Iron Isotope Fractionation during Skarn Cu-Fe Mineralization

Fe isotopes have been applied to the petrogenesis of ore deposits. However, the behavior of iron isotopes in the mineralization of porphyry-skarn deposits is still poorly understood. In this study, we report the Fe isotopes of ore mineral separations (magnetite, pyrite, chalcopyrite and pyrrhotite) from two different skarn deposits, i.e., the Tonglvshan Cu-Fe skarn deposit developed in an oxidized hydrothermal system and the Anqing Cu skarn deposit developed in a reduced hydrothermal system. In both deposits, the Fe isotopes of calculated equilibrium fluids are lighter than those of the intrusions responsible for the skarn and porphyry mineralization, corroborating the “light-Fe fluid” hypothesis. Interestingly, chalcopyrite in the oxidized-Tonglvshan skarn deposit has lighter Fe than chalcopyrite in the reduced-Anqing skarn deposit, which is best understood as the result of the prior precipitation of magnetite (heavy Fe) from the ore fluid in the oxidized-Tonglvshan systems and the prior precipitation of pyrrhotite (light Fe) from the ore fluid in the reduced-Anqing system. The δ56Fe for pyrite shows an inverse correlation with δ56Fe of magnetite in the Tonglvshan. In both deposits, the Fe isotope fractionation between chalcopyrite and pyrite is offset from the equilibrium line at 350 °C and lies between the FeS-chalcopyrite equilibrium line and pyrite-chalcopyrite equilibrium line at 350 °C. These observations are consistent with the FeS pathway towards pyrite formation. That is, Fe isotopes fractionation during pyrite formation depends on a path from the initial FeS-fluid equilibrium towards the pyrite-fluid equilibrium due to the increasing extent of Fe isotopic exchange with fluids. This finding, together with the data from other deposits, allows us to propose that the pathway effect of pyrite formation in the Porphyry-skarn deposit mineralization is the dominant mechanism that controls Fe isotope characteristics.

The impact of depositional conditions on biogeochemical cycling of iron and stable iron signatures in sediments of the Argentina Continental Margin

<p>The Argentina Continental Margin represents a unique geologic setting to study interactions between bottom currents and sediment deposition as well as their impact on (bio)geochemical processes, particularly the cycling of iron (Fe). Our aim was to determine (1) how different depositional conditions control post-depositional (bio)geochemical processes and (2) how stable Fe isotopes (δ<sup>56</sup>Fe) of pore water and solid phases are affected accordingly. Furthermore, we (3) evaluated the applicability of δ<sup>56</sup>Fe of solid Fe pools as a proxy to trace past diagenetic alteration of Fe, which might be decoupled from current redox conditions. Sediments from two different depositional environments were sampled during RV SONNE expedition SO260: a site dominated by contouritic deposition on a terrace (Contourite Site) and the lower continental slope (Slope Site) dominated by hemipelagic sedimentation. Sequentially extracted sedimentary Fe [1] and δ<sup>56</sup>Fe analyses of extracts and pore water [2,3] were combined with sedimentological, radioisotope, geochemical and magnetic data. Our study presents the first sedimentary δ<sup>56</sup>Fe dataset at the Argentina Continental Margin.</p><p>The depositional conditions differed between and within both sites as evidenced by variable grain sizes, organic carbon contents and sedimentation rates. At the Contourite Site, non-steady state pore-water conditions and diagenetic overprint occurs in the post-oxic zone and the sulfate-methane transition (SMT). In contrast, pore-water profiles at the Slope Site suggest that currently steady-state conditions prevail, leading to a strong diagenetic overprint of Fe oxides at the SMT. Pore-water δ<sup>56</sup>Fe values at the Slope Site are mostly negative, which is typical for on-going microbial Fe reduction. At the Contourite Site the pore-water δ<sup>56</sup>Fe values are mostly positive and range between -0.35‰ to 1.82‰. Positive δ<sup>56</sup>Fe values are related to high sulfate reduction rates that dominate over Fe reduction in the post-oxic zone. The HS<sup>- </sup>liberated during organoclastic sulfate reduction or sulfate-mediated anaerobic oxidation of methane (AOM) reacts with Fe<sup>2+</sup> to form Fe sulfides. Hereby, light Fe isotopes are preferentially removed from the dissolved pool. The isotopically light Fe sulfides drive the acetate-leached Fe pool towards negative values. Isotopic trends were absent in other extracted Fe pools, partly due to unintended dissolution of silicate Fe masking the composition of targeted Fe oxides. Significant amounts of reactive Fe phases are preserved below the SMT and are possibly available for reduction processes, such as Fe-mediated AOM [4]. Fe<sup>2+</sup> in the methanic zone is isotopically light at both sites, which is indicative for a microbial Fe reduction process.</p><p>Our results demonstrate that depositional conditions exert a significant control on geochemical conditions and dominant (bio)geochemical processes in the sediments of both contrasting sites. We conclude that the applicability of sedimentary δ<sup>56</sup>Fe signatures as a proxy to trace diagenetic Fe overprint is limited to distinct Fe pools. The development into a useful tool depends on the refining of extraction methods or other means to analyse δ<sup>56</sup>Fe in specific sedimentary Fe phases.</p><p> </p><p>References:</p><p>[1]Poulton and Canfield, 2005. Chemical Geology 214: 209-221.<br>[2]Henkel et al., 2016. Chemical Geology 421: 93-102.<br>[3]Homoky et al., 2013. Nature Communications 4: 1-10.<br>[4]Riedinger et al., 2014. Geobiology 12: 172-181.</p>

Rodingitization of mafic and ultramafic rocks in ophiolites from Northern Greece, seen by non-traditional stable isotopes, such as Cu, Fe and Zn.

<p>Rodingites are metasomatic rocks, frequently found in ophiolitic complexes. They offer important information about the interaction between ultramafic-mafic rocks and metasomatizing fluids, as well as about the post-magmatic evolution of ophiolitic suites (Tsikouras et al., 2009; Hu & Santosh, 2017; Surour, 2019; Laborda-Lopez et al., 2020). Metasomatism, such as rodingitization, is a very intricate process, which depends on the mineralogy of the initial rock, the nature of the metasomatic agent, the fluid/rock ratio, the duration of metasomatism and the chemical disequilibrium at the time of metasomatism between the host rock and the metasomatic medium (Poitrasson et al., 2013). Rodingites from the Veria-Naousa and Edessa ophiolites, in Northern Greece, were geochemically analyzed and characterized by substantial overprint of primary textures. Their field observation, their neoblastic mineral assemblages and metasomatic textures reveal that they derived from ultramafic and mafic protoliths. The mineral phases in the ultramafic derived rodingites (UDR) include mainly diopside, garnet, chlorite, epidote, tremolite and Fe-Ti oxides whereas mafic derived rodingites (MDR) consist of diopside, garnet, vesuvianite, chlorite, quartz, prehnite and actinolite. The studied rodingites present δ<sup>65</sup>Cu values varying from -0.17‰ to 0.62‰ and for ultramafic and mafic parent-rocks from -0.49‰ to +0.50‰. The UDR and MDR from both ophiolites display δ<sup>66</sup>Zn range from -0.06‰ to 0.74‰ and their photoliths present a narrower range from +0.04‰ to +0.41‰. Rodingitization affects in different way UDR and MDR samples. On one hand, Cu isotope ratios are systematically heavier in rodingites compared to their respective protoliths, except for one rodingite sample that requires confirmation due to large error bar. On the other hand, Zn isotopes show enrichment in light isotopes (group 1: comprising all UDR and some MDR samples), or in heavy isotopes (group 2, only MDR samples). Intriguingly, the same protolith can lead to both group 1 and 2 rodingites, as defined here.  No mineralogical or geochemical trend can be found to understand the dual behavior of Zn stable isotopes during rodingitization so far. Fe isotopes do not show any significant fractionation of δ<sup>56</sup>Fe, ranging from +0.07‰ to +0.19‰ for the rodingites and from +0.12‰ to +0.23‰ for their protoliths, indicating that Fe isotopes are highly resistant to rodingitization. Our study shows that rodingitization enriches metasomatized samples in heavy Cu isotopes and has no impact on Fe isotopes. It remains unclear why Zn isotopes can be affected both ways.</p>

More than redox, biological organic ligands control iron isotope fractionation in the riparian wetland

Although redox reactions are recognized to fractionate iron (Fe) isotopes, the dominant mechanisms controlling the Fe isotope fractionation and notably the role of organic matter (OM) are still debated. Here, we demonstrate how binding to organic ligands governs Fe isotope fractionation beyond that arising from redox reactions. The reductive biodissolution of soil Fe(III) enriched the solution in light Fe isotopes, whereas, with the extended reduction, the preferential binding of heavy Fe isotopes to large biological organic ligands enriched the solution in heavy Fe isotopes. Under oxic conditions, the aggregation/sedimentation of Fe(III) nano-oxides with OM resulted in an initial enrichment of the solution in light Fe isotopes. However, heavy Fe isotopes progressively dominate the solution composition in response to their binding with large biologically-derived organic ligands. Confronted with field data, these results demonstrate that Fe isotope systematics in wetlands are controlled by the OM flux, masking Fe isotope fractionation arising from redox reactions. This work sheds light on an overseen aspect of Fe isotopic fractionation and calls for a reevaluation of the parameters controlling the Fe isotopes fractionation to clarify the interpretation of the Fe isotopic signature.