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.     

Seasonal dynamics of CO2 profiles across a soil chronosequence,Santa Cruz,California

Concentrations of CO₂ in soil atmosphere and CO₂ efflux were measured across a marine terrace soil chronosequence near Santa Cruz, California. Soil development, specifically the formation of an argillic horizon, has created a two-tier soil gas profile in the older terrace soils. The soil above the argillic horizon has seasonal variations in soil CO₂ associated with plant respiration. The older soils with dense argillic horizons maintain a year round ～1%CO₂ below the argillic horizon. The CO₂efflux during the growing season is higher on the older terraces.     

Phase shift interference microscope study of dissolution-precipitation processes of nonhydrostatically stressed halite crystals in solution

Halite single crystals in saturated solution were used to study dissolution precipitation creep (DPC) at conditions where plastic deformation is negligible. Specifically, the free unloaded surfaces of these crystals were investigated by a novel Linnik-based phase shift interference microscope. The method allows observations of the crystal surface in-situ and with an axial resolution in the nanometer scale. Transport phenomena in open systems, temperature gradients, and gradients in strain energy density were found to cause morphological changes on the free crystal surface by dissolution/reprecipitation. We did not find evidence for DPC by applying a homogeneous stress field to the crystal as long as plastic deformation was avoided. These findings suggest that deformation of rocks by DPC in situations where dislocation creep is not activated, but is rather promoted by fluid transport through the rock or by episodic changes of extensive parameters affecting solubility than by homogeneous stress alone.Editorial responsibility: J. Hoefs     

Apophyllite (001) surface alteration in aqueous solutions studied by HAFM

Depending on pH and temperature, two different types of surface reactions occur on the apophyllite (001) surface in aqueous HCl-solutions at temperatures from 20 to 130 °C. At low pH, laterally spreading hillocks cover the surface. The hillocks are softer than the pristine surface, chemical analysis shows a depletion in Ca + K, and the spreading velocity of hillocks depends on pH. This indicates a change in chemical bond strength, non-stoichiometric dissolution and a mechanism involving protons. External disturbances such as the AFM scanning tip cause the upper surface layers to peel off revealing that the active sites of hillock formation are between the silicate layers of apophyllite. The observed process can therefore be described by a penetrative ion-replacement reaction which proceeds well below the surface monolayer. By this ion-replacement, the silicate layers eventually become destabilised. The observed reaction, therefore, is equivalent to an incongruent dissolution process. Despite structural similarities, this process is only superficially similar to the ion-exchange occurring in clay minerals or zeolites. In these minerals, the structural backbone is not destabilized. At a more neutral pH and high temperatures, step retreat and etch pit formation can be observed on the apophyllite (001) surface thus indicating a more congruent dissolution mechanism.     

Lake morphometry and wind exposure may shape the plankton community structure in acidic mining lakes

Acidic mining lakes (pH <3) are specific habitats exhibiting particular chemical and biological characteristics. The species richness is low and mixotrophy and omnivory are common features of the plankton food web in such lakes. The plankton community structure of mining lakes of different morphometry and mixing type but similar chemical characteristics (Lake 130, Germany and Lake Langau, Austria) was investigated. The focus was laid on the species composition, the trophic relationship between the phago-mixotrophic flagellate Ochromonas sp. and bacteria and the formation of a deep chlorophyll maximum along a vertical pH-gradient. The shallow wind-exposed Lake 130 exhibited a higher species richness than Lake Langau. This increase in species richness was made up mainly by mero-planktic species, suggesting a strong benthic/littoral - pelagic coupling. Based on the field data from both lakes, a nonlinear, negative relation between bacteria and Ochromonas biomass was found, suggesting that at an Ochromonas biomass below 50 μg C L⁻¹, the grazing pressure on bacteria is low and with increasing Ochromonas biomass bacteria decline. Furthermore, in Lake Langau, a prominent deep chlorophyll maximum was found with chlorophyll concentrations ca. 50 times higher than in the epilimnion which was build up by the euglenophyte Lepocinclis sp. We conclude that lake morphometry, and specific abiotic characteristics such as mixing behaviour influence the community structure in these mining lakes.     

Dissolution rates and activation energy for dissolution of brucite (001) : A new method based on the microtopography of crystal surfaces

Scanning Force Microscopy (SFM) was used to develop a method which can provide quantitative kinetic data of crystal growth and dissolution. Based on observations of single crystal faces in monolayer resolution, morphology and temperature dependent growth and dissolution rates can be obtained. From these kinetic data activation energies can be calculated and compared with existing theories. The experimental method works by extracting grown or dissolved terrace areas and step densities from image sequences taken at different temperatures. As an example, the method is applied for dissolution on the brucite (001) surface in acidic water (pH 2.7) within the temperature range of 21 to 35°C. At these conditions the dissolution rate depends nonlinearly on the step density and gives evidence for interstep interaction. The calculated activation energy for dissolution is 60 ± 12 kJ mol⁻¹. With this high activation energy, dissolution cannot be regarded as a transport-controlled process, and is therefore surface controlled.     

Magnesite growth rates as a function of temperature and saturation state

Magnesite growth rates and step velocities have been measured systematically as a function of temperature from 80 to 105 °C and saturation state in 0.1 M NaCl solutions using hydrothermal atomic force microscopy (HAFM). The observations indicate that at these conditions magnesite precipitation is dominated by the coupling of step generation via spiral growth at screw dislocations and step advancement away from these dislocations. As these two processes occur in series the slowest of these dominates precipitation rates. At 100 °C magnesite growth rates (r) determined by HAFM are consistent with

r=k(Ω-1)²,