Simon Emmanuel

Implications from concentrations and isotopic data for Pb partitioning processes in soils

Abstract Lead concentrations and stable isotopic measurements were examined in the different chemical fractions of Czech forest soils to investigate the mechanisms of Pb partitioning. A method of selective sequential dissolution (SSD) was employed that distinguished between five different fractions: exchangeable, surface bound, organic matter, Fe-oxides, and silicates (non-labile). From an analysis of the concentrations and isotopic compositions associated with the different fractions, it is apparent that Pb in the deep Czech mineral soils is of predominantly natural origin and is primarily associated with silicates (69–81%) and Fe-oxides (11–19%). Natural Pb associated with surface bound and organic matter fractions in mineral soils accounts for only 7 to 15%. Anthropogenic Pb in the Czech soils is concentrated primarily in the organic horizons and is strongly associated with the surface-bound and organic matter fractions in which the proportion of total Pb is 33 to 50% and 23 to 47%, respectively. At high and low levels of contamination, Pb isotopic signatures within the labile fractions of the same soil samples are generally homogenous, although a degree of heterogeneity among these fractions is noted in samples of intermediate degrees of contamination. Such heterogeneity probably reflects different levels of natural and anthropogenic Pb mixing. Determination of the mass-normalized affinity of Pb to the primary components using solid-solution distribution coefficients suggests that in Czech forest soils, the order of affinity may be summarized as Fe-oxides > organic matter > silicates. A similar treatment of the data reported for semiarid Mediterranean soils indicates the prevailing order to be Fe-oxides > carbonates > organic matter > silicates. The general similarity of the behaviour of Pb with respect to the different soil components in both temperate and semiarid soils suggests that these orders of affinity may have wider significance for a variety of other soil types.

Nanograins form carbonate fault mirrors

Many faults are characterized by naturally polished, reflective, glossy surfaces, termed fault mirrors (FMs), that form during slip. Recent experiments also find that FMs form during rapid sliding between rock surfaces, and that FM formation coincides with pronounced friction reduction. The structure of FMs and the mechanism of their formation are thus important for understanding the mechanics of frictional sliding, particularly during earthquakes. Here we characterize the small-scale structure of natural carbonate FMs from three different faults along a tectonically active region of the Dead Sea transform. Atomic force microscopy measurements indicate that the FMs have extremely smooth surface topography, accounting for their mirror-like appearance. Electron microscope characterization revealed a thin (

Limestone weathering rates accelerated by micron-scale grain detachment

The weathering of carbonate rocks plays a critical role in the evolution of landscapes, the erosion of buildings and monuments, and the global-scale shifting of carbon from the atmosphere to the ocean. Chemical dissolution is often assumed to govern the rates of weathering of carbonate rocks, although some studies have suggested that mechanical erosion could also play an important role. Quantifying the rates of the different processes has proved challenging, in part due to the high degree of variability encountered across different scales in both field and laboratory conditions. To constrain the rates and mechanisms controlling long-term limestone weathering, we analyze a lidar scan of the Western Wall, a Roman-period edifice located in Jerusalem. We find that extreme erosion rates in fine-grained micritic limestone blocks are as much as two orders of magnitude higher than the average rates estimated for coarse-grained limestone blocks at the same site. Atomic force microscope imaging of dissolving micritic limestone suggests that these elevated reaction rates are likely to be the result of rapid dissolution along micron-scale grain boundaries, followed by mechanical detachment of tiny particles from the surface. Our analysis indicates that such grain detachment could be the dominant erosional mode for fine-grained carbonate rocks in many regions on Earth.

Calcite dissolution rates in texturally diverse calcareous rocks

Abstract The injection of reactive fluids into carbonate reservoirs during enhanced recovery operations can induce important changes in rock permeability. However, reliably predicting these changes requires accurate knowledge of calcite reaction rates. While numerous studies have examined calcium carbonate dissolution rates, most have focused on pure calcite crystals rather than actual rocks. In this study, two types of flow-through experiments were carried out to determine the calcite dissolution rates in texturally diverse calcareous rocks: the first type of experiment had a duration of 3 days, while the second type ran for 3 months. Our experiments show that rocks with differing textures and roughness (samples included coarse-grained oolitic limestone, fine-grained Solnhofen limestone, marble and calcite spar) do in fact dissolve by different mechanisms. However, despite these differences, bulk reaction rates were found to be remarkably similar (with a relative standard deviation of <20%) and consistent with previously reported reaction rates for calcite. Thus, our results suggest that textural differences between rock types are unlikely to have an important impact on overall reaction rates in fractured carbonate reservoirs.

Softening of organic matter in shales at reservoir temperatures

The elastic modulus of organic matter can strongly influence the mechanical behaviour of source rocks. Although recent advances have shed crucial light on the mechanical properties of natural organic matter under ambient conditions, the elastic properties of kerogen and bitumen at reservoir temperatures remain poorly constrained. In this paper, we use a novel atomic force microscope technique to measure the changes to organic matter during the heating of an organic-rich shale. Our measurements show that bitumen becomes more compliant with heating and in an experiment during which the temperature was increased from 25 to 225°C, the reduced elastic modulus dropped from 6.3 to 0.8 GPa. In contrast to bitumen, we were unable to discern any significant changes to the elastic modulus of kerogen with increasing temperature. Our results suggest that the temperature dependence of the elastic properties could be used as an additional method to differentiate between bitumen and kerogen in shales. Moreover, our analysis indicates that temperature should be taken into account when modelling the elastic properties of bitumen under reservoir conditions.

Weathering resistance of carbonate fault mirrors promotes rupture localization

Fractured rocks in fault zones regain their mechanical strength through a process called healing. A central pathway for healing involves the dissolution and reprecipitation of minerals in the fault zone which cements the fractured rocks during interseismic periods. However, some faults contain highly polished surfaces—coated in a thin nanoparticle layer—along which slip is localized. Crucially, these surfaces show little evidence of postseismic mineralization and healing. Here we use atomic force microscopy to show that naturally polished rocks from carbonate fault zones are resistant to dissolution, in stark contrast to the reactive minerals that make up the fault breccia. Our results suggest that the low reactivity of the nanoparticle layer could retard healing, helping to maintain the localization of the fault zone between seismic slip events. As fault localization affects seismic motion, the geochemical reactivity of fault mirrors could be an important control on seismicity along faults.

Release of Particulate Iron Sulfide during Shale-Fluid Interaction

During hydraulic fracturing, a technique often used to extract hydrocarbons from shales, large volumes of water are injected into the subsurface. Although the injected fluid typically contains various reagents, it can become further contaminated by interaction with minerals present in the rocks. Pyrite, which is common in organic-rich shales, is a potential source of toxic elements, including arsenic and lead, and it is generally thought that for these elements to become mobilized, pyrite must first dissolve. Here, we use atomic force microscopy and environmental scanning electron microscopy to show that during fluid-rock interaction, the dissolution of carbonate minerals in Eagle Ford shale leads to the physical detachment, and mobilization, of embedded pyrite grains. In experiments carried out over a range of pH, salinity, and temperature we found that in all cases pyrite particles became detached from the shale surfaces. On average, the amount of pyrite detached was equivalent to 6.5 × 10-11 mol m-2 s-1, which is over an order of magnitude greater than the rate of pyrite oxidation expected under similar conditions. This result suggests that mechanical detachment of pyrite grains could be an important pathway for the mobilization of arsenic in hydraulic fracturing operations and in groundwater systems containing shales.