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Mudstones from the Argiles de Châtillon Formation exposed in the Boulonnais region of Northern France represent a proximal lateral equivalent of the organic-rich Kimmeridge Clay Formation. The Argiles de Châtillon Formation is composed of two subunits that straddle the Kimmeridgian–Tithonian boundary. Each subunit contains an organic-rich interval. The two conspicuous organic-rich intervals have been linked to either periods of high sea level or greenhouse warming. Here, we use palynology to further understand climate and environmental mechanisms that drove organic matter enrichment. We use bulk organic carbon isotope records (δ13Corg) to correlate the Boulonnais sections with those of the Kimmeridge Clay Formation. The palynological results suggest that the stratigraphically lower organic-rich interval (Kimmeridgian) was deposited under suboxic to anoxic stratified conditions. A large-scale climate shift from cooler/humid to warmer/arid conditions marked the Kimmeridgian–Tithonian boundary, influencing organic matter enrichment in the stratigraphically higher organic-rich interval (Tithonian). In contrast with the lower organic-rich interval, there are no indications of stratified conditions for the higher organic-rich interval. Within this thicker organic-rich interval, cyclic variations in amorphous organic matter distribution, total organic carbon and δ13Corg trends on a 2 m scale are observed. They co-occur with fluctuations of the palynological assemblages, indicative of more humid versus arid climate conditions, likely alternating on a ∼100 kyr eccentricity timescale. Our results show that under the most humid phases of these overall arid climate conditions, sulfurization of carbohydrates was the dominant control on organic matter preservation. This climate-controlled process that drives organic matter enrichment in the Tithonian can be recognized on a basin-wide scale. [ABSTRACT FROM AUTHOR]

Laser desorption-ionization mass spectrometry (MS) shows great potential for in situ molecular analysis of planetary surfaces and microanalysis of space-returned samples or (micro)fossils. Coupled with pyrolysis gas chromatography-mass spectrometry (Py-GC-MS) in ESA's ExoMars project, this technique could help assess further the origin of sulfur-bearing organic matter (OM) recently detected on Mars. To unravel this potential, we analyzed sulfurized microbial OM from ca. 150 million year-old carbonates with laser desorption-ionization mass spectrometry (single- and two-step: LDI-MS and L2MS), in comparison with time-of-flight secondary-ion mass spectrometry (ToF-SIMS), gas chromatography-mass spectrometry (GC-MS), and Py-GC-MS. We show that LDI-MS and L2MS readily detect sulfur-bearing moieties such as (alkyl)thiophenes and (alkyl)benzothiophenes. The mineral matrix, however, made the identification of sulfur-bearing molecules challenging in our L2MS experiment. The dominance of small aromatic hydrocarbons (≤14 carbons) in the LDI-MS and L2MS of the extracted soluble and insoluble OM and of the bulk rock is consistent with the low thermal maturity of the sediment and contrasts with the predominance of larger polycyclic aromatic structures commonly observed in meteorites with these techniques. We detected inorganic ions, in particular VO + , in demineralized OM that likely originate from geoporphyrins, which derive from chlorophylls during sediment diagenesis. Finally, insoluble OM yielded distinct compositions compared with extracted soluble OM, with a greater abundance of ions of mass-to-charge ratio ( m / z ) over 175 and additional N-moieties. This highlights the potential of laser-assisted MS to decipher the composition of macromolecular OM, in particular to investigate the preservation of biomacromolecules in microfossils. Studies comparing diverse biogenic and abiogenic OM are needed to further assess the use of this technique to search for biosignatures.