Redox-independent chromium isotope fractionation induced by ligand-promoted dissolution

December 31, 1969 |

The chromium (Cr) isotope system has emerged as a potential proxy for tracing the Earth’s atmospheric evolution based on a redox-dependent framework for Cr mobilization and isotope fractionation. Although studies have demonstrated that redox-independent pathways can also mobilize Cr, no quantitative constraints exist on the associated isotope fractionations. Here we survey the effects of common environmental ligands on the dissolution of Cr(III)-(oxy)hydroxide solids and associated Cr isotope fractionation. For a variety of organic acids and siderophores, δ53Cr values of dissolved Cr(III) are −0.27 to 1.23‰, within the range of previously observed Cr isotope signatures in rock records linked to Cr redox cycling. Thus, ligand-promoted dissolution of Cr-containing solids, a redox-independent process, must be taken into account when using sedimentary Cr isotope signatures to diagnose atmospheric oxygen levels. This work provides a step towards establishing a more robust framework for using Cr isotopes to track the evolution of the Earth’s atmosphere.

Introduction:

The chromium (Cr) isotope system has been exploited as a highly discriminating tracer of redox processes in the Earth’s surface environments, and is under development as a novel paleobarometer for atmospheric oxygen levels1,2,3,4,5. Many of these applications are based on the assumption that Cr isotope fractionations are linked predominantly to Cr redox transformations. Consistent with this view, theoretical and experimental studies have suggested very little Cr fractionation during redox-independent processes, such as adsorption6, though recent experimental studies demonstrated large equilibrium fractionations between various Cr–Cl species7. Cr isotopes have been extensively employed in environmental geochemistry as a quantitative proxy for Cr transport and remediation efficiency (see ref. 8 and references therein). However, in order to quantitatively apply this isotope system as a tracer for Earth’s surface processes, it is critical to more precisely quantify a wider range of factors controlling the global Cr cycle and isotope budget9. Indeed, since the early proposed uses of the Cr isotope system, there have been several studies recognizing the need to account for other biogeochemical processes in addition to the redox pathway-based framework of this isotope system7,10,11,12,13,14.

The two most common oxidation states of Cr in natural environments are Cr(III) and Cr(VI). Cr(III) is typically insoluble and is the most common form of Cr in rocks and minerals at the Earth’s surface. Cr(VI) is typically soluble and is the dominant form of mobile Cr in natural environments. The standard view of the Cr isotope paleoredox proxy is grounded in the idea that oxidative weathering of Cr(III)-containing minerals by manganese (Mn) oxides, the formation of which requires free oxygen, is required for Cr redox cycling and Cr isotope fractionations. During this oxidation process, soluble Cr(VI) is released and transported to oceans, reduced to Cr(III) under reducing environments, and deposited in marine sediments1,15. Thus, authigenic marine sediments capture an integrated isotopic signature reflective of the redox processes involved in Cr(III) oxidative mobilization, downstream Cr(VI) reduction, and ultimate Cr(III) burial in sediments1.

The redox transformation between Cr(III) and Cr(VI) causes a significant change in the local coordination environment of Cr. Cr(III) typically occurs as an octahedrally coordinated cation, whereas Cr(VI) primarily occurs as a tetrahedrally coordinated oxyanion. The large change in coordination environment during redox transformations leads to significant isotopic fractionation, similar to other redox-sensitive elements16. Unweathered igneous rocks, with limited exceptions17, exhibit a narrow range of δ53Cr values of −0.124 ± 0.101‰ (defined as δ53Cr = [(53Cr/52Cr)sample/(53Cr/52Cr)standard −1] × 1000)15. Cr(III) oxidation to Cr(VI) can result in significant isotopic fractionations, both negative and positive (53εCr(VI)-Cr(III) ranging from −2.5 to +1.1‰), depending on the reaction conditions; while reduction of Cr(VI) to Cr(III) has consistently been shown to leave the remaining Cr(VI) isotopically heavy (53εCr(III)–Cr(VI) ranging from −7.6 to −0.4‰) (see, e.g., ref. 8). Because the isotopic exchange and subsequent isotopic equilibrium between Cr(III) and Cr(VI) requires three electron transfer with a significant coordination reconfiguration, the isotopic exchange rate of these species is extremely slow18,19. However, when dissolved Cr(VI)- and Cr(III)-containing solids are in contact for long periods, equilibrium fractionation may become relevant. The significance of such a process under actual environmental settings (e.g., during the weathering of Cr-containing rocks/minerals) can vary and is dependent on many factors, such as the relative ratio of the exchanging Cr(VI) and Cr(III) species19. Therefore, Cr isotope systematics during the Earth’s surface processes are generally assumed to be dominated by kinetic fractionations. Regardless, current experimental and empirical results suggest that both kinetic and equilibrium processes tend to lead to Cr(VI) that is isotopically heavy19,20.

One generally overlooked mechanism for Cr(III) mobilization is ligand complexation. Indeed, measurements on natural waters have revealed elevated concentrations of dissolved Cr(III) that are higher than the solubility of Cr(OH)3 solids, one common sink phase of Cr(III), and suggest the likely complexation of Cr(III) by inorganic21 and/or organic molecules (e.g., refs. 22,23,24). The speciation of Cr in hydrothermal fluids, and marine settings more broadly, is also thought to be influenced by organically complexed Cr(III)25,26. Two classes of organic ligands, siderophores (e.g., desferrioxamine B, rhizoferrin, protochelin)27 and organic acids (e.g., citric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid)28, have been shown to be capable of solubilizing Cr(III) from the Cr(OH)3 solid phase under environmentally relevant conditions. Both siderophores and organic acids are ubiquitous organic molecules in natural environments and are produced by a wide range of microorganisms and often co-exuded29. Siderophores are organic chelating agents with a high affinity for Fe(III) for enhancing Fe dissolution from low-solubility Fe(III)-mineral phases30. Siderophores have also been shown to have strong affinities for other trivalent metal cations such as Cr(III) due to their structural similarity (e.g., size, coordination environment) to Fe(III)31. Organic acids are known to contribute to the mobilization of metals in soils32, and a wide range of organic acids (e.g., oxalic, citric, fulvic, and humic acids) have been shown to complex with Cr(III)33,34,35. Organic acids are likely to have been present throughout the Earth’s history through abiotic or biotic synthesis pathways (see, e.g., refs. 36, 37) and may have played important roles in the weathering38 of poorly soluble transition metals.

Despite the potential importance of Cr(III)–ligand complexes in Earth’s surface, Cr isotope fractionation during Cr(III) complexation with organic ligands has not been experimentally measured, although the potential for fractionation upon complexation with inorganic ligands has been previously suggested by theoretical studies19,20 and observed experimentally7. Additionally, several recent studies have inferred redox-independent Cr cycling in the interpretation of relevant rock records based on the site-specific geochemistry and Cr isotope dynamics10,11.

Here, we survey the extent of Cr isotope fractionation that occurs during ligand complexation and dissolution of Cr(III)-containing solid phases. Given the potential for analytically significant fractionations, these redox-independent processes may add complexity when using Cr isotopes to track Cr oxidative mobilization and Cr reduction during environmental remediation. We systematically characterize the dissolution of a Cr(III)-containing solid by a wide range of organic ligands, and quantified the attendant isotope effects with an eye toward better understanding the potential impact of Cr(III)–ligand complexation on global Cr cycling and interpretation of isotope signatures.