Grain size and organic carbon controls polyaromatic hydrocarbons (PAH), mercury (Hg) and toxicity of surface sediments in the River Conwy Estuary, Wales, UK

The Conwy estuary was evaluated for sediment quality. Microtox bioassay revealed 38 of 39 sites were non-toxic. Hg ranged from 0.001 to 0.153 μg kg−1, mean 0.026 mg kg−1, Σ16 PAH from 18 to 1578 μg kg−1, mean 269 μg kg−1, Σ22 PAH, 18 to 1871 μg kg−1 mean to 312 μg kg−1, two sites had high perylene relative to ΣPAH. Σ22PAH correlated positively with TOC, clay and silt (R2 0.89, 0.92, 0.90) and negatively with sand. Multivariate statistics, delineated four spatial (site) and five variable (measurements) clusters. Spatial clustering relates to sediment grain size, in response to hydrodynamic processes in estuary; fine (clay to silt) sized sediments exhibit the highest Hg and PAH content, because these components partitioned into the fine fraction. Comparison to national and international environmental standards suggests Hg and PAH content of Conwy sediments are unlikely to harm ecology or transfer up into the human food chain

Origin and implications of early diagenetic quartz in the Mississippian Bowland Shale formation, Craven Basin, UK

Silica cementation exerts a key control on the compaction and geotechnical properties of mudstones, and by extension, the style of hydrocarbon and/or mineral systems present in a given sedimentary basin. Integrated microscopic and bulk geochemical observations demonstrate that siliceous mudstones in the Bowland Shale Formation, a target for UK shale gas extraction, exhibit abundant dispersed, discrete, μm-scale quartz cements, and exhibit silica enrichment (‘excess’) above a local detrital Si/Al threshold of 2.5. Dissolution of siliceous radiolarian tests during early diagenesis is identified as the main source of silica (opal A) required for quartz precipitation, either via opal CT or directly to quartz, and potentially generated as a product of anoxic marine ‘weathering’ (dissolution) of reactive silicates during early diagenesis. Excess silica correlates with free hydrocarbons (S1) normalised to total organic carbon (oil saturation index; OSI); we propose early diagenetic quartz precipitation suppressed pore collapse (‘buttress effect’), retaining the pore space capacity to host oil. Quartz precipitation was likely catalysed, for example via low porewater pH, elevated Al and/or Fe oxide content, and/or abundant labile organic matter. Juxtaposition of siliceous mudstones and mudstones lacking quartz cement indicates silica was immobile beyond the bed scale. Thus metre-scale siliceous packages likely represent more prospective units within the Bowland Shale (in terms of unconventional hydrocarbons), on the basis of early diagenetic biogenic-derived quartz cementation leading to improved hydrocarbon storage capacity coupled to enhanced brittleness. These findings are relevant for shale oil and shale gas systems, specifically where oil retained in pores subsequently cracks to generate gas. These findings also suggest the Bowland Shale is a sub-class of black shale, defined by the potential to host a relatively large volume of early diagenetic fluids, derived from anoxic bottom waters, which were potentially S- and/or metal-bearing. This is potentially relevant for understanding the genesis of adjacent and related Pb-Zn mineral deposits

Pyrite mega-analysis reveals modes of anoxia through geological time

The redox structure of the water column in anoxic basins through geological time remains poorly resolved despite its importance to biological evolution/extinction and biogeochemical cycling. Here, we provide a temporal record of bottom and pore water redox conditions by analyzing the temporal distribution and chemistry of sedimentary pyrite. We combine machine-reading techniques, applied over a large library of published literature, with statistical analysis of element concentrations in databases of sedimentary pyrite and bulk sedimentary rocks to generate a scaled analysis spanning the majority of Earth’s history. This analysis delineates the prevalent anoxic basin states from the Archaean to present day, which are associated with diagnostic combinations of five types of syngenetic pyrite. The underlying driver(s) for the pyrite types are unresolved but plausibly includes the ambient seawater inventory, precipitation kinetics, and the (co)location of organic matter degradation coupled to sulfate reduction, iron (oxyhydr)oxide dissolution, and pyrite precipitation

Late Glacial and Holocene Palaeolake History of the Última Esperanza Region of Southern Patagonia

We undertook multi-proxy analyses on two sediment cores from Lago Pato, a small lake basin at 51°S topographically separated from Lago del Toro in Torres del Paine (TdP), to provide insights into glacier dynamics and lake-level change in the TdP and Última Esperanza region over the last ∼30,000 cal a BP (30 ka). Lago Pato is situated in a region overridden by the Southern Patagonian Ice Field during the Last Glacial and in a transitional climatic zone of Southern Patagonia sensitive to seasonal- to millennial-scale changes in the Southern Hemisphere Westerly Winds (SWW). Results show that a deep ice-dammed and enlarged palaeolake encompassed Lago del Toro and Lago Pato c. 30–20 ka after the ice had retreated from local-Last Glacial Maximum (l-LGM) limits at c. 48–34 ka and during the build-up to the global-Last Glacial Maximum (g-LGM), c. 26–19 ka. Gaps in both sediment records between c. 20–13.4 ka and c. 20–10 ka suggest hiatuses in sediment accumulation during the g-LGM and Antarctic Cold Reversal (ACR) readvances and/or removal by lake lowering or flushing during the Late Glacial–early Holocene. The palaeolake level dropped from >100 m a.s.l. to ∼40–50 m a.s.l. towards the end of the ACR c. 13.4–13.0 ka, creating a shallower glaciolacustrine environment dammed by an ice tongue in the Estancia Puerto Consuelo–Última Esperanza fjord. Further lowering of the enlarged palaeolake level occurred when the ice thinned to <40 m a.s.l., eventually isolating Lago Pato from Lago del Toro and glaciogenic sediment input at c. 11.7 ka. After isolation, the ecology and water levels in Lago Pato became sensitive to regional climate shifts. The shallow, stable, and highly anoxic environment that developed after c. 11.7 ka is associated with weaker (or poleward shifted) SWW at 51°S and was replaced at c. 10 ka by an increasingly productive shallow-littoral lake with a variable lake-level and periodic shifts in anoxic-oxic bottom water conditions and ratios of benthic-planktonic diatoms. A more open Nothofagus forest, established at c. 8.6–7.5 ka, and more arid conditions c. 7.5–5.7 cal ka BP are linked to another phase of weaker (or poleward shifted) SWW at 51°S. More persistently wet conditions from c. 5.7 ka, with extensive closed Nothofagus forests and planktonic diatoms dominant, are associated with stronger (or equatorward shifted) SWW over 51°S. The abrupt return of benthic-to-tychoplanktonic diatoms after c. 3 ka reflects enhanced SWW at 51°S. Increasingly stable lacustrine and littoral wetland conditions established in the last ∼500 years reflect weaker SWW and lasted until recent decades

A Mississippian black shale record of redox oscillation in the Craven Basin, UK

Early diagenetic redox oscillation processes have been rarely recognised in the ancient rock record but potentially exert an important control on mineral authigenesis, hydrocarbon prospectivity and supply of metals and/or reduced S as part of associated mineral systems. The upper unit of the Mississippian Bowland Shale Formation is a candidate record of diagenetic redox oscillation processes because it was deposited under a relatively high sediment accumulation rate linked to a large delta system, and under dominantly anoxic and intermittently sulphidic bottom-water conditions. In order to characterise the syngenetic and early diagenetic processes, sedimentological and geochemical data were integrated through the Upper Bowland Shale at three sites in the Craven Basin (Lancashire, UK). Organic matter (OM) comprises a mixture of Type II, II-S, II/III and III OM. ‘Redox zones’ are defined by patterns of Fe-speciation and redox-sensitive trace element enrichment and split into two groups. ‘Sulphidic’ zones (EUX, AN-III, AN-I and AN-IT) represent sediments deposited under conditions of at least intermittently active sulphate-reduction in bottom-waters. ‘Non-sulphidic’ zones (OX-RX, OX-F and OX) represent sediments deposited under non-sulphidic (oxic to ferruginous anoxic) bottom-waters. Operation of a shelf-to-basin ‘reactive Fe’ (FeHR) shuttle, moderated by sea level fluctuation and delta proximity, controlled the position and stability of redoxclines between zones of Fe and sulphate reduction, and methanogenesis. Early diagenetic redoxclines were capable of migration through the shallow sediment column relatively quickly, in response to sea level fluctuation. Preservation of syngenetic and early diagenetic geochemical signals shows redoxclines between Fe and sulphate reduction, and the upper boundary of sulphate-methane transition zone, were positioned within decimetres (i.e., 10 s cm) of seabed. Falling sea level and increasing FeHR supply is recognised as a switch from zones EUX (high sea level), AN-III and ultimately AN-I and AN-IT (low sea level). Zone AN-I defines the operation of ‘redox oscillation’, between zones of Fe and sulphate reduction in shallow porewaters, associated with enhanced degradation of OM and complete dissolution of primary carbonate. Preservation of OM and carbonate, in this system, was a function of changing bottom and pore water redox processes. Redox oscillation operated in a siliciclastic, prodeltaic environment associated with a relatively high sediment accumulation rate and high loadings of labile organic matter and metal oxides. These findings are important for understanding Late Palaeozoic black shales in the context of hydrocarbon and mineral systems

Stream and slope weathering effects on organic-rich mudstone geochemistry and implications for hydrocarbon source rock assessment: a Bowland Shale case study

This study contributes to the exploration and quantification of the weathering of organic-rich mudstones under temperate climatic conditions. Bowland Shales, exposed by a stream and slope, were sampled in order to develop a model for the effects of weathering on the mudstone geochemistry, including major and trace element geochemistry, Rock-Eval pyrolysis and δ13Corg. Four weathering grades (I – IV) are defined using a visual classification scheme; visually fresh and unaltered (I), chemically altered (II, III) and ‘paper shale’ that typifies weathered mudstone on slopes (IV). Bedload abrasion in the stream exposes of visually fresh and geochemically unaltered mudstone. Natural fractures are conduits for oxidising meteoric waters that promote leaching at the millimetre scale and/or precipitation of iron oxide coatings along fracture surfaces. On the slope, bedding-parallel fractures formed (and may continue to form) in response to chemical and/or physical weathering processes. These fractures develop along planes of weakness, typically along laminae comprising detrital grains, and exhibit millimetre- and centimetre-scale leached layers and iron oxide coatings. Fracture surfaces are progressively exposed to physical weathering processes towards the outcrop surface, and results in disintegration of the altered material along fracture surfaces. Grade IV, ‘paper shale’ mudstone is chemically unaltered but represents a biased record driven by initial heterogeneity in the sedimentary fabric. Chemically weathered outcrop samples exhibit lower concentrations of both ‘free’ (S1) (up to 0.6 mgHC/g rock) and ‘bound’ (S2) (up to 3.2 mgHC/g rock) hydrocarbon, reduced total organic carbon content (up to 0.34 wt%), reduced hydrogen index (up to 58 mgHC/gTOC), increased oxygen index (up to 19 mgCO + CO2/gTOC) and increased Tmax (up to 11 °C) compared with unaltered samples. If analysis of chemically weathered samples is unavoidable, back-extrapolation of Rock-Eval parameters can assist in the estimation of pre-weathering organic compositions. Combining Cs/Cu with oxygen index is a proxy for identifying the weathering progression from fresh material (I) to ‘paper shale’ (IV). This study demonstrates that outcrop samples in temperate climates can provide information for assessing hydrocarbon potential of organic-rich mudstones

Guide to key Bowland Shale Formation outcrop localities in the Craven and Edale basins

This is a guide to the key exposures of the Bowland Shale Formation present within the Craven and Edale basins of England, providing contrasting settings from respectively the northern and southern parts of the Craven Group extent. It provides a description of the evolution of the deposition of the hemipelagic mudstone-dominated components of the Craven Group during the Visean to early Namurian (Mississippian to early Pennsylvanian). It explains the significance of the chosen localities in understanding the development of the Bowland Shale Formation and gives details on the sections visible at the time of compilation, providing useful guidance for field visits

Geochemical X ray fluorescence log ratio time series data for two sediment cores, LP08 and LP16, extracted from Lago Pato, Torres del Paine, Southern Chile

The dataset comprises of X ray fluorescence log ratio time series data for two sediment cores from Lago Pato, a small lake basin at 51.3003 S, 72.6786 W and approx 33 m a.s.l., which is topographically separated from Lago del Toro in Torres del Paine (TdP). The data are used to constrain glacier dynamics and lake level change in the TdP and Ultima Esperanza region over the last approx 30,000 cal a BP (30 ka). LP08 was extracted from the current depocentre in November 2007 to March 2008. LP16 was extracted the terrestrial shoreline in November 2015. This project was funded by the Natural Environment Research Council (NERC) through the British Antarctic Survey (BAS) and an UGent BOF bilateral collaboration project. RMcC was supported by Programa Regional R17A10002 and R20F0002 (PATSER) ANID. We gratefully acknowledge the University of Magallanes (UMAG) and the University of Santiago (Carolina Diaz) for assistance with fieldwork; the NERC/SUERC AMS Radiocarbon Facility for providing initial range-finder radiocarbon dates; the NERC Isotope Geosciences Laboratory (NIGL, now National Environmental Isotope Facility, NEIF, at the British Geological Survey) and Melanie Lang for stable carbon isotope analysis; Aberystwyth University (David Kelly), Durham University (Neil Tunstall and Christopher Longley) and Edinburgh University (Chris Hayward) for use of their core scanning and microprobe facilities and technical support