Abstract

Abstract. The coupled biogeochemical cycles of iron and sulfur are central to the long-term biogeochemical evolution of Earth's oceans. For instance, before the development of a persistently oxygenated deep ocean, the ocean interior likely alternated between states buffered by reduced sulfur (“euxinic”) and buffered by reduced iron (“ferruginous”), with important implications for the cycles and hence bioavailability of dissolved iron (and phosphate). Even after atmospheric oxygen concentrations rose to modern-like values, the ocean episodically continued to develop regions of euxinic or ferruginous conditions, such as those associated with past key intervals of organic carbon deposition (e.g. during the Cretaceous) and extinction events (e.g. at the Permian–Triassic boundary). A better understanding of the cycling of iron and sulfur in an anoxic ocean, how geochemical patterns in the ocean relate to the available spatially heterogeneous geological observations, and quantification of the feedback strengths between nutrient cycling, biological productivity, and ocean redox requires a spatially resolved representation of ocean circulation together with an extended set of (bio)geochemical reactions. Here, we extend the “muffin” release of the intermediate-complexity Earth system model cGENIE to now include an anoxic iron and sulfur cycle (expanding the existing oxic iron and sulfur cycles), enabling the model to simulate ferruginous and euxinic redox states as well as the precipitation of reduced iron and sulfur minerals (pyrite, siderite, greenalite) and attendant iron and sulfur isotope signatures, which we describe in full. Because tests against present-day (oxic) ocean iron cycling exercises only a small part of the new code, we use an idealized ocean configuration to explore model sensitivity across a selection of key parameters. We also present the spatial patterns of concentrations and δ56Fe and δ34S isotope signatures of both dissolved and solid-phase Fe and S species in an anoxic ocean as an example application. Our sensitivity analyses show that the first-order results of the model are relatively robust against the choice of kinetic parameter values within the Fe–S system and that simulated concentrations and reaction rates are comparable to those observed in process analogues for ancient oceans (i.e. anoxic lakes). Future model developments will address sedimentary recycling and benthic iron fluxes back to the water column, together with the coupling of nutrient (in particular phosphate) cycling to the iron cycle.

Highlights

  • The biogeochemical cycles of iron and sulfur are tightly coupled in the marine environment and play fundamental roles in the evolution and functioning of the Earth system (Raiswell and Canfield, 2012)

  • We present the development of a coupled anoxic oceanic iron and sulfur cycle embedded within the “muffin” release of the carbon-centric Grid-ENabled Integrated Earth system model, cGENIE

  • The absence of an anoxic iron cycle limits the suitability of cGENIE for simulating low-oxygen worlds in which the ocean interior is pervasively anoxic and iron and sulfur cycling would have dominated ocean biogeochemistry (Poulton and Canfield, 2011; Raiswell and Canfield, 2012)

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Summary

Introduction

The biogeochemical cycles of iron and sulfur are tightly coupled in the marine environment and play fundamental roles in the evolution and functioning of the Earth system (Raiswell and Canfield, 2012). In contrast to the earlier view, the Proterozoic eon appears to have been dominated by ferruginous conditions (Canfield et al, 2008; Planavsky et al, 2011; Poulton and Canfield, 2011; Guilbaud et al, 2015), likely interspersed with euxinic excursions along the shelf (Canfield et al, 2008; Poulton et al, 2010; Raiswell and Canfield, 2012) (Fig. 1) To date, these redox landscapes have been largely qualitative, since field-based observations are restricted by the limited number of available unaltered deposits from a certain point in time and sample acquisition for a depth transect is an enormously labour-intensive task Key boundary conditions and parameter values for these periods of Earth’s history are often poorly constrained, necessitating large model ensembles in order to adequately assess the robustness of any given result

Continental configuration and climatology
The biological carbon pump
Oceanic iron and sulfur cycling
The iron cycle
The oxic iron cycle
The anoxic iron cycle
Reduced iron mineral formation
The sulfur cycle
Isotope geochemistry
56 Fe 54Fe ref
Model testing
The contemporary ocean
An anoxic ocean
Sensitivity analysis
Findings
Outlook and conclusions
Full Text
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