Influence of Hyper-Alkaline pH Leachate on Mineral and Porosity Evolution in the Chemically Disturbed Zone Developed in the Near-Field Host Rock for a Nuclear Waste Repository

This paper evaluates the effect of hyper-alkaline (NaOH/KOH) leachate on the mineralogy and porosity of a generic quartzo-feldspathic host rock for intermediate- and low-level nuclear waste disposal following permeation of the cementitious repository barrier by groundwater. The analysis is made with reference to expected fluid compositions that may develop by contact of groundwater with the cementitious barrier to form a chemically disturbed zone (CDZ) in the adjacent host rock, as informed by relevant natural analogue sites. Theoretical analysis and numerical modelling is used to explore the influence of different host rock mineral assemblages on changes in pore fluid chemistry, multiple mineral dissolution and precipitation reactions and matrix porosity within the CDZ under these conditions. The numerical modelling accounts for kinetic and surface area effects on the mineral transformation and porosity development for periods of up to 10,000 years travel time from the repository and ambient temperature of 20∘C. The analysis shows that dissolution of quartz, feldspar and muscovite in the host rock, by the hyper-alkaline waste leachate, will create relatively high concentrations of dissolved Si and Al in the pore fluid, which migrates as chemical fronts within the CDZ. Precipitation of secondary mineral phases is predicted to occur under these conditions. The increase in matrix porosity that arises from dissolution of primary aluminosilicate minerals is compensated by a reduction in porosity due to precipitation of the secondary phases, but with a net overall increase in matrix porosity. These coupled physical and geochemical processes are most important for contaminant transport in the near-field zone of the CDZ and are eventually buffered by the host rock within 70 m of the repository for the 10,000 year travel time scenario. The predicted changes in matrix porosity may contribute to increased transport of radionuclides in the host rock, in the absence of attenuation by other mechanisms in the CDZ

Organic matter and palaeoenvironmental signals during the Early Triassic biotic recovery: the Salt Range and Surghar Range records

Latest Permian to the Middle Triassic mixed siliciclastic–carbonate shelf deposits of the northern Gondwana margin have been studied in four sections (Nammal, Chhidru, Chitta–Landu, and Narmia) in the Salt Range and Surghar Range of Pakistan. Sedimentological and palynofacies patterns combined with a high resolution ammonoid based age control have been used to assess environmental changes such as sea-level change, distance from the shore, and oxygenation conditions of the sections in the aftermath of the end-Permian mass extinction. The base and the top of the Early Triassic are marked by second order sequence boundaries (SRT1, SRT8). Within the Early Triassic two third order sequence boundaries could be delineated by means of palynofacies analysis and sedimentology, one near the Dienerian–Smithian (SRT2) and the second one near the Smithian–Spathian boundary (SRT5). The extinction event at the Smithian–Spathian boundary seems to be closely associated to the latter globally recorded sea-level low stand. Five additional sequences of undetermined order (SRT3, SRT 4, SRT5/1, SRT6, and SRT7) are reflected in the sedimentological record of the studied sections. The observed changes in the composition of the particulate organic matter (POM) indicate a general shallowing upward trend, which is modulated by smaller transgressive–regressive cycles supporting the sedimentologically defined sequences. The POM is mostly dominated by terrestrial phytoclasts and sporomorphs. The strongest marine signal is reflected by increased abundance of amorphous organic matter (AOM) in the lower part of the Ceratite Marls at Nammal (late Dienerian) and Chhidru (earliest Smithian) and the Lower Ceratite Limestone at Chitta–Landu (late Dienerian). AOM of marine origin is characteristic for deeper, distal basinal settings and is preferentially preserved under dysoxic and anoxic conditions, indicating reduced oxygen conditions during these intervals. Up-section transgressive events are reflected by increased numbers of acritarchs, reaching up to 50% of the POM. Well oxygenated conditions and low total organic carbon contents (TOC) continue up to the top of the Early Triassic (Mianwali Formation). The most pronounced terrestrial influx is expressed in the Middle Triassic. Organic carbon isotope data parallel the carbonate carbon isotope records from the Tethyan realm; therefore, they reflect real global changes in the carbon cycle independent of the OM composition. The biomarker study of the apolar hydrocarbons of three samples from the Nammal section indicates an enhanced bacterial productivity, especially in the Smithian and Spathian, reflected in high relative abundances of hopanes. POM, TOC data and redox sensitive biomarkers together with high resolution biostratigraphy demonstrate that well-oxygenated environmental conditions prevailed in the Early Triassic with the exception of the Dienerian to earliest Smithian interval. The POM assemblages of Late Permian to late Griesbachian age indicate well oxygenated conditions during this time interval. There is no evidence in support of an anoxic event in the late Griesbachian in these sections