Carbonaceous matter in ∼ 3.5 Ga black bedded barite from the Dresser Formation (Pilbara Craton, Western Australia) – Insights into organic cycling on the juvenile Earth

Abstract

Carbonaceous matter (CM) in Archean rocks represents a valuable archive for the reconstruction of early life. Here we investigate the nature of CM preserved in ∼ 3.5 Ga old black bedded barites from the Dresser Formation (Pilbara Carton, Western Australia). Using light microscopy and high-resolution Raman mapping, three populations of CM were recognized: (i) CM at the edges of single growth bands of barite crystals (most frequent), (ii) CM within the barite matrix, and (iii) CM in 50–300 µm wide secondary quartz veins that cross-cut the black bedded barite. Raman spectra of CM inside black bedded barite indicated peak metamorphic temperatures of ∼ 350 °C, consistent with those reached during the main metamorphic event in the area ∼ 3.3 Ga ago. By contrast, CM in quartz veins yielded much lower temperatures of ∼ 220 °C, suggesting that quartz-vein associated CM entered the barite after 3.3 Ga. Near edge X-ray absorption fine structure (NEXAFS) and solid-state nuclear magnetic resonance (NMR) revealed a highly aromatic nature of the CM with a lower aliphatic content, which is in line with the relatively elevated thermal maturity. Catalytic hydropyrolysis (HyPy) did not yield any hydrocarbons detectable with gas chromatography–mass spectrometry (GC–MS). Secondary ion mass spectrometry (SIMS) based δ13C values of individual CM particles ranged from − 33.4 ± 1.2 ‰ to − 16.5 ± 0.6 ‰ and are thus in accordance with a biogenic origin, which is also consistent with stromatolitic microbialites associated with the black bedded barite. Based on these results we conclude that CM at growth bands and inside the barite matrix is syngenetic and only the CM inside quartz veins, which represents a minor portion of the total CM, is a later addition to the system. Furthermore, we discuss different pathways for the input of CM into the barite-forming environment, including the cycling of biological organic material within the hydrothermal system.