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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. Image 1 • The UK Bowland Shale is a target for unconventional hydrocarbon extraction. • The Bowland Shale exhibits 'excess silica' and widespread μm-scale quartz cements. • Early diagenetic dissolution of siliceous radiolarian tests was a key silica source. • Excess silica positively correlates with oil saturation index, up to a threshold. • Therefore pre-compactional early diagenetic precipitation enhanced fluid storativity. [ABSTRACT FROM AUTHOR]