Association between catastrophic paleovegetation changes during Devonian–Carboniferous boundary and the formation of giant massive sulfide deposits

The Iberian Pyrite Belt (SW Iberia) is one of the largest sulfur anomalies in the Earthʹs crust. In the southern Iberian Pyrite Belt, more than 820 Mt of exhalative massive sulfides were deposited in less than one million years at the Devonian–Carboniferous boundary. The shale of the ore-bearing horizon contains biomarkers indicating major biogenic activity in a methanogenic setting, including a five-fold increase in typical vascular plant biomarkers and a significant anomaly in those probably indicating the presence of thermophilic Archaea. This contrasts with signatures in the average sedimentary rocks of the basin that indicate the sediments settled in oxic to sub-oxic environments, and that they have only minor biomarkers derived from continental paleoflora. These data show that the formation of the mineralization was not only related to major hydrothermal activity synchronous with volcanism but may also have been controlled by the input of large amounts of organic matter, mostly derived from the degradation of woodland detritus sourced in the nearby continent. This massive influx of organic matter could have accelerated extremophilic microbial activity that used short-chain hydrocarbons as electron donors for seawater sulfate reduction, resulting in concomitant massive sulfide precipitation. We propose that the giant massive sulfide deposits resulted from overlapping of geological and biological processes that occurred at the Devonian to Carboniferous transition, including: (1) continent collision during the onset of the Variscan orogeny leading to major paleogeographic changes and volcanism; (2) dramatic stress of continental ecosystems due to the combination of climatic change, volcanism, variations in the sea level and erosion on a regional scale; (3) major biomass destruction and increase of organic supply to marine environments; and, (4) generation of anoxic conditions and the thriving of sulfate reducing microorganisms. Under these conditions, massive sulfide deposits formed where venting sulfur-poor but metal-rich hydrothermal brines flowed into a hydrogen sulfide-rich anoxic water column. The data presented strongly suggest that there was a temporal and causal relationship between the Devonian–Carboniferous geotectonic, climatic and biological crises and the formation of the giant volcano-sedimentary massive sulfide deposits of the southern Iberian Pyrite Belt.