Abstract: Organic compounds are ubiquitous in the Earth’s surface, sediments and many rocks, and preserve records of geological, geochemical and biological history; they are also critical natural resources and major environmental pollutants. The naturally occurring stable isotopes of volatile elements (D, 13 C, 15 N, 17,18 O, 33,34,36 S) provide one way of studying the origin, evolution and migration of geological organic compounds. The study of bulk stable isotope compositions (i.e. averaged across all possible molecular isotopic forms) is well established and widely practised, but frequently results in non-unique interpretations. Increasingly, researchers are reading the organic isotopic record with greater depth and specificity by characterizing stable isotope ‘structures’ – the proportions of site-specific and multiply substituted isotopologues that contribute to the total rare-isotope inventory of each compound. Most of the technologies for measuring stable isotope structures of organic molecules have been only recently developed and to date have been applied only in an exploratory way. Nevertheless, recent advances have demonstrated that molecular isotopic structures provide distinctive records of biosynthetic origins, conditions and mechanisms of chemical transformation during burial, and forensic fingerprints of exceptional specificity. This paper provides a review of this young field, which is organized to follow the evolution of molecular isotopic structure from biosynthesis, through diagenesis, catagenesis and metamorphism.

Abstract Graphitization in fault zones is associated both with fault weakening and orogenic gold mineralization. We examine processes of graphitic carbon emplacement and deformation in the active Alpine Fault Zone, New Zealand by analysing samples obtained from Deep Fault Drilling Project (DFDP) boreholes. Optical and scanning electron microscopy reveal a microtextural record of graphite mobilization as a function of temperature and ductile then brittle shear strain. Raman spectroscopy allowed interpretation of the degree of graphite crystallinity, which reflects both thermal and mechanical processes. In the amphibolite-facies Alpine Schist, highly crystalline graphite, indicating peak metamorphic temperatures up to 640°C, occurs mainly on grain boundaries within quartzo-feldspathic domains. The subsequent mylonitization process resulted in the reworking of graphite under lower temperature conditions (500–600°C), resulting in clustered (in protomylonites) and foliation-aligned graphite (in mylonites). In cataclasites, derived from the mylonitized schists, graphite is most abundant (<50% as opposed to <10% elsewhere), and has two different habits: inherited mylonitic graphite and less mature patches of potentially hydrothermal graphitic carbon. Tectonic–hydrothermal fluid flow was probably important in graphite deposition throughout the examined rock sequences. The increasing abundance of graphite towards the fault zone core may be a significant source of strain localization, allowing fault weakening. Supplementary material: Raman spectra of graphite from the Alpine Fault rocks is available at https://doi.org/10.6084/m9.figshare.c.3911797