ALBERT

Description: X-ray absorption spectroscopy, scanning electron microscopy (SEM) and X-ray diffractometry (XRD) have been used to study the solid-phase speciation of Zn in urban road dust sediments (RDS) in Manchester, UK. X-ray absorption near-edge structure (XANES) analysis using linear combination modelling suggest that the soluble species Zn(NO3)2{middle dot}6H2O and ZnCl2 represent 70-83%, and Zn-sorbed goethite 17-30%, of the Zn species present. The presence of goethite is not corroborated by extended X-ray absorption fine structure (EXAFS) modelled first shell scattering Zn-O distances of 2.01-2.03 A, but this may be due to distortion of the Zn octahedra on the goethite surface, or the existence of Zn-sorbed species with other metal hydrous oxides, as inferred by the EXAFS-modelled second shell Fe and Al scatterers. Analysis by EXAFS also suggests that metallic Zn-Cu-Sn-Pb and Zn-silicate phases are present in the RDS, and this is corroborated by SEM and XRD. Other phases suggested by EXAFS include ZnO, franklinite, Zn-sorbed birnessite and zinc formate. Differences between the XANES and other results suggest that model compounds such as Zn-bearing phyllosilicates and metallic Zn phases may have been missing from the XANES fitting. Long-term low-level exposure to the RDS Zn phases identified may lead to an increased risk of cardiovascular or pulmonary diseases.

Description: Diagenesis significantly impacts mudstone lithofacies. Processes operating to control diagenetic pathways in mudstones are poorly known compared to analogous processes occurring in other sedimentary rocks. Selected organic-carbon-rich mudstones, from the Kimmeridge Clay and Monterey Formations, have been investigated to determine how varying starting compositions influence diagenesis. The sampled Kimmeridge Clay Formation mudstones are organized into thin homogenous beds, composed mainly of siliciclastic detritus, with some constituents derived from water-column production (e.g., coccoliths, S-depleted type-II kerogen, as much as 52.6% total organic carbon [TOC]) and others from diagenesis (e.g., pyrite, carbonate, and kaolinite). The sampled Monterey Formation mudstones are organized into thin beds that exhibit pelleted wavy lamination, and are predominantly composed of production-derived components including diatoms, coccoliths, and foraminifera, in addition to type-IIS kerogen (as much as 16.5% TOC), and apatite and silica cements. During early burial of the studied Kimmeridge Clay Formation mudstones, the availability of detrital Fe(III) and reactive clay minerals caused carbonate- and silicate-buffering reactions to operate effectively and the pore waters to be Fe(II) rich. These conditions led to pyrite, iron-poor carbonates, and kaolinite cements precipitating, preserved organic carbon being S-depleted, and sweet hydrocarbons being generated. In contrast, during the diagenesis of the sampled Monterey Formation mudstones, sulfide oxidation, coupled with opal dissolution and the reduced availability of both Fe(III) and reactive siliciclastic detritus, meant that the pore waters were poorly buffered and locally acidic. These conditions resulted in local carbonate dissolution, apatite and silica cements precipitation, natural kerogen sulfurization, and sour hydrocarbons generation. Differences in mud composition at deposition significantly influence subsequent diagenesis. These differences impact their source rock attributes and mechanical properties.

Description: As the fastest growing energy sector globally, shale and shale reservoirs have attracted the attention of both industry and scholars. However, the strong heterogeneity at different scales and the extremely fine-grained nature of shales makes macroscopic and microscopic characterization highly challenging. Recent advances in imaging techniques have provided many novel characterization opportunities of shale components and microstructures at multiple scales. Correlative imaging, where multiple techniques are combined, is playing an increasingly important role in the imaging and quantification of shale microstructures (e.g. one can combine optical microscopy, scanning electron microscopy/transmission electron microscopy and X-ray radiography in 2D, or X-ray computed tomography and electron microscopy in 3D). Combined utilization of these techniques can characterize the heterogeneity of shale microstructures over a large range of scales, from macroscale to nanoscale ( c. 10 0 –10 –9 m). Other chemical and physical measurements can be correlated to imaging techniques to provide complementary information for minerals, organic matter and pores. These imaging techniques and subsequent quantification methods are critically reviewed to provide an overview of the correlative imaging workflow. Applications of the above techniques for imaging particular features in different shales are demonstrated, and key limitations and benefits summarized. Current challenges and future perspectives in shale imaging techniques and their applications are discussed.

Description: An understanding of the nature and scales of diagenetic variability within organic-rich mudstones is critical to the accurate assessment of shale-gas reservoir properties, as well as for elucidating chemical evolution pathways within mudstones. Here we integrate field observations with thin section descriptions (optical and electron optical techniques) and mineralogical data for the Blackhawk Member time-equivalent Mancos Shale in Book Cliffs, Utah, to determine the impacts of early and burial diagenesis on this mudstone succession. The detrital assemblage in the Mancos Shale comprises quartz-silt, feldspar, clay minerals, dolomite and organic matter (TOC of 1 to 2.5%). Biogenic silica is negligible. Field mapping reveals laterally continuous (km scale), ferroan dolomite cemented units up to 0.3 m thick, are present. These cemented units cap both coarsening-upward units (1 to 3 m thick), and stacked successions of coarsening-upward units (5 to 15 m thick). These upward-coarsening sediment packages, capped by dolomite cemented strata, correlate to bedsets and parasequences in updip settings. Pervasive cementation in these dolomite-cemented units is likely to have occurred prior to compaction as a result of bacterially mediated respiratory processes. Cementation at these levels is particularly evident because cement precipitation occurred during breaks in sediment accumulation below marine flooding surfaces. The abundance of dolomite cements highlights the importance of macroscopic-scale diagenetic carbonate mobility in these mudstones. In addition to carbonate-cements, diagenetic alteration and precipitation of quartz and aluminasilicate minerals are also important in these mudstones. Kaolinite is present both in uncompacted test of organisms and as vein fills in septarian concretions. Kaolinite precipitation is interpreted to have occurred prior to significant compaction and indicates that both silicon and aluminium were mobile during early diagenesis. We interpret the abundance of early diagenetic kaolinite cement to be the result of Al-mobilization by organic acids generated during organic matter oxidation reactions, with the Al sourced from poorly crystalline detrital aluminium oxides and clay minerals. There is also indirect evidence for burial diagenetic kaolinitization of feldspar grains. Quartz cement takes the form of quartz overgrowths and microcrystalline quartz crystals. Textures and CL spectra for the quartz microcrystalline cement suggests that recrystallization of biogenic silica (opal-A) was likely to have been an important source for quartz cements, although smectite-to-illite transformation may have contributed some. These mineral phases highlight that microscopic-scale diagenetic mobility of silica is important, even within mudstones lacking obvious sources of biogenic silica and is likely to be an important processes in a wide range of mudstones.

Description: Several field and laboratory studies have demonstrated that secondary Fe-bearing minerals such as goethite, lepidocrocite and mackinawite have a high capacity for the uptake of As, but little work has been carried out to examine the capacity of the mineral vivianite [Fe3(PO4)2·8H2O] for this element. We report here preliminary results of an experimental study designed to test the efficiency of As(III) and As(V) uptake by natural vivianite at acid, near-neutral and alkaline pH at T = 4ºC, which is representative of Lake Baikal-type environments, where natural vivianite is reported to occur. The vivianite takes up between 0 and 5% As(III), and between 21 and 45% As(V), from 200 ppb solutions of these As species. Further work at 25ºC and other solution concentrations, together with characterization of the post-sorption solids, will yield information on the efficiencies and mechanisms of As uptake by natural vivianite.

Description: X-ray absorption spectroscopy, scanning electron microscopy (SEM) and X-ray diffractometry (XRD) have been used to study the solid-phase speciation of Zn in urban road dust sediments (RDS) in Manchester, UK. X-ray absorption near-edge structure (XANES) analysis using linear combination modelling suggest that the soluble species Zn(NO3)2·6H2O and ZnCl2 represent 70—83%, and Zn-sorbed goethite 17—30%, of the Zn species present. The presence of goethite is not corroborated by extended X-ray absorption fine structure (EXAFS) modelled first shell scattering Zn—O distances of 2.01—2.03 Å, but this may be due to distortion of the Zn octahedra on the goethite surface, or the existence of Zn-sorbed species with other metal hydrous oxides, as inferred by the EXAFS-modelled second shell Fe and Al scatterers. Analysis by EXAFS also suggests that metallic Zn-Cu-Sn-Pb and Zn-silicate phases are present in the RDS, and this is corroborated by SEM and XRD. Other phases suggested by EXAFS include ZnO, franklinite, Zn-sorbed birnessite and zinc formate. Differences between the XANES and other results suggest that model compounds such as Zn-bearing phyllosilicates and metallic Zn phases may have been missing from the XANES fitting. Long-term low-level exposure to the RDS Zn phases identified may lead to an increased risk of cardiovascular or pulmonary diseases.