Sedimentary Iron Cycling and the Origin and Preservation of Magnetization in Platform Carbonate Muds, Andros Island, Bahamas

Carbonate muds deposited on continental shelves are abundant and well-preserved throughout the geologic record because shelf strata are difficult to subduct and peritidal carbonate units often form thick, rheologically strong units that resist penetrative deformation. Much of what we know about pre-Mesozoic ocean chemistry, carbon cycling, and global change is derived from isotope and trace element geochemistry of platform carbonates. Paleomagnetic data from the same sediments would be invaluable, placing records of paleolatitude, paleogeography, and perturbations to the geomagnetic field in the context and relative chronology of chemostratigraphy. To investigate the depositional and early diagenetic processes that contribute to magneitzation in carbonates, we surveyed over 500 core and surface samples of peritidal, often microbially bound carbonate muds spanning the last not, vert, similar 1000 yr and deposited on top of Pleistocene aeolianites in the Triple Goose Creek region of northwest Andros Island, Bahamas. Sedimentological, geochemical, magnetic and ferromagnetic resonance properties divide the sediment columns into three biogeochemical zones. In the upper sediments, the dominant magnetic mineral is magnetite, produced by magnetotactic bacteria and dissimiliatory microbial iron metabolism. At lower depths, above or near mean tide level, microbial iron reduction dissolves most of the magnetic particles in the sediment. In some cores, magnetic iron sulfides precipitate in a bottom zone of sulfate reduction, likely coupled to the oxidation of decaying mangrove roots. The remanent magnetization preserved in all oriented samples appears indistinguishable from the modern local geomagnetic field, which reflects the post-depositional origin of magnetic particles in the lower zone of the parasequence. While we cannot comment on the effects of late-stage diagenesis or metamorphism on remanence in carbonates, we postulate that early-cemented, thin-laminated parasequence tops in ancient peritidal carbonates are mostly likely to preserve syn-depositional paleomagnetic directions and magnetofossil stratigraphies

Significance of perylene for source allocation of terrigenous organic matter in aquatic sediments.

Author Posting. © American Chemical Society, 2019. This is an open access article published under an ACS AuthorChoice License. The definitive version was published in Environmental Science and Technology 53(14), (2019):8244-8251, doi:10.1021/acs.est.9b02344.Perylene is a frequently abundant, and sometimes the only polycyclic aromatic hydrocarbon (PAH) in aquatic sediments, but its origin has been subject of a longstanding debate in geochemical research and pollutant forensics because its historical record differs markedly from typical anthropogenic PAHs. Here we investigate whether perylene serves as a source-specific molecular marker of fungal activity in forest soils. We use a well-characterized sedimentary record (1735 to 1999) from the anoxic-bottom waters of the Pettaquamscutt River basin, RI, USA to examine mass accumulation rates and isotope records of perylene, and compare them with total organic carbon and the anthropogenic PAH fluoranthene. We support our arguments with radiocarbon (14C) data of higher plant leaf-wax n-alkanoic acids. Isotope-mass balance calculations of perylene and n-alkanoic acids indicate that ~40 % of sedimentary organic matter is of terrestrial origin. Further, both terrestrial markers are pre-aged on millennial time-scales prior to burial in sediments and insensitive to elevated 14C concentrations following nuclear weapons testing in the mid-20th Century. Instead, changes coincide with enhanced erosional flux during urban sprawl. These findings suggest that perylene is definitely a product of soil derived fungi, and a powerful chemical tracer to study spatial and temporal connectivity between terrestrial and aquatic environments.We thank John King, Sean Sylva, Brad Hubeny, Peter Sauer, and Jim Broda for their help in sampling; Carl Johnson and Daniel Montluçon for their incessant help with analyses; as well as Mark Yunker for critical discussion on the perils of perylene. Professor Phil Meyers and two anonymous reviewers provided comments that improved the quality of the manuscript. U.M.H. acknowledges the Swiss National Science Foundation for his postdoctoral fellowship and T.I.E. and K.A.H. acknowledges the NSF for research grants CHE-0089172 and OCE-9708478.2020-06-1