Preservation of biosignatures in Neoproterozoic phosphorites metamorphosed at temperatures >450 °C

Abstract

There is still much controversy over whether apatite and graphite can be used as fingerprint mineral assemblages to preserve biosignatures in ancient sedimentary rocks that experienced medium- to high-grade metamorphism. Herein, we present a comprehensive analysis of graphite and associated phases from meta-phosphorites of the Huangmailing Formation in the South Dabie Orogen to assess possible preservation of biosignatures. Stratigraphic correlations and previous geochronological data suggest that the protoliths of Huangmailing Formation was deposited in the Ediacaran, and was metamorphosed during the Triassic Dabie Orogeny as documented by our apatite UPb dating. Microcrystalline graphite occurs both as inclusions within metamorphic minerals like apatite, and as matrix-hosted disseminations at grain boundaries of other phases. Bulk organic carbon isotopic analyses yield δ13C values between −26.0 ‰ and − 15.2 ‰ and total organic carbon contents from 0.33 to 3.27 wt%. Raman spectra of the two types of graphites yield an average peak metamorphic temperature of 452 °C and 473 °C, consistent with the upper greenschist facies to lower amphibolite facies metamorphic conditions in the area. However, the matrix graphites show a wider range of peak temperature variations, likely containing graphitic carbon with lower crystallinity that was affected by retrograde metamorphic fluids. Notably, two prominent Raman bands at around 325 cm−1 and 395 cm−1 are observed for the graphite hosted in apatite. This, along with the presence of a peak at 2473 eV in the sulfur K-edge XANES spectra of some graphite in apatite, and the co-occurrence of 12C and 14N and local association of 32S with 12C in graphite inclusions determined by TOF-SIMS, suggest the possible presence of C-S-Fe and N-bearing compounds and functional groups. TEM and EDS analysis reveal that graphite inclusions in apatite are closely associated with amorphous silica, and mainly occur as well crystallized, polygonal grains around 100 to 200 nm across and has an expanded (002) lattice spacing between 3.43 Å and 3.64 Å. This lattice expansion is attributable to the presence of heteroatoms such as S, Fe and Si, and N, in the graphene interlayers. In contrast, matrix graphites exhibit a wider range of structural and compositional variations than their counterpart as inclusion in apatite, which probably arise from interactions with metamorphic fluids or incorporation of fluid-deposited graphitic carbon. Our study documents the ubiquitous preservation of biological carbon as graphite inclusions in apatite from Huangmailing meta-phosphorites, likely as a result of metamorphic recrystallization of organic-bearing Ediacaran phosphorites. This suggests that the organic matter trapped in sedimentary apatite during their co-precipitation or early diagenesis was probably less modified during metamorphic recrystallization, thus facilitating the preservation of biosignatures.