Combining thermal hydrolysis and methylation-gas chromatography/mass spectrometry with X-ray photoelectron spectroscopy to characterise complex organic assemblages in geological material.

What follows is a method applicable generically to the analysis of low levels of organic matter that is embedded in either loose fine-grained or solid geological material. Initially, the range of organic compounds that could be detected in a geological sample using conventional pyrolysis chromatography/mass spectrometry was compared to the range that was detected using thermally assisted hydrolysis and methylation-gas chromatography/mass spectrometry (THM-GC/MS). This method was used to validate the synthetic components fitted to X-ray photoelectron spectroscopy (XPS) carbon spectra of the sample. Reciprocally, XPS analysis was able to identify the constituent carbon-carbon, carbon-oxygen and carbon-nitrogen bonds of the functional groups in the compounds identified by THM-GC/MS. The two independently derived outputs from the THM-GC/MS and the XPS techniques mutually validated the identification of organic compounds in our geological samples. We describe in detail the improvements to: •The preparation of geological samples for analysis by XPS.•Measurements of organic material in geological samples using GC/MS.•The use of THM-GC/MS and XPS data used together to characterise low levels of organic material in geological samples.

The organic stratigraphy of Ontong Java Plateau Tuff correlated with the depth-related presence and absence of putative microbial alteration structures.

Structures in geological samples are often interpreted as fossilised life; however, such interpretations are equivocal, as abiotic processes can be invoked to explain their presence. Thus, additional lines of chemical evidence are invaluable in confirming or refuting such morphological evidence. Glass shards in tuff from the Ontong Java Plateau (OJP) contain microtubular structures that are in close proximity to functionalised nitrogen substituted aromatic compounds that may be indicative of the chemical remnants of biological activity. The organic composition of the OJP tuff containing microtubular alteration structures was compared with tuff without such features. In addition, organic matter associated with horizons with compacted remnants of woody material buried in the OJP tuff and overlying pelagic calcareous foraminifer sediment were also characterised, to ascertain the provenance of the organic matter found in the OJP tuff. As a further control, the organic material in submarine and terrestrial basalts from other locations were also characterised providing further evidence to support the view that the organic matter in the OJP tuff is authigenic. Carbon-nitrogen chemistry was detected across all OJP tuff samples irrespective of the presence or absence of microtubular features, but was not detected in either the wood material, the overlying pelagic sediments or in the basalts from other locations. The results indicate no direct link between the OJP nitrogenous organic compounds and the presence or absence of microtubular features.