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

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

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

The composition and weathering of the continents over geologic time

The composition of continental crust records the balance between construction by tectonics and destruction by physical and chemical erosion. Quantitative constraints on how igneous addition and chemical weathering have modified the continents’ bulk composition are essential for understanding the evolution of geodynamics and climate. Using novel data-analytic techniques we have extracted temporal trends in sediments’ protolith composition and weathering intensity from the largest available compilation of sedimentary major-element compositions: ∼ 15,000 samples from 4.0 Ga to the present. We find that the average Archean upper continental crust was silica rich and had a similar compositional diversity to modern continents. This is consistent with an early-Archean, or earlier, onset of plate tectonics. In the Archean, chemical weathering sequestered ∼ 25 % more CO2 per mass eroded for the same weathering intensity than in subsequent time periods, consistent with carbon mass-balance despite higher Archean outgassing rates and more limited continental exposure. Since 2.0 Ga, over long (> 0.5 Ga) timescales, crustal weathering intensity has remained relatively constant. On shorter timescales over the Phanerozoic, weathering intensity is correlated to global climate state, consistent with a weathering feedback acting in response to changes in CO2 sources or sinks

From marine bands to hybrid flows: sedimentology of a Mississippian black shale

Organic‐rich mudstones have long been of interest as conventional and unconventional source rocks and are an important organic carbon sink. Yet the processes that deposited organic‐rich muds in epicontinental seaways are poorly understood, partly because few modern analogues exist. This study investigates the processes that transported and deposited sediment and organic matter through part of the Bowland Shale Formation, from the Mississippian Rheic–Tethys seaway. Field to micron‐scale sedimentological analysis reveals a heterogeneous succession of carbonate‐rich, siliceous, and siliciclastic, argillaceous muds. Deposition of these facies at basinal and slope locations was moderated by progradation of the nearby Pendle delta system, fourth‐order eustatic sea‐level fluctuation and localized block and basin tectonism. Marine transgressions deposited bioclastic ‘marine band’ (hemi)pelagic packages. These include abundant euhaline macrofaunal tests, and phosphatic concretions of organic matter and radiolarian tests interpreted as faecal pellets sourced from a productive water column. Lens‐rich (lenticular) mudstones, hybrid, debrite and turbidite beds successively overlie marine band packages and suggest reducing basin accommodation promoted sediment deposition via laminar and hybrid flows sourced from the basin margins. Mud lenses in lenticular mudstones lack organic linings and bioclasts and are equant in early‐cemented lenses and in plan‐view, and are largest and most abundant in mudstones overlying marine band packages. Thus, lenses likely represent partially consolidated mud clasts that were scoured and transported in bedload from the shelf or proximal slope, as a ‘shelf to basin’ conveyor, during periods of reduced basin accommodation. Candidate in situ microbial mats in strongly lenticular mudstones, and as rip‐up fragments in the down‐dip hybrid beds, suggest that these were potentially key biostabilizers of mud. Deltaic mud export was fast, despite the intrabasinal complexity, likely an order of magnitude higher than similar successions deposited in North America. Epicontinental basins remotely linked to delta systems were therefore capable of rapidly accumulating both sediment and organic matter

The composition and weathering of the continents over geologic time

The composition of continental crust records the balance between construction by tectonics and destruction by physical and chemical erosion. Quantitative constraints on how igneous addition and chemical weathering have modified the continents’ bulk composition are essential for understanding the evolution of geodynamics and climate. Using novel data analytic techniques we have extracted temporal trends in sediments’ protolith composition and weathering intensity from the largest available compilation of sedimentary major element compositions: ∼15,000 samples from 4.0 Ga to the present. We find that the average Archean upper continental crust was silica-rich and had a similar compositional diversity to modern continents. This is consistent with an early Archean, or earlier, onset of plate tectonics. In the Archean, chemical weathering sequestered ∼25 % more CO2 per mass eroded for the same weathering intensity than in subsequent time periods, consistent with carbon mass balance despite higher Archean outgassing rates and more limited continental exposure. Since 2.0 Ga, over long (>0.5 Gyr) timescales, crustal weathering intensity has remained relatively constant. On shorter timescales over the Phanerozoic, weathering intensity is correlated to global climate state, consistent with a weathering feedback acting in response to changes in CO2 sources or sinks