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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 alumina-silicate 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.

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.

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.

A B S T R A C T: A thin (15-20 cm) Fe-rich intraformational conglomerate in the fresh- to brackishwater Early Cretaceous succession of south-east England contains pisoids and pseudo-ooids of a green clay mineral which has been identified as berthierine. The pisoids (up to 0-5 cm in size) are concentrically laminated, have complex structure, and are frequently nucleated around a sandstone fragment. They show evidence of weathering due to a change in their environment after formation. The ooids have well to moderately well developed concentric lamination, are very often multinucleated and do not always completely cover the nucleus. They suggest formation as a result of mineral precipitation as opposed to agitation and accretion. The climate and environment during the Wealden were suited to the formation of Fe-rich soils and it is likely that the pisoids and ooids were originally composed of iron oxyhydroxide and kaolinite, having formed in soil in the Weald Basin. They were then eroded and deposited in the base of a large scour structure as part of the conglomerate. On burial, and the attainment of low Eh conditions, berthierine formed by diagenetic transformation of the pre-existing minerals. Berthierine is a trioctahedral Fe-rich clay mineral with the general formula X3Y205(OH)4 , where X = Fe, Mg or ALl, and Y = Si or A1. It has a 1 : 1 type structure and a basal spacing of 7 A, and is related to the kaolinite-serpentine subgroup of clay minerals. It is a common mineral in marine oolitic ironstones (see Van Houten & Purucker, 1984 for a review), but reports of berthierine in non-marine sediments are very few. Thurrel etal. (1970) described an example of berthierine (which they named chamosite, but this term is now properly restricted to an Fe-rich chlorite with a basal spacing of 14 A) in the brackish-water sediments of the Early Cretaceous Weald Clay of south-east England. Worssam & Ivimey-Cook (1971) reported "chamosite" ooids from the Wealden sediments of the Wartingham Bore, but these were identified purely on petrographic observations. Nikitina & Zvyagin (1972) described berthierine from a Carboniferous laterite, and Kodama & Foscolos (1981) reported it in a Canadian arctic soil. These reports suggest that berthierine may form in a wide range of environments. This paper describes an occurrence of berthierine in non-marine Wealden sediments in England, and suggests a possible genesis.