Towards the establishment of a reliable proxy for the reactive surface area of smectite

Reactive surface area is one of the key parameters for studying the kinetics of mineral dissolution. The common practice in experimental kinetics is to normalize the dissolution rate to the surface area measured by the BET method. The relationship between BET surface area and the reactive surface area is not trivial in minerals such as smectites, which possess both internal and external surface areas, and in which the dissolution is controlled by the chemical attack on the edge surface. The present study examines two proxies for the reactive surface area of the Clay Mineral Society reference smectite SAz-1: BET surface area and the edge surface area measured using AFM.Since smectites are very microporous, their BET surface area is strongly influenced by the degassing procedure. It is demonstrated that outgassing the smectite powder at 135°C in a 15 mL min⁻¹ N₂ gas flow for at least 24 hours minimizes contribution from micropores to less than 11% of the BET surface area.Following dissolution experiments in solutions with a low electrolyte concentration, the BET surface area increased from 34 ± 2 m² g⁻¹ in raw SAz-1 to 127 ± 13 m² g⁻¹ in SAz-1 sample recovered from dissolution experiments. This increase in BET surface area is explained by a decrease in the average size of the smectite aggregates, and by an increase in microporosity due to the depletion in the major interlayer cation, i.e., Ca²⁺. As the BET surface area of the raw smectite sample includes considerably less microporosity compared to the BET surface area of the smectite recovered from dissolution experiments, the former is a better approximation of the external surface area of the dried sample powder.AFM measurements show that there is no correlation between the specific external surface area of the sample and its specific edge surface area. This observation is explained by the platy morphology of the smectite particle in which the specific external surface area depends linearly on the height reciprocal, whereas the specific edge surface area is independent of the particles height and depends linearly on the sum of the reciprocals of the length of the axes. Therefore, there is no reason to expect a correlation between the BET and the edge surface area. Our results show that the edge surface area (4.9 ± 0.7 m² g⁻¹) of the smectite particles cannot be predicted based on its external surface area (136 ± 20 m² g⁻¹). Therefore, the BET surface area cannot serve as a proxy for the reactive surface area. We suggest using AFM measurements of the specific edge surface area as an alternative proxy for the reactive surface area of smectite.     

Construing and constructing the South China Sea beyond state-led environmentalism: Vernacularizing geographical,geopolitical and sociotechnical imaginaries of territory

During the 2010s, the South China Sea (SCS) became a geopolitical flashpoint over the sovereignty of the Paracels and Spratlys. China envisioned its transformation of coral reefs into military bases and island cities as an SCS ‘green construction’ project. This article analyses how the SCS is discursively construed and practically constructed as maritime national territory, by mobilizing fishing legacies and extending state limits through ‘state-led environmentalism’ rhetoric. Drawing on ethnographic fieldwork in China, I show that state-led environmentalism is a hierarchical process that intermittently co-opts and excludes local populations to advance the state's territorial ambitions, which are anchored in geographical, geopolitical and socio-technical imaginaries of ‘maritime civilization’. Yet, I also show that in this process, the SCS emerges as spaces of vernacularized political claims. Thus, I argue that territory is not only a political technology of control but also vernacular practice through which universalizing discourses— whether on the Exclusive Economic Zone regime, sovereignty or nature—are adapted and modified.     

Automatic estimation of olive tree dendrometric parameters based on airborne laser scanning data using alpha-shape and principal component analysis

The aim of this study is to present an automatic approach for olive tree dendrometric parameter estimation from airborne laser scanning (ALS) data. The proposed method is based on a unique combination of the alpha-shape algorithm applied to normalized point cloud and principal component analysis. A key issue of the alpha-shape algorithm is to define the α parameter, as it directly affects the crown delineation results. We propose to adjust this parameter based on a group of representative trees in an orchard for which the classical field measurements were performed. The best value of the α parameter is one whose correlation coefficient of dendrometric parameters between field measurements and estimated values is the highest. We determined crown diameters as principal components of ALS points representing a delineated crown. The method was applied to a test area of an olive orchard in Spain. The tree dendrometric parameters estimated from ALS data were compared with field measurements to assess the quality of the developed approach. We found the method to be equally good or even superior to previously investigated semi-automatic methods. The average error is 19% for tree height, 53% for crown base height, and 13% and 9% for the length of the longer diameter and perpendicular diameter, respectively.     

Reaction of soil enzymes and spring barley to copper chloride and copper sulphate

Study was carried out to compare the effect of the degree of contamination of soil with copper on the soil enzyme activity, depending on the type of chemical compound with which a metal reaches the soil and on the method of soil use. An effect of increasing doses of copper on growth and the development of spring barley has been studied. The study was carried out as a pot experiment on two types of soil: loamy sand and light loam. Copper was introduced to soil as copper(II) sulphate(VI) and copper(II) chloride at four doses: 150, 300, 450 and 600 mg Cu²⁺ kg^?1 d.m. of soil. Soil without copper was used as a control sample. The experiment showed that contamination of soil with copper applied as CuCl₂ and CuSO₄·5H₂O upset the homeostasis of soil. Dehydrogenases and urease were the most sensitive to contamination of soil with Cu²⁺, both as copper(II) chloride and as copper(II) sulphate(VI), and acid phosphatase and alkaline phosphatase were the least sensitive. Greater changes in enzymatic activity were observed in loamy sand than in light loam. The differences in the impact of copper(II) sulphate(VI) and copper(II) chloride on the soil microbiome were relatively small, because mean ED₅₀ for copper(II) chloride was 341 mg Cu²⁺ kg^?1 d.m. of soil, and for copper(II) sulphate(VI) it was 364 mg Cu²⁺ kg^?1 d.m. of soil. This inhibitory effect of copper persisted throughout the period of the experiment. The sensitivity of spring barley to copper compounds was lower than the enzymes under study.     

Tight Reservoir Properties Derived by Nuclear Magnetic Resonance,Mercury Porosimetry and Computed Microtomography Laboratory Techniques. Case Study of Palaeozoic Clastic Rocks

Results of the nuclear magnetic resonance (NMR) investigations, mercury porosimetry measurements (MP) and computed microtomography (micro-CT), applied to the tight Palaeozoic rocks from the depths lower than 3000 m, were presented to estimate their reservoir potential. NMR signal analysis and interpretation were performed. Based on NMR driven models, permeability and Free Fluid Index were calculated for data sets divided into homogeneous clusters. Computerized mercury porosimetry results visualization and processing provided useful information, as the automatically determined Swanson parameter is correlated with petrophysical properties of rocks. Micro-CT enriched the image of porous space in qualitative and quantitative ways. Homogeneity of pore space structure was discussed using micro-CT approach. Integration of the results in the frame of reservoir parameters from standard laboratory methods and the modern ones resulted in the improvement of methodology for determining the old, deep-seated, hard sedimentary rocks reservoir potential.     

Evaluating the impact of increasing temperatures on changes in Soil Organic Carbon stocks: sensitivity analysis and non-standard discrete approximation

Computational Geosciences - The SOC change index, defined as the normalized difference between the actual Soil Organic Carbon and the value assumed at an initial reference year, is here tailored to...