Iron cycling in a late Paleozoic dust bowl

The late Paleozoic glaciation (~300 million years ago) marks the last major, pre-Cenozoic icehouse climate. In addition, emerging research suggests that this was a particularly dusty time, evinced by abundant dust (loessite) deposits throughout western equatorial Pangaea. Delivery of reactive Fe-rich eolian particles to the nutrient-depleted open ocean potentially stimulates primary production during glacial intervals, yet the details remain unclear for recent glaciations and completely unknown for the ancient. Bioavailable Fe is a limiting nutrient in high nitrate, low chlorophyll portions of the open ocean. Because primary abundances of the most labile forms of Fe are not easily assessed in ancient sediments, we use highly reactive Fe (FeHR) (mostly crystalline oxides, some or most of which might have been more soluble precursors at the time of deposition) as determined by a well-calibrated sequential extraction scheme as a proxy for bioavailable Fe. Here we present data from multiple Pennsylvanian-Permian loess and intercalated paleosol (ancient soil) deposits, as well as a modern dust site. We also compare ratios of total Fe (FeT) to Al to ratios of FeHR to FeT to assess whether increased Fe reactivity in dust reflects a net Fe addition or internal mineral repartitioning. We are finding that these paired proxies may provide a unique fingerprint of source relationships. Modern arid Saharan soil dust deposited in the Turks and Caicos Islands has high FeT/Al ratios (0.75 versus ~0.5 for average continental crust), with corresponding FeHR/FeT enrichments (0.48 compared to ~0.38 for typical riverine input). The ancient loessite samples do not show a similar pattern, instead suggesting an antithetic relationship between FeT/Al and FeHR/FeT. Therefore, FeHR was enriched and, by inference, bioavailable despite net Fe loss reflected in sub-crustal FeT/Al ratios. Most work to date has presumed an arid soil source for most bioavailable Fe. However, in light of our work and recent studies in modern glacial settings, we are exploring the possibility that ancient loessites may have a more direct tie to glacial processes.