chemical compositions may occur in one plagioclase crystal. The spinel compositions form a clear extended single trend corresponding to the solvus zone of a solid solution that has not been described in the literature. The existence of this spinel trend in the solvus zone might have been due to early capturing of spinel grains by growing plagioclase crystals and their rapid cooling soon after eruption, resulting in hardening of the metastable solution. These spinels are supposed to form synchronously with plagioclase crystallization. The diversity of spinel compositions is explained by thermo diffusive equalizing of originally zonal spinel crystals after they were captured by plagioclase crystals or by their growth in crystallization haloes of anorthite.     

From surface acidity to surface reactivity; inhibition of oxide dissolution

Paul Schindler's early work on the acid-base chemistry of oxides was instrumental for the development of the concept of surface complexation. This approach has not only been important in establishing a theory on the adsorption of metal ions and ligands as a function of pH and solution variables, but has become essential in establishing surface speciation (coordinative structural and electronic arrangement at the solidwater interface) which in turn determines surface reactivity. The factors that affect dissolution of Fe(III) (hydr)oxides and inhibition of dissolution are discussed. A few examples for the inhibition of reductive and ligand-promoted dissolution by binuclear complexes of oxoanions (phosphate, borate) and of protonpromoted dissolution by Cr(III) are given.     

Role of sediment in solute acquisition in the Himalayan glacier meltwater stream,Gangotri glacier,Uttarakhand, India

Low temperature in-stream solute acquisition in a glacial environment with very high suspended sediment is critical for downstream evolution of water chemistry. Present work is carried out on 18 km headwater reach from Gomukh (snout of the Gangotri glacier) to Gangotri along River Bhagirathi, India for understanding the hydrological processes controlling the solute acquisition in the glacial environment. This is the first attempt to conduct dissolution experiments with river bed sediments and meltwater considering different operating variables namely; contact time, seasonality, different sediment particle sizes, different sediment dose, effect of pH, wetting and crushing of bed sediments of the glacial stream. The role of sediment in low temperature solute acquisition process is characterized by sudden release of ions from the sediment in initial few seconds. Equilibrium time was observed to be 600 s (10 min). Further progressive increase in EC was observed from Gomukh to Gangotri, suggesting change in sediment surface characteristics/or source. Higher dissolution was observed from the bed sediments collected in June. It is found that the dissolution increases with increase in sediment doses but decreases with an increase in sediment particle size fraction. Higher solute acquisition was observed from crushed sediment because of an abundance of very fine particles having fresh, aggressive/reactive mineral surfaces which are capable of dissolution. The solute released from wetted sediment is significantly lower than the fresh sediment, which may be attributed to the destruction of microparticles adhering to mineral grains, the removal of fresh reactive surface sites, dissolution of rapidly weathered minerals such as calcite and evolution towards to equilibrium of the solution. Further, higher dissolution was observed with decrease in pH, which may be attributed to the availability of more hydrogen ion concentration of the solution, which favours more solute acquisition from sediment into meltwater.     

The influence of wettability on NAPL dissolution fingering

Laboratory experiments and numerical simulations in homogeneous porous media were used to investigate the influence of porous medium wettability on the formation and growth of preferential dissolution pathways, dissolution fingers, during nonaqueous phase liquid (NAPL) dissolution. As the porous medium became increasingly NAPL-wet, dissolution fingers grew wider and slower. This result was observed in physical experiments with 0% and 100% NAPL-wet conditions and confirmed with numerical simulations at these and intermediate wettabilities. A previously derived expression for an upscaled mass transfer rate coefficient that accounts for the growth of dissolution fingers was used to quantify the effect of fingering on overall NAPL removal rates. For the test cases evaluated, NAPL dissolution fingering controlled the overall rate of NAPL dissolution after the dissolution front moved 4 cm in 0% NAPL-wet conditions and 18 cm in 100% NAPL-wet conditions. Thus, even in completely NAPL-wet media dissolution fingering may control the overall rate of NAPL dissolution after relatively short travel distances. The importance of NAPL dissolution fingering in heterogeneous systems with spatially varying NAPL saturations, though, remains an important question for future work.     

Reactive transport modeling of the clogging process at Maqarin natural analogue site

The Maqarin site in Jordan has been investigated for three decades as a natural analogue for the long term changes of materials in contact with hyper-alkaline solutions. Similar processes are expected in radioactive waste disposal sites, where cement based materials are in contact with natural rocks or other e.g. clay based materials. In this context, a numerical reactive transport model was used to study local geochemical alterations and induced porosity changes for the Maqarin marl rock in contact with the hyper-alkaline solution. The geochemical setup for the rock mineralogy and the pore water was calibrated to match measurements from the Maqarin site. The setup includes several clay and zeolite minerals, considers cation exchange processes, and a state-of-the-art model for cement phases. Similar to earlier calculations by Steefel and Lichtner (1998) who used a much simpler geochemical model, the pore clogging occurred after several hundred years at a distance of 5–10 mm from the contact to the hyper-alkaline solution. In our calculations, this was caused by a massive precipitation of ettringite and C–S–H minerals. We performed a sensitivity study by varying the intrinsic diffusion coefficient, the Archie’s law exponential factor, and the mineral surface area available for dissolution and precipitation. We found that the dissolution of clay minerals controls the availability of Al, which is needed for ettringite and C–S–H phase precipitation. Thus, the amount and kinetically controlled dissolution of clay minerals controls the spatial and temporal evolution of porosity changes. The simulations reveal that neither cation exchange processes nor the formation of zeolite minerals strongly influence the geochemical evolution of the system.     

Magnetite dissolution,diachronous greigite formation,and secondary magnetizations from pyrite oxidation: Unravelling complex magnetizations in Neogene marine sediments from New Zealand

Detailed rock magnetic and electron microscope analyses indicate that the magnetic signature of Neogene marine sediments from the east coast of New Zealand is dominated by the authigenic iron sulphide greigite. The greigite is present as a mixed population of stable single domain and superparamagnetic grains, which is consistent with authigenic growth from solution. This growth can result from pyritization reactions soon after deposition, which also leads to dissolution of most detrital magnetite; however, where constrained by field tests, our data suggest that remanence acquisition can occur > 1 Myr after deposition, and can vary in timing at the outcrop scale. Strong viscous overprints result from oxidation of the iron sulphides, probably during percolation of oxic ground water. This process can sometimes destroy any ancient remanent magnetization. This complex magnetic behaviour, particularly the presence of late-forming magnetizations carried by greigite, means that the remanence in New Zealand Cenozoic sediments, and in similar sediments elsewhere, cannot be assumed to be primary without confirmation by field tests. The reversals test should be employed with caution in such sediments, as patchy remagnetizations can lead to false polarity stratigraphies.