Molecular fingerprinting of wetland organic matter using pyrolysis-GC/MS: an example from the southern Cape coastline of South Africa

Pyrolysis–gas chromatography mass spectrometry (py-GC/MS) allows the characterisation of complex macromolecular organic matter. In lakes and wetlands this can potentially be used to assess the preservation/diagenesis and provenance of sediment organic matter. It can complement palaeoenvironmental investigations utilising ‘bulk’ sediment variables such as total organic carbon (TOC) and TOC/total nitrogen ratios. We applied py-GC/MS analyses to a ~32,000-year sediment record from the southern Cape coastline of South Africa. We used the results to evaluate the sources and extent of degradation of organic matter in this semi-arid environment. Marked down-core changes in the relative abundance of multiple pyrolysis products were observed. Correspondence analysis revealed that the major driver of this down-core variability in OM composition was selective preservation/degradation. Samples comprising highly degraded OM are primarily confined to the lower half of the core, older than ~12,000 years, and are characterised by suites of low-molecular-weight aromatic pyrolysis products. Samples rich in organic matter, e.g. surface sediments, are characterised by products derived from fresh emergent or terrestrial vegetation, which include lignin monomers, plant-derived fatty acids and long-chain n-alkanes. Pyrolysates from the late glacial-early Holocene period, approximately mid-way down the core are characterised by distinct suites of long-chain n-alkene/n-alkane doublets, which may reflect the selective preservation of recalcitrant aliphatic macromolecules and/or enhanced inputs of the algal macromolecule algaenan/polymerised algal lipids. Increased TOC, lower δ¹³C and increased abundance of more labile lignin and fatty acid products at the same depths suggest this period was associated with increased lake primary productivity and enhanced inputs of terrestrial OM. TOC is the only ‘bulk’ parameter correlated with the correspondence analysis axes extracted from the py-GC/MS data. Distinct fluctuations in TOC/total nitrogen ratio are not explained by variation in organo-nitrogen pyrolysis products. Notwithstanding, the study suggests that py-GC/MS has potential to complement palaeolimnological investigations, particularly in regions such as southern Africa, where other paleoenvironmental proxy variables in sediments may be lacking or equivocal.     

Evolution of a carbonate delta generated by gateway‐funnelling of episodic currents

Cool‐water carbonate sedimentation has dominated Mediterranean shelves since the Early Pliocene. Skeletal sand and gravel herein consist of remains of heterozoan organisms, which are susceptible to reworking due to weak early cementation in non‐tropical waters. This study documents the Lower Pleistocene carbonate wedge of Favignana Island (Italy), which prograded from a 5   km wide passage between two palaeo‐islands into a perpendicular, 10 to 15   km wide strait between the palaeo‐islands at one side and Sicily at the other during the Emilian highstand (1·6   Ma to 1·1   Ma). The clinoformed carbonate wedge, which is 50   m thick and 6   km long, formed by east/south‐east progradation of a platform on the submarine sill by currents that were funnelled between the two palaeo‐islands. Platform‐slope clinoforms evolved from initial aggradation (thin and low‐angle) into a progradation phase (thick and high‐angle). Both clinoform types are characterized by a bimodal facies stacking pattern defined by sedimentary structures created by: (i) subaqueous dunes associated with dilute subcritical currents; and (ii) upper‐flow‐regime bedforms associated with sediment‐laden supercritical turbidity currents. Focusing of episodic currents on the platform by funnelling between the islands controlled the downstream formation of a sediment body, here named carbonate delta. The carbonate delta interfingers with subaqueous dune deposits formed in the perpendicular strait. This study uses a reconstruction of bedform dynamics to unravel the evolution of this gateway‐related carbonate accumulation.