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

Petrogenetic implications of Ti, Zr, Y, and Nb variations in volcanic rocks

Data from experimental runs, coexisting phases in ultramafic rocks and phenocryst-matrix pairs in volcanic rocks have been used to compile a table of mineral-liquid distribution coefficients for Ti, Zr, Y, and Nb for basic, intermediate and acid melt compositions. These values have then been used to interpret variations of these elements, first in basalts and second, during fractional crystallization from basic to acid magmas. For basalts, petrogenetic modelling of Zr/Y, Zr/Ti, and Zr/Nb ratios, when used in conjunction with REE, Cr and isotopic variations, suggests that: (1) the increase in Zr/Y ratio from mid-ocean ridge to within plate basalts and the low Zr/Nb ratios of alkalic basalts are due to (fluid controlled) source heterogeneities; (2) the low Zr and Zr/Y ratio of volcanic arc basalts results from high degree of partial melting of a depleted source; and (3) the high Zr and similar Zr/Y ratio of basalts from fast spreading relative to slow spreading ridges results from open-system fractional crystallization. Modelling of fractionation trends in more evolved rocks using Y-Zr, Ti-Zr and Nb-Zr diagrams highlights in particular the change in crystallizing mafic phases from island arcs (clinopyroxene-dominated) to Andean-type arcs (amphibole±biotite-dominated). These methods can be applied to altered lavas of unknown affinities to provide additional information on their genesis and eruptive environment