Geometry and grain-size sorting of ripples on low-energy sandy beaches: field observations and model predictions

ABSTRACT There are very few field measurements of nearshore bedforms and grain‐size distribution on low‐energy microtidal beaches that experience low‐amplitude, long‐period waves. Field observations are needed to determine grain‐size distribution over nearshore bedforms, which may be important for understanding the mechanisms responsible for ripple development and migration. Additional nearshore field observations of ripple geometry are needed to test predictive models of ripple geometry. Ripple height, length and sediment composition were measured in the nearshore of several low‐energy beaches with concurrent measurements of incident waves. The distribution of sediment sizes over individual ripples was investigated, and the performance of several models of ripple geometry prediction was tested both spatially and temporally. Sediment samples were collected from the crest and trough of 164 ripples. The sand‐sized sediment was separated from the small amount (generally <3%) of coarser material (>2 mm) that was present. Within the sand‐sized fraction, the ripple crests were found to be significantly coarser, better sorted and more positively skewed than the troughs. Overall, the troughs were finer than the crests but contained a greater proportion of the small fraction of sediment larger than 2 mm. The field model of Nielsen (1981 ) and the model of Wiberg & Harris (1994 ) were found to be the most accurate models for predicting the wavelength of parallel ripples in the nearshore of the low‐energy microtidal environments surveyed. The Wiberg & Harris (1994 ) model was also the most accurate model for predicting ripple height. Temporal changes in ripple wavelength appear to be dependent on the morphological history of the bed.     

A surface complexation and ion exchange model of Pb and Cd competitive sorption on natural soils

The bioavailability and fate of heavy metals in the environment are often controlled by sorption reactions on the reactive surfaces of soil minerals. We have developed a non-electrostatic equilibrium model (NEM) with both surface complexation and ion exchange reactions to describe the sorption of Pb and Cd in single- and binary-metal systems over a range of pH and metal concentration. Mineralogical and exchange properties of three different acidic soils were used to constrain surface reactions in the model and to estimate surface densities for sorption sites, rather than treating them as adjustable parameters. Soil heterogeneity was modeled with >FeOH and >SOH functional groups, representing Fe- and Al-oxyhydroxide minerals and phyllosilicate clay mineral edge sites, and two ion exchange sites (X⁻ and Y⁻), representing clay mineral exchange. An optimization process was carried out using the entire experimental sorption data set to determine the binding constants for Pb and Cd surface complexation and ion exchange reactions.Modeling results showed that the adsorption of Pb and Cd was distributed between ion exchange sites at low pH values and specific adsorption sites at higher pH values, mainly associated with >FeOH sites. Modeling results confirmed the greater tendency of Cd to be retained on exchange sites compared to Pb, which had a higher affinity than Cd for specific adsorption on >FeOH sites. Lead retention on >FeOH occurred at lower pH than for Cd, suggesting that Pb sorbs to surface hydroxyl groups at pH values at which Cd interacts only with exchange sites. The results from the binary system (both Pb and Cd present) showed that Cd retained in >FeOH sites decreased significantly in the presence of Pb, while the occupancy of Pb in these sites did not change in the presence of Cd. As a consequence of this competition, Cd was shifted to ion exchange sites, where it competes with Pb and possibly Ca (from the background electrolyte). Sorption on >SOH functional groups increased with increasing pH but was small compared to >FeOH sites, with little difference between single- and binary-metal systems. Model reactions and conditional sorption constants for Pb and Cd sorption were tested on a fourth soil that was not used for model optimization. The same reactions and constants were used successfully without adjustment by estimating surface site concentrations from soil mineralogy. The model formulation developed in this study is applicable to acidic mineral soils with low organic matter content. Extension of the model to soils of different composition may require selection of surface reactions that account for differences in clay and oxide mineral composition and organic matter content.     

Experimental and modelling studies of caesium sorption on illite

A natural illite (illite du Puy) was purified and converted to the homo-ionic Na form. The conditioned Na–illite was characterised in terms of its mineralogy, chemical inventory, and surface properties. The structural formula was determined from EDS analyses (SEM/TEM) and bulk chemistry. A cation exchange capacity of 127 mEq/kg was determined by the Na isotope dilution method at neutral pH.The sorption of Cs was measured as a function of NaClO₄ background electrolyte concentration (1.0, 0.1 and 0.01 M), Cs concentration and pH in the range ≈3 to ≈10. Before obtaining these measurements the kinetics of Cs uptake were determined at initial concentrations of 2 × 10⁻⁸ M and 7 × 10⁻⁵ M, representing the extremes of the range investigated, and was found to be concentration dependent. The supernatant solutions after centrifugation were analysed for major cations in all of the sorption tests.A two-site cation exchange model was developed to describe the sorption of Cs over the whole range of experimental conditions. The two-site types were termed frayed edge sites, FES (high affinity/low capacity) and type II sites (low affinity/high capacity). At low NaClO₄ concentrations, Cs sorption decreased at pH values less than neutral. This was interpreted in terms of competitive effects from H, and K released by the partial dissolution of illite, which cannot be avoided at low and high pH values. Selectivity coefficient values for Cs–Na, Cs–K, K–Na, and H–Na exchange equilibria on the FES sites, and Cs–Na exchange on the type II sites are given for illite together with the corresponding site capacities.     

Experimental measurements and modeling of sorption competition on montmorillonite

The source terms arising from radioactive/toxic metal waste repositories will contain a multitude of dissolved metal species, as do natural systems. The influence of sorption competition on the uptake of safety-relevant metals, and the effects this may have on transport rates to the biosphere, is an important repository performance assessment issue which has not, as yet, been resolved. The main aim of this work was to quantify the influence of competition between metals in different valence states on their individual sorption characteristics under conditions dominated by pH-dependent sorption. The sorption experiments were carried out on Na- and Ca-montmorillonites using various combinations and concentrations of Co(II), Ni(II), Zn(II), Eu(III), Nd(III), Am(III), Th(IV), and U(VI). For metals sorbing at trace concentrations in a background electrolyte containing a competing metal up to mmolar concentrations, and pH values generally greater than 6, all of the experimental results were consistent with the observation that metals with similar chemistries (valence state, hydrolysis behavior) compete with one another, but metals with dissimilar chemistries do not compete, i.e., competition is selective. For example Eu, Nd, and Am exhibit unambiguous sorption competition effects, as do Ni, Co, and Zn. On the basis of the above preliminary criteria, competition between divalent transition metals and trivalent lanthanides, Th(IV), and U(VI) and between Th (IV) and U(VI) would not be expected, and this is found experimentally. In general, neither single-fixed-site capacity models nor two-site (strong/weak) models with fixed capacities, whether with or without electrostatic terms, are capable of modeling the spectrum of experimental results presented here. To explain the competitive effects observed it is proposed that multiple sets of strong sites exist as subsets of the 40 mmol kg⁻¹ of weak sites present in the montmorillonite conceptual model. It is shown that if the 2SPNE SC/CE sorption model is extended to include multiple strong sites, and the average site capacity and protolysis constant values defined in previous publications are assigned to each of the sets of strong sites, then the model can be used to reproduce all of the experimental data, provided it can be specified which groups of metals are competitive and which are not.     

A model for trace metal sorption processes at the calcite surface: Adsorption of Cd2+ and subsequent solid solution formation

The rate of Cd²⁺ sorption by calcite was determined as a function of pH and Mg²⁺ in aqueous solutions saturated with respect to calcite but undersaturated with respect to CdCO₃. The sorption is characterized by two reaction steps, with the first reaching completion within 24 hours. The second step proceeded at a slow and nearly constant rate for at least 7 days. The rate of calcite recrystallization was also studied, using a Ca²⁺ isotopic exchange technique. Both the recrystallization rate of calcite and the rate of slow Cd²⁺ sorption decrease with increasing pH or with increasing Mg²⁺. The recrystallization rate could be predicted from the number of moles of Ca present in the hydrated surface layer.A model is presented which is consistent with the rates of Cd²⁺ sorption and Ca²⁺ isotopic exchange. In the model, the first step in Cd²⁺ sorption involves a fast adsorption reaction that is followed by diffusion of Cd²⁺ into a surface layer of hydrated CaCO₃ that overlies crystalline calcite. Desorption of Cd²⁺ from the hydrated layer is slow. The second step is solid solution formation in new crystalline material, which grows from the disordered mixture of Cd and Ca carbonate in the hydrated surface layer. Calculated distribution coefficients for solid solutions formed at the surface are slightly greater than the ratio of equilibrium constants for dissolution of calcite and CdCO₃, which is the value that would be expected for an ideal solid solution in equilibrium with the aqueous solution.     

Experimental modeling of platinum sorption on organic matter

In connection with the discovery of a new type of Pt deposit in low-rank brown coals and black shales, the interaction of Pt-bearing aqueous solutions with fractionated organic matter (asphaltenes and asphaltenic acids) was studied at 200–400°C and 1 kbar total pressure. It was found that chemical sorption onto the organic matter lowers Pt content in the aqueous solutions by about two orders of magnitude relative to organic-free systems. Thermal maturation of the asphaltenes leads to its aromatization and concomitant sorption of Pt from n×10⁻⁴ mPt (mol per kg of dry matter) at 200°C to n×10⁻² mPt at 400°C. Thus, the Pt chemisorption on activated carbonized organic matter may be an effective mechanism of Pt accumulation in C-bearing rocks.     

Kinetics of Cd sorption, desorption and fixation by calcite: A long-term radiotracer study

Time-dependent sorption and desorption of Cd on calcite was studied over 210 days utilizing ¹⁰⁹Cd as a tracer to distinguish between ‘labile’ and ‘non-labile’ forms of sorbed Cd. Stabilizing the calcite suspensions for 12 months under atmospheric P_CO2 and controlled temperature was necessary to reliably follow Cd dynamics following initial sorption. Results revealed time-dependant Cd sorption and marked desorption hysteresis by calcite under environmentally relevant conditions. Data obtained were fitted to a first-order kinetic model and a concentric shell diffusion model. Both models described the progressive transfer of Cd²⁺ to a less reactive form within calcite and subsequent desorption of Cd subject to different initial contact times. The kinetic model provided a better fit to the combined sorption and desorption data (R² = 0.992). It differentiates between two ‘pools’ of sorbed Cd²⁺ on calcite, ‘labile’ and ‘non-labile’, in which labile sorbed Cd is in immediate equilibrium with the free Cd²⁺ ion activity in solution whereas non-labile Cd is kinetically restricted. For the diffusion model (R² = 0.959), the rate constants describing Cd dynamics in calcite produced a half-life for Cd desorption of ∼175 d, for release to a ‘zero-sink’ solution. Results from this study allow comment on the likely mechanisms occurring at the calcite surface following long-term Cd sorption.     

Uptake of dissolved Cd by biogenic and abiogenic aragonite: a comparison with sorption onto calcite

The uptake of Cd²⁺ by aragonite and calcite is investigated by combining macroscopic measurements with some qualitative sorption experiments performed in a hydrogel medium. Both biogenic and abiogenic aragonites were studied in order to evaluate the process on materials with different textures. Assuming that sorption occurs by surface precipitation of metal-bearing solids, the gel produces a drastic decrease in the nucleation density, which allows for the precipitation of crystallites that are large enough to be analysed by scanning electron microscopy and characterized by glancing-incidence X-ray techniques. The macroscopic study reveals that aragonite is a powerful sorbent for cadmium in aqueous environments. Microscopic observations indicate that cadmium is sorbed onto aragonite by surface precipitation of (Cd, Ca)CO₃ solid solutions with a calcite-type structure. The precipitating individuals grow randomly oriented on the surface to reach sizes in the micrometre range. As a consequence, the concentration of cadmium in the aqueous solution decreases dramatically to values controlled by the low solubility of the cadmium-rich end member. This mechanism involves simultaneous dissolution-crystallization and is the same for both abiogenic and biogenic aragonites, the only difference being a result of the higher specific surface area of the biogenic starting material. Long-term uptake of cadmium by calcite occurs through a similar dissolution-crystallization mechanism, the final outcome being virtually the same, that is, surface precipitation of (Cd,Ca)CO₃ solid solutions. In this case, however, substrate and precipitate are isostructural and the process occurs by oriented overgrowth of thin lamellar crystallites, which spread to quickly cover the surface by a layer a few nanometers thick. This epitaxial layer armors the substrate from further dissolution, so that the process stops when only a small amount of cadmium has been removed from the fluid. As a result, the “sorption capacity” of calcite is considerably lower than that of aragonite. The study illustrates reaction pathways and “partial” equilibrium endpoints in surface-precipitation processes involving solid solutions.     

Diffusion of Li in olivine. Part I: Experimental observations and a multi species diffusion model

There are an increasing number of studies that focus on the systematics of the distribution of Li and its isotopes among different geochemical reservoirs. These studies have found that Li is relatively mobile compared to many other elements (e.g., Fe, Mg), and diffusion has been considered as a mechanism to generate large isotopic fractionations even at high temperatures. In order to quantify some of these aspects, we have measured Li diffusion rates experimentally along [0 0 1] of single crystals of olivines from San Carlos, Arizona and Pakistan, at 800-1200 °C at a total pressure of 100 kPa and fO₂ ≈ WM buffer. A complex diffusion behavior of Li is observed, indicating that two mechanisms of diffusion (a fast and a slower one) operate simultaneously. The behavior is well described by a model that partitions Li between two different sites in olivine - an octahedral site (Li_Me) and an interstitial site (Li_i). Transport of Li is a combination of hopping within and between each of these kinds of sites involving also vacancies on the octahedral site (V_Me). It is assumed that the homogeneous reaction (Li_Me = V_Me + Li_i) that maintains equilibrium distribution of Li between the sites is instantaneous compared to the timescales of all other processes associated with diffusive transport. One consequence of this mode of transport of Li in olivine is that the shape and length of diffusion profiles depend on the boundary conditions imposed at the surface of a crystal; i.e., the chemical environment (e.g., fO₂, aLi₄SiO₄), in addition to temperature and pressure. Our model describes the variable experimentally determined Li-profile shapes produced at different temperatures and with different boundary conditions, as well as their time evolution, quantitatively. Modeling the observed isotopic fractionation shows that ⁶Li diffuses about 5% faster than ⁷Li on the interstitial site. Inspection of published data on Li distribution in natural olivines that are available until now indicates that the fast (interstitial) mechanism of Li diffusion is unlikely to be dominant in most natural systems; Li rich, oxidizing environments (e.g., fluids?) may be exceptions. However, when it operates it can decouple the equilibration of Li isotopic gradients from the time scale of equilibration of overall Li concentrations. Diffusion dominated by the slower mechanism will occur on the average at a rate that is about an order of magnitude faster than diffusion of Fe, Mg and most other divalent cations in olivine; such diffusion of Li in olivine will be much slower than the rates of diffusion in clinopyroxene and plagioclase crystals at the same conditions. Fractionation of isotopes of Li by diffusion is likely to be a transient phenomenon and is more likely to be observed in crystals showing zoning of Li concentrations.     

岩石强度时效性演化模型

在一定的外界荷载作用下,岩石材料的强度会随时间不断降低,在工程上常表现为由于强度的弱化而导致岩体的突发性破坏行为以及岩体的长期强度等不同现象和问题。因此,岩石强度的时间效应研究对岩体工程施工安全和工程长期稳定性都具有重要的指导意义。在对大量试验结果分析的基础上,总结了岩石强度演化规律与内在机制,发现岩石强度的损失与岩石本身的固有强度、所受应力状态（屈服接近度）以及应力作用的持续时间有关,在此基础上,提出了以岩石凝聚力和内摩擦角随上述因素变化为核心的岩石强度时效性演化模型。通过对多组试验数据的模拟分析表明,提出的岩石强度时效性演化模型能很好地描述岩石强度的演化规律,可以较好地定量反映不同应力水平下岩石强度弱化过程,且物理意义明确,为岩石强度的时间效应研究开拓了一个新的思路和方法。     

Uranium(6+) sorption on montmorillonite: Experimental and surface complexation modeling study

Sorption interactions with montmorillonite and other clay minerals in soils, sediments, and rocks are potentially important mechanisms for attenuating the mobility of U(6+) and other radionuclides through the subsurface environment. Batch experiments were conducted (in equilibrium with atmospheric % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiiYdd9qrFfea0dXdf9vqai-hEir8Ve% ea0de9qq-hbrpepeea0db9q8as0-LqLs-Jirpepeea0-as0Fb9pgea% 0lrP0xe9Fve9Fve9qapdbaqaaeGacaGaaiaabeqaamaabaabcaGcba% acbiGaiWiG-bfadaWgaaWcbaacbaGaa43qaiaa+9eadaWgaaqaaiaa% +jdaaWqabaaaleqaaaaa!400D!\[P_{CO_2 } \])to determine the effects of varying pH (2 to 9), solid-mass to solution-volume ratio (M/V = 0.028 to 3.2 g/L), and solution concentration (2 × 10^–7 and 2 × 10^–6 M ²³³U) on U(6+) sorption on SAz-1 montmorillonite. The study focused on U(6+) surface complexation on hydroxylated edge sites as the sorption mechanism of interest because it is expected to be the predominant sorption mechanism at pHs typical of natural waters (pH 6 to 9). Thus, the experiments were conducted with a 0.1 M NaNO₃ matrix to suppress ion-exchange between U(6+) in solution and interlayer cations. The results show that U(6+) sorption on montmorillonite is a strong function of pH, reaching a maximum at near-neutral pH (6 to 6.5) and decreasing sharply towards more acidic or more alkaline conditions. A comparison of the pH-dependence of U(6+) sorption with that of U(6+) aqueous speciation indicates a close correspondence between U(6+) sorption and the predominance field of U(6+)-hydroxy complexes. At high pH, sorption is inhibited due to formation of aqueous U(6+)-carbonate complexes. At low pH, the low sorption values indicate that the 0.1 M NaNO₃ matrix was effective in suppressing ion-exchange between the uranyl (UO₂ ²⁺) species and interlayer cations in montmorillonite. At pH and carbonate concentrations typical of natural waters, sorption of U(6+) on montmorillonite can vary by four orders of magnitude and can become negligible at high pH.The experimental results were used to develop a thermodynamic model based on a surface complexation approach to permit predictions of U(6+) sorption at differing physicochemical conditions. A Diffuse-Layer model (DLM) assuming aluminol (>AlOH) and silanol (>SiOH) edge sites and two U(6+) surface complexation reactions per site effectively simulates the complex sorption behavior observed in the U(6+)-H₂O-CO₂-montmorillonite system at an ionic strength of 0.1 M and pH > 3.5. A comparison of model predictions with data from this study and from published literature shows good agreement and suggests that surface complexation models based on parameters derived from a limited set of data could be useful in extrapolating radionuclide sorption over a range of geochemical conditions. Such an approach could be used to support transport modeling by providing a better alternative to the use of constant K _d s in transport calculations.     

Processes and kinetics of Cd2+ sorption by a calcareous aquifer sand

The rate of Cd²⁺ sorption by a calcareous aquifer sand was characterized by two reaction steps, with the first step reaching completion in 24 hours. The second step proceeded at a slow and nearly constant rate for at least seven days. The first step includes a fast adsorption reaction which is followed by diffusive transport into either a disordered surface film of hydrated calcium carbonate or into pore spaces. After 24 hours the rate of Cd²⁺ sorption was constant and controlled by the rate of surface coprecipitation, as a solid solution of CdCO₃ in CaCO₃ formed in recrystallizing material. Desorption of Cd²⁺ from the sand was slow. Clean grains of primary minerals, e.g. quartz and aluminosilicates. sorbed much less Cd²⁺ than grains which had surface patches of secondary minerals, e.g. carbonates, iron and manganese oxides. Calcite grains sorbed the greatest amount of Cd²⁺ on a weight-normalized basis despite the greater abundance of quartz. A method is illustrated for determining empirical binding constants for trace metals at in situ pH values without introducing the experimental problem of supersaturation. The binding constants are useful for solute transport models which include a computation of aqueous speciation.     

Uranium(6+) sorption on montmorillonite: Experimental and surface complexation modeling study

Sorption interactions with montmorillonite and other clay minerals in soils, sediments, and rocks are potentially important mechanisms for attenuating the mobility of U(6+) and other radionuclides through the subsurface environment. Batch experiments were conducted (in equilibrium with atmospheric % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiiYdd9qrFfea0dXdf9vqai-hEir8Ve% ea0de9qq-hbrpepeea0db9q8as0-LqLs-Jirpepeea0-as0Fb9pgea% 0lrP0xe9Fve9Fve9qapdbaqaaeGacaGaaiaabeqaamaabaabcaGcba% acbiGaiWiG-bfadaWgaaWcbaacbaGaa43qaiaa+9eadaWgaaqaaiaa% +jdaaWqabaaaleqaaaaa!400D!\[P_{CO_2 } \])to determine the effects of varying pH (2 to 9), solid-mass to solution-volume ratio (M/V = 0.028 to 3.2 g/L), and solution concentration (2 × 10^?7 and 2 × 10^?6 M ²³³U) on U(6+) sorption on SAz-1 montmorillonite. The study focused on U(6+) surface complexation on hydroxylated edge sites as the sorption mechanism of interest because it is expected to be the predominant sorption mechanism at pHs typical of natural waters (pH ≈6 to ≈9). Thus, the experiments were conducted with a 0.1 M NaNO₃ matrix to suppress ion-exchange between U(6+) in solution and interlayer cations. The results show that U(6+) sorption on montmorillonite is a strong function of pH, reaching a maximum at near-neutral pH (≈6 to ≈6.5) and decreasing sharply towards more acidic or more alkaline conditions. A comparison of the pH-dependence of U(6+) sorption with that of U(6+) aqueous speciation indicates a close correspondence between U(6+) sorption and the predominance field of U(6+)-hydroxy complexes. At high pH, sorption is inhibited due to formation of aqueous U(6+)-carbonate complexes. At low pH, the low sorption values indicate that the 0.1 M NaNO₃ matrix was effective in suppressing ion-exchange between the uranyl (UO₂ ²⁺) species and interlayer cations in montmorillonite. At pH and carbonate concentrations typical of natural waters, sorption of U(6+) on montmorillonite can vary by four orders of magnitude and can become negligible at high pH. The experimental results were used to develop a thermodynamic model based on a surface complexation approach to permit predictions of U(6+) sorption at differing physicochemical conditions. A Diffuse-Layer model (DLM) assuming aluminol (>AlOH^?) and silanol (>SiOH^?) edge sites and two U(6+) surface complexation reactions per site effectively simulates the complex sorption behavior observed in the U(6+)-H₂O-CO₂-montmorillonite system at an ionic strength of 0.1 M and pH > 3.5. A comparison of model predictions with data from this study and from published literature shows good agreement and suggests that surface complexation models based on parameters derived from a limited set of data could be useful in extrapolating radionuclide sorption over a range of geochemical conditions. Such an approach could be used to support transport modeling by providing a better alternative to the use of constant K _d s in transport calculations.     

The sorption of toxic elements onto natural zeolite,synthetic goethite and modified powdered block carbon

Inorganic elements analyses of Carapicuíba lake reveal that As, Cr, Pb and Mn are above the recommended drinking water standards. The mean total concentrations of toxic elements in surface water decrease in the order Mn > Cr > Pb > As. At elevated concentrations, toxic elements like Cr can accumulate in soils and enter the food chain, leading to serious health hazards and threatening the long-term sustainability of the local ecosystem. Absorbing materials has often been used to improve water quality. In this investigation three types of material were studied: the natural zeolite (mordenite); synthetic goethite and the powdered block carbon modified. The adsorption of Pb²⁺ and Mn²⁺ onto natural zeolite as a function of their concentrations was studied at 24°C by varying the metal concentration from 100 to 400 mg L⁻¹ while keeping all other parameters constant. The low-cost zeolites removed Pb from water without any pretreatment at pH values <6. The maximum adsorption attained was as follows: Pb²⁺ 78.7% and Mn²⁺ 19.6%. The modified powdered block carbon effectively removed As(V) and Cr(VI) while goethite removed more chromate than arsenate in the pH range 5–6. Results of this study will be used to evaluate the application these materials for the treatment of the Carapicuíba lake’s water.     

Shock metamorphism of some rock-forming minerals: Experimental results and natural observations

The products of shock metamorphism in the Jänisjärvi astrobleme in Karelia, Russia, are compared with the results of experiments in which spherical converging shock waves affected a spherical rock sample. The sample was loaded by a broad spectrum of shock pressures, which increased from ～20 GPa at the periphery of the rock sphere to > 200 GPa at its center. Experiments with rocks metamorphosed under the effect of spherical converging shock waves imitate collisions of cosmic bodies with the Earth’s surface, when transformations in rocks and minerals are induced by a single impact event. The shock-thermal decomposition of mafic minerals occurs in the same succession in nature and the experiments, with some differences between natural and experimentally produced shock-thermal aggregates likely accounted for by the smaller sizes of the experimental impact rock sample and, correspondingly, its more rapid quenching. Our shock experiments were the first to synthesize ringwoodite that was rich in Al₂O₃ and should be referred to as aluminous ringwoodite. The mineral was produced not via the martensite transition of olivine but by means of biotite replacement coupled with the migration of elements. The transformations of minerals by shock waves (amorphization and shock-thermal decomposition) were determined to be controlled mainly by the crystal structures of these minerals. The experimental products provide evidence of the migration of chemical elements within the crystal structure. The structural setting of ions in a mineral determines the onset of element migrations and the intensity of this process.     

Effects of spatial data resolution on runoff predictions by the BASINS model

The BASINS model, developed by the United States EPA, is a popular simulation tool for predicting watershed responses, such as runoff, pollution exports, and water quality. It requires large amounts of data to set parameters. Many studies state that model input is a major source of model uncertainty. Thus, improvements to the quality and completeness of the data will improve the certainty of the model. The objective of this study is to discuss the effects of spatial data, including digital elevation models (DEMs) and spatial rainfall records, on predictions of runoff from the BASINS model. The result shows that both DEMs and rainfall data can significantly influence peak flow and runoff volume. Rainfall input has more influence on the curve shape of hydrograph than DEM resolution. DEM resolution can have more impact on peak flow predictions than rainfall input. Because the model uncertainties from DEMs and rainfall records influence each other, the prediction error does not always decrease when DEM resolution increases. The present results show that the BASINS model produces reliable answers in the case area when the grid size is less than 100 m × 100 m and the precipitation records from the Bihu Rainfall Station are correct and complete.     

Self-limiting growth on dolomite: Experimental observations with in situ atomic force microscopy

In situ Atomic Force Microscopy (AFM) and Lateral Force Microscopy (LFM) studies on dolomite (101?4) were performed during exposure to supersaturated aqueous solutions (supersaturated in dolomite, calcite, aragonite, vaterite, huntite and magnesite) at pH = 9 at various Ca²⁺/Mg²⁺ aqueous ion activity ratios. At high saturation ratios, rapid growth of a single layer (∼3 Å thick) of a carbonate followed by much slower growth of a second layer was observed. Growth of the second layer was highly inhibited, suggesting that the first layer was essentially self-limited, and inhibited further layer-by-layer growth. The growth of the first layer was observed over a wide range of Ca²⁺/Mg²⁺ ratios, suggesting that the dolomite surface is favorable to formation of a range of Ca-Mg carbonates. LFM data revealed contrast in the tip-surface frictional forces on the first grown layer, but this contrast was only observed in layers grown from middle to high Ca²⁺/Mg²⁺ solutions. Thus, LFM may have detected or responded to differences in the structure and/or composition between the first layer relative and the dolomite substrate. Dissolution of the first layer occurred from significantly supersaturated solutions relative to ordered stoichiometric dolomite permitting an estimate of the excess interfacial strain energy of up to 10 mJ/m².     

Experimental observations on carbon isotope exchange in carbonate-water systems

This study presents data from experiments investigating carbon isotope exchange between carbonate solution and solid calcite using carbon-13 as a tracer. All experiments were done with calcite saturated solutions and results show that a two-step adsorption-recrystallization reaction takes place. Isotope effects are caused by exchange by carbonate on the solid surface with carbon in the aqueous phase. Adsorption reactions are characterized by a maximum isotopic exchange capacity (IEC) on crystal surfaces of about 10¹¹ reaction sites per cm², following a second order rate law with respect to ¹³C concentration in solution ($\text{constant}\text{kex ? 10}{}^6\text{cm}{}^5\text{mole}{}^{\mathrm{?1}}\text{s}{}^{\mathrm{?1}}$ and $\text{half-life}\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 700}\text{s}$). The adsorption reaction was followed by a first order recrystallization which is characterized by a rate constant of the order of 10^?8 s^?1 and a $\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ of 10⁷ s. Negative isotopic gradient experiments and runs with calcite crystals in Mg²⁺ spiked solutions provided the preliminary basis for the characterization of the mechanisms of both proposed reactions.