Abstract
Oxidized, sulfur-rich arc magmas are ubiquitous in modern subduction-zone environments. These magmas are thought to form when the fluids released during prograde metamorphism of subducting oceanic crust and overlying sediments oxidize and hydrate the asthenospheric mantle. In contrast, Archaean arc-type magmas are thought to be relatively reduced and sulfur poor, owing to the lower concentrations of marine sulfate and limited oxidative seafloor alteration in the anoxic ocean before the Great Oxidation Event some 2.4 billion years ago (Ga). Here we measure the total sulfur concentration and relative abundances of S6+, S4+ and S2− in zircon-hosted apatite grains from sodic and potassic intrusive rocks from the ~2.7 Ga southeastern Superior Province, Canada. We find that, rather than being reduced and sulfur poor, the sulfur budget of the Neoarchaean magmas was dominated by S6+ and abruptly increased to concentrations comparable to Phanerozoic arc magmas following the interpreted onset of subduction at approximately 2.7 Ga, coincident with the first global pulse of crust generation. These findings indicate that oxidized, sulfur-rich magmas formed in subduction zones independent of ocean redox state and could have influenced oceanic–atmospheric and metallogenic evolution in the Neoarchaean.
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The data that support the findings of this study are available at https://doi.org/10.5281/zenodo.7151046.
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Acknowledgements
The research was funded by Canada First Research Excellence Fund via a Metal Earth (CFREF-2015-00005) thematic project to J.P.R., the National Natural Science Foundation of China (grant number 41820104010, J.M.), the US National Science Foundation EAR (grant number 1924192, A.C.S.) and a China Scholarship Council Ph.D. scholarship (X.M.). We thank D. Crabtree at Ontario GeoLabs for assistance in electron microprobe analysis and A. Lanzirotti and M. Newville at Advanced Photon Sources in the United States for µ-XANES analysis. The research used synchrotron resources (Sector 13-ID-E) of Advanced Photon Source in Argonne National Laboratory under contract number DE-AC02-06CH11357. We thank the Geological Survey of Canada, Ontario Geological Survey, Jack Satterley Geochronology Laboratory (University of Toronto), Ministère de lʼÉnergie et des Ressources Naturelles and the Centre de recherche sur la dynamique du système Terre (GEOTOP; University of Quebec at Montreal) for provision of sample materials. This is a contribution of MERC-ME-2022-31 from Mineral Exploration Research Centre, Harquail School of Earth Sciences.
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X.M. conceived the project and wrote the first version of the manuscript. J.P.R. assisted X.M. in designing an initial project. X.M. identified and measured the composition of the zircon-hosted apatite inclusions and worked with A.C.S. and J.M.K. to complete the µ-XANES analysis. D.R.M. mounted the zircon grains that were previously used for the Hf–O isotopic mapping project of the southeastern Superior Province. All of the authors, including J.M., D.J.K. and P.J.J. contributed to interpreting the data and revising the manuscript.
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Extended data
Extended Data Fig. 1 Simplified geological map of the southeastern Superior Province80 and the spatial distribution of the estimated crustal thickness.
a, Lithology; b, Crustal thickness at >2.685 Ga; c, Crustal thickness at <2.685 Ga. See crustal thickness estimation in the ‘Methods’ section.
Extended Data Fig. 2 Backscattered electron or cathodoluminescence images of zircons with apatite inclusions used for µ-XANES analyses that were separated from representative granitoid rocks from the southeastern Superior Province.
The samples have been grouped into (a) pre-tectonic, syn-volcanic TTG rocks; (b) syn-tectonic TTG rocks; (c) syn- to late-tectonic potassic rocks including (d) late-tectonic alkalic rocks. Insets are mainly BSE images for the analyzed apatite inclusions with a few CL images for the zircon hosts (a8 and b4). Note that the low S concentrations in apatite inclusions in a1 and a8 make the S-XANES spectra undetectable, whereas spectra for the apatite inclusions in c7 and c9 have been contaminated by the zircon hosts and were excluded. Abbreviations: Ap = apatite, Zrn = zircon. See sample information in Supplementary Table 1.
Extended Data Fig. 3 Box charts and histograms for the calculated apatite saturation temperatures estimated for TTG (in red; 898 ± 50 °C, 1σ, n = 1924), potassic (in light blue; 896 ± 69 °C, 1σ, n = 460), and sanukitoid (in blue; 920 ± 45 °C, 1σ, n = 38) rocks in the southeastern Superior Province.
The average values of Ti-in-zircon (764 ± 30 °C, 1σ, n = 50) and zircon saturation temperatures (741 ± 54 °C, 1σ, n = 50, n = 1822) for all of the available samples are calculated and plotted for comparison. The zircon saturation temperature and Ti-in-zircon temperature are calculated using methods of ref. 32 and ref. 33, respectively. Box-and-whisker plots in (a) indicate the median, first and third quartiles, and lower to upper whiskers (±1.5×interquartile range). IQR = interquartile range. The square dots and black diamonds represent mean values and outliers, respectively. The error bands for the zircon saturation and Ti-in-zircon temperatures in (b-d) represent standard deviations.
Extended Data Fig. 4 Normalized apatite µ-XANES spectra at S K-edge for representative intermediate-felsic rocks from the southeastern Superior Province (Canada).
a, pre-tectonic TTG (in pink). b, syn-tectonic TTG (in red). c, potassic rocks (in blue). The analysis numbers are consistent with the sample numbers in Extended Data Fig. 2. Peak positions for S2−, S4+, S6+ are at 2470 eV, 2477 eV, and 2482 eV, respectively, and are shown as dotted gray lines. The calculated S6+/ΣS ratios are shown on right of each spectra. See sample information in Supplementary Table 1.
Extended Data Fig. 6 Box charts and histograms for the crustal thickness of southeastern Superior Province at >2.685 Ga and <2.685 Ga estimated based on compositions of TTG (in red; 48 ± 21 km, 1σ, n = 773) and potassic (including sanukitoid, in blue; to 65 ± 14 km, 1σ, n = 135) rocks, respectively.
Box-and-whisker plots in (a) indicate the median, first and third quartiles, and lower to upper whiskers (±1.5×interquartile range). IQR = interquartile range. The square dots and black diamonds represent mean values and outliers, respectively.
Supplementary information
Supplementary Table 1
Summary of the sample locations and information for this study.
Supplementary Table 2
Electron probe micro-analyses of zircon-hosted apatite grains for representative sodic and potassic rocks from the southeastern Superior Province.
Supplementary Table 3
The average magmatic values (relatively to FMQ redox buffer) estimated using a zircon Ce–Ti–Ui oxybarometer for representative Phanerozoic arc magmas.
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Meng, X., Simon, A.C., Kleinsasser, J.M. et al. Formation of oxidized sulfur-rich magmas in Neoarchaean subduction zones. Nat. Geosci. 15, 1064–1070 (2022). https://doi.org/10.1038/s41561-022-01071-5
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DOI: https://doi.org/10.1038/s41561-022-01071-5
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