Coupled Fe and S isotope variations in pyrite nodules from Archean shale

Marin‐Carbonne, Johanna; Rollion‐Bard, Claire; Bekker, Andrey; Rouxel, Olivier; Agangi, Andrea; Cavalazzi, Barbara; Wohlgemuth‐Ueberwasser, Cora C.; Hofmann, Axel; McKeegan, Kevin D.

doi:10.1016/j.epsl.2014.02.009

Cited by 95 publications

(64 citation statements)

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“…The lowest content of Hg, ~0.01-10 ppm, was reported for pyrite from porphyry (Cu-Au-Mo) deposits, sedimentary pyrite, and orogenic Au deposits (Pass 2010;Franchini et al 2015;Marin-Carbonne et al 2014;Palenova et al 2015). In contrast, the highest amounts of Hg were found in pyrite from Carlin-type and epithermal…”

Section: Mercurymentioning

confidence: 82%

Constraints on the solid solubility of Hg, Tl, and Cd in arsenian pyrite

Deditius

Reich²

2016

American Mineralogist

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Arsenic-rich (arsenian) pyrite can contain up to tens of thousands of parts per million (ppm) of toxic heavy metals such as Hg, Tl, and Cd, although few data are available on their solid solubility behavior. When a compilation of Hg, Tl, and Cd analyses from different environments are plotted along with As in a M(Hg, Tl, and Cd)-As log-log space, the resulting wedge-shaped distribution of data points suggests that the solid solubility of the aforementioned metals is strongly dependent on the As concentration of pyrite. The solid solubility limits of Hg in arsenian pyrite-i.e., the upper limit of the wedge-shaped zone in compositional space-are similar to the one previously defined for Au by ), whereas the solubility limit of Tl in arsenian pyrite is approximated by a ratio of Tl/As = 1. In contrast, and despite a wedge-shaped distribution of Cd-As data points for pyrite in Cd-As log-log space, the majority of Cd analyses reflect the presence of mineral particles of Cd-rich sphalerite and/or CdS. Based on these data, we show that arsenian pyrite with M/As ratios above the solubility limit of Hg and Tl contain nanoparticles of HgS, and multimetallic Tl-Hg mineral nanoparticles. These results indicate that the uptake of Hg and Tl in pyrite is strongly dependent on As contents, as it has been previously documented for metals such as Au and Cu. Cadmium, on the other hand, follows a different behavior and its incorporation into the pyrite structure is most likely limited by the precipitation of Cd-rich nanoparticulate sphalerite. The distribution of metal concentrations below the solubility limit suggests that hydrothermal fluids from which pyrite precipitate are dominantly undersaturated with respect to species of Hg and Tl, favoring the incorporation of these metals into the pyrite structure as solid solution. In contrast, the formation of metallic aggregates of Hg and Tl or mineral nanoparticles in the pyrite matrix occurs when Hg and Tl locally oversaturate with respect to their solid phases at constant temperature. This process can be kinetically enhanced by high-to-medium temperature metamorphism and thermal processing or combustion, which demonstrates a retrograde solubility for these metals in pyrite.

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Section: Mercurymentioning

confidence: 82%

Constraints on the solid solubility of Hg, Tl, and Cd in arsenian pyrite

Deditius

Reich²

2016

American Mineralogist

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“…S19). Such a gradient, similar to those observed in larger pyrite nodules of Archean age (Fischer et al ., ; Marin‐Carbonne et al ., ), requires local heterogeneities in Δ 33 S of pore fluids, changes in S‐MIF production on the time scale of nodule growth, or an as yet unconstrained biological effect.…”

Section: Resultsmentioning

confidence: 99%

Carbon and sulfur isotopic signatures of ancient life and environment at the microbial scale: Neoarchean shales and carbonates

et al. 2015

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An approach to coordinated, spatially resolved, in situ carbon isotope analysis of organic matter and carbonate minerals, and sulfur three- and four-isotope analysis of pyrite with an unprecedented combination of spatial resolution, precision, and accuracy is described. Organic matter and pyrite from eleven rock samples of Neoarchean drill core express nearly the entire range of δ(13) C, δ(34) S, Δ(33) S, and Δ(36) S known from the geologic record, commonly in correlation with morphology, mineralogy, and elemental composition. A new analytical approach (including a set of organic calibration standards) to account for a strong correlation between H/C and instrumental bias in SIMS δ(13) C measurement of organic matter is identified. Small (2-3 μm) organic domains in carbonate matrices are analyzed with sub-permil accuracy and precision. Separate 20- to 50-μm domains of kerogen in a single ~0.5 cm(3) sample of the ~2.7 Ga Tumbiana Formation have δ(13) C = -52.3 ± 0.1‰ and -34.4 ± 0.1‰, likely preserving distinct signatures of methanotrophy and photoautotrophy. Pyrobitumen in the ~2.6 Ga Jeerinah Formation and the ~2.5 Ga Mount McRae Shale is systematically (13) C-enriched relative to co-occurring kerogen, and associations with uraniferous mineral grains suggest radiolytic alteration. A large range in sulfur isotopic compositions (including higher Δ(33) S and more extreme spatial gradients in Δ(33) S and Δ(36) S than any previously reported) are observed in correlation with morphology and associated mineralogy. Changing systematics of δ(34) S, Δ(33) S, and Δ(36) S, previously investigated at the millimeter to centimeter scale using bulk analysis, are shown to occur at the micrometer scale of individual pyrite grains. These results support the emerging view that the dampened signature of mass-independent sulfur isotope fractionation (S-MIF) associated with the Mesoarchean continued into the early Neoarchean, and that the connections between methane and sulfur metabolism affected the production and preservation of S-MIF during the first half of the planet's history.

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“…Isotopic compositions of iron and sulphur in pyrites from sedimentary rocks have been proposed as potential proxies to assess the redox state of ancient oceans (Rouxel et al, 2005;Reinhard et al, 2009;Marin-Carbonne et al, 2014), the oxygen outgrowth in the atmosphere (Catling and Claire, 2005;Ohmoto et al, 2006) and early microbial metabolisms (Johnson et al, 2008). Moreover, trace metals incorporated in pyrite have been recognised as proxies for ancient ocean chemistry (Large et al, 2017).…”

Section: Introductionmentioning

confidence: 99%

Nickel accelerates pyrite nucleation at ambient temperature

Morin¹,

Noël²,

Menguy³

et al. 2017

Geochem. Persp. Let.

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Chemical and isotopic compositions of pyrites are used as biogeochemical tracers in Archean to modern sediments. Moreover, pyrite formation from monosulphide precursors has been proposed to be involved in prebiotic chemistry. However, the factors controlling pyrite formation and distribution in the sedimentary record are incompletely understood. Here, we show that Ni 2+ ions accelerate ~5 times the nucleation of pyrite at ambient temperature. Using Fe and Ni K-edge EXAFS and TEM-EDXS we demonstrate that Ni(II) is directly involved in the nucleation of pyrite synthesised by reacting Fe(III) with Na 2 S in the presence of aqueous Ni(II) impurity. Initial formation of a Ni-enriched pyrite core is followed by overgrowth of a Ni-depleted pyrite shell, leading to compositional zoning of the Fe 1-x Ni x S 2 nanocrystals (x = 0.05 to 0.0004). The molar Ni/Fe ratio in the final aqueous solution was then 2000 times lower than the starting ratio of 0.01. This enhanced and accelerated trapping of Ni by pyrite could be of prime importance in controlling Ni concentration in the ocean during early diagenesis of marine sediments, and could thus have important implications for interpreting abundances of Ni and pyrite in the sedimentary record. In addition, acceleration of pyrite nucleation in the presence of nickel could help understanding the role of Fe-Ni sulphides in catalysing potential prebiotic reactions.

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Coupled Fe and S isotope variations in pyrite nodules from Archean shale

Cited by 95 publications

References 64 publications

Constraints on the solid solubility of Hg, Tl, and Cd in arsenian pyrite

Constraints on the solid solubility of Hg, Tl, and Cd in arsenian pyrite

Carbon and sulfur isotopic signatures of ancient life and environment at the microbial scale: Neoarchean shales and carbonates

Nickel accelerates pyrite nucleation at ambient temperature

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