Abstract
Seafloor-derived silicified volcanic and sedimentary rocks provide unique records of hydrothermal systems that operated at the top of the Paleoarchean submerged crust. Based on petrographic, thermometric, and geochemical analyses, we distinguish the signatures of Paleoarchean hydrothermal activity from those due to subsequent metamorphism and weathering in silicified volcanic and sedimentary rocks sampled from the 3.5–3.2 Ga Barberton Greenstone Belt. Measured 138La-138Ce and 147Sm-143Nd isotopic compositions indicate that weathering by post-Archean oxidised fluids modified LREE abundances in samples displaying Ce anomalies. Raman spectroscopy of carbonaceous material, chlorite thermometry and oxygen isotope thermometry provide evidence for mineralogical resetting by regional metamorphism at ∼350 ± 50 °C, which arguably did not modify the bulk-rock geochemistry. Oxygen isotope fractionation in a quartz-carbonate assemblage preserved from subsequent resetting provides a minimum temperature of ∼110 ± 50 °C interpreted as the highest possible temperature of the Paleoarchean silicifying hydrothermal fluids. Y/Ho and Zr/Hf ratios are chondritic in silicified volcanic and clastic sedimentary rocks, which differentiates them from Archean orthochemical cherts with suprachondritic Y/Ho and Zr/Hf ratios. Finally, silicified volcanic rocks that are free of Ce anomalies (mostly unweathered by oxidising fluids) display slightly lower Sm/Nd ratios and more variable Lu/Hf ratios than non-silicified counterparts, which we ascribe to differential REE mobilisation by silicifying hydrothermal fluids. The modification of Sm/Nd and Lu/Hf ratios during Paleoarchean hydrothermal activity should be integrated in future Sm-Nd and Lu-Hf isotopic investigations of hydrothermal inputs to Archean ocean chemistry and of recycled seafloor-derived rocks.
References
Abraham, K., Hofmann, A., Foley, S. F., Cardinal, D., Harris, C., Barth, M. G., & André, L. (2011). Coupled silicon–oxygen isotope fractionation traces Archaean silicification. Earth and Planetary Science Letters, 301(1–2), 222–230. https://doi.org/10.1016/j.epsl.2010.11.002
Aguirre, L. (1988). Chemical mobility during low-grade metamorphism of a Jurassic lava flow: Río Grande Formation, Peru. Journal of South American Earth Sciences, 1(4), 343–361. https://doi.org/10.1016/0895-9811(88)90022-3
Alibo, D. S., & Nozaki, Y. (1999). Rare earth elements in seawater: particle association, shale-normalization, and Ce oxidation. Geochimica et Cosmochimica Acta, 63(3–4), 363–372. https://doi.org/10.1016/s0016-7037(98)00279-8
Alleon, J., Bernard, S., Olivier, N., Thomazo, C., & Marin-Carbonne, J. (2021). Inherited geochemical diversity of 3.4 Ga organic films from the Buck Reef Chert, South Africa. Communications Earth and Environment, 2(1), 4–10. https://doi.org/10.1038/s43247-020-00066-7
Allwood, A. C., Kamber, B. S., Walter, M. R., Burch, I. W., & Kanik, I. (2010). Trace elements record depositional history of an Early Archean stromatolitic carbonate platform. Chemical Geology, 270(1–4), 148–163. https://doi.org/10.1016/j.chemgeo.2009.11.013
Alt, J. C., Laverne, C., Coggon, R. M., Teagle, D. A. H., Banerjee, N. R., Morgan, S., Smith‐Duque, C. E., Harris, M., & Galli, L. (2010). Subsurface structure of a submarine hydrothermal system in ocean crust formed at the East Pacific Rise, ODP/IODP Site 1256. Geochemistry, Geophysics, Geosystems, 11(10), 1–28. https://doi.org/10.1029/2010gc003144
Anders, E., & Grevesse, N. (1989). Abundances of the elements: Meteoritic and solar. Geochimica et Cosmochimica Acta, 53(1), 197–214. https://doi.org/10.1016/0016-7037(89)90286-x
André, L., Abraham, K., Hofmann, A., Monin, L., Kleinhanns, I. C., & Foley, S. (2019). Early continental crust generated by reworking of basalts variably silicified by seawater. Nature Geoscience, 12(9), 769–773. https://doi.org/10.1038/s41561-019-0408-5
André, L., Monin, L., & Hofmann, A. (2022). The origin of early continental crust: New clues from coupling Ge/Si ratios with silicon isotopes. Earth and Planetary Science Letters, 582, 117415. https://doi.org/10.1016/j.epsl.2022.117415
Anhaeusser, C. R. (1981). Chapter 6 Geotectonic Evolution of the Archaean Successions in the Barberton Mountain Land, South Africa. In Developments in Precambrian Geology (Vol. 4, pp. 137–160). Elsevier. https://doi.org/10.1016/s0166-2635(08)70011-2
Armstrong, R. A., Compston, W., de Wit, M. J., & Williams, I. S. (1990). The stratigraphy of the 3.5-3.2 Ga Barberton Greenstone Belt revisited: A single zircon ion microprobe study. Earth and Planetary Science Letters, 101(1), 90–106. https://doi.org/10.1016/0012-821x(90)90127-j
Bach, W., Peucker‐Ehrenbrink, B., Hart, S. R., & Blusztajn, J. S. (2003). Geochemistry of hydrothermally altered oceanic crust: DSDP/ODP Hole 504B – Implications for seawater‐crust exchange budgets and Sr‐ and Pb‐isotopic evolution of the mantle. Geochemistry, Geophysics, Geosystems, 4(3), 40–55. https://doi.org/10.1029/2002gc000419
Banerjee, A., Chakrabarti, R., & Mandal, S. (2016). Geochemical anatomy of a spheroidally weathered diabase. Chemical Geology, 440, 124–138. https://doi.org/10.1016/j.chemgeo.2016.07.008
Bau, M. (1996). Controls on the fractionation of isovalent trace elements in magmatic and aqueous systems: evidence from Y/Ho, Zr/Hf, and lanthanide tetrad effect. Contributions to Mineralogy and Petrology, 123(3), 323–333. https://doi.org/10.1007/s004100050159
Bea, F., Montero, P., Barcos, L., Cambeses, A., Molina, J. F., & Morales, I. (2023). Understanding Nd model ages of granite rocks: The effects of the 147Sm/144Nd variability during partial melting and crystallization. Lithos, 436–437, 106940. https://doi.org/10.1016/j.lithos.2022.106940
Bégué, F., Baumgartner, L. P., Bouvier, A.-S., & Robyr, M. (2019). Reactive fluid infiltration along fractures: Textural observations coupled to in-situ isotopic analyses. Earth and Planetary Science Letters, 519, 264–273. https://doi.org/10.1016/j.epsl.2019.05.024
Beyssac, O., Goffé, B., Chopin, C., & Rouzaud, J. N. (2002). Raman spectra of carbonaceous material in metasediments: a new geothermometer. Journal of Metamorphic Geology, 20(9), 859–871. https://doi.org/10.1046/j.1525-1314.2002.00408.x
Bindeman, I. N., & O’Neil, J. (2022). Earth’s earliest hydrosphere recorded by the oldest hydrothermally-altered oceanic crust: Triple oxygen and hydrogen isotopes in the 4.3-3.8 Ga Nuvvuagittuq belt, Canada. Earth and Planetary Science Letters, 586, 117539. https://doi.org/10.1016/j.epsl.2022.117539
Bolhar, R., Kamber, B. S., Moorbath, S., Fedo, C. M., & Whitehouse, M. J. (2004). Characterisation of early Archaean chemical sediments by trace element signatures. Earth and Planetary Science Letters, 222(1), 43–60. https://doi.org/10.1016/j.epsl.2004.02.016
Bonnand, P., Israel, C., Boyet, M., Doucelance, R., & Auclair, D. (2019). Radiogenic and stable Ce isotope measurements by thermal ionisation mass spectrometry. Journal of Analytical Atomic Spectrometry, 34(3), 504–516. https://doi.org/10.1039/c8ja00362a
Bonnand, P., Lalonde, S. V., Boyet, M., Heubeck, C., Homann, M., Nonnotte, P., Foster, I., Konhauser, K. O., & Köhler, I. (2020). Post-depositional REE mobility in a Paleoarchean banded iron formation revealed by La-Ce geochronology: A cautionary tale for signals of ancient oxygenation. Earth and Planetary Science Letters, 547, 116452. https://doi.org/10.1016/j.epsl.2020.116452
Bourdelle, F. (2021). Low-Temperature Chlorite Geothermometry and Related Recent Analytical Advances: A Review. Minerals, 11(2), 130. https://doi.org/10.3390/min11020130
Bouvier, A., Vervoort, J. D., & Patchett, P. J. (2008). The Lu–Hf and Sm–Nd isotopic composition of CHUR: Constraints from unequilibrated chondrites and implications for the bulk composition of terrestrial planets. Earth and Planetary Science Letters, 273(1–2), 48–57. https://doi.org/10.1016/j.epsl.2008.06.010
Brengman, L. A., & Fedo, C. M. (2018). Development of a mixed seawater-hydrothermal fluid geochemical signature during alteration of volcanic rocks in the Archean (sim2.7 Ga) Abitibi Greenstone Belt, Canada. Geochimica et Cosmochimica Acta, 227, 227–245. https://doi.org/10.1016/j.gca.2018.02.019
Byerly, G. R., Lowe, D. R., & Heubeck, C. (2019). Geologic Evolution of the Barberton Greenstone Belt—A Unique Record of Crustal Development, Surface Processes, and Early Life 3.55–3.20 Ga. In Earth’s Oldest Rocks (pp. 569–613). Elsevier. https://doi.org/10.1016/b978-0-444-63901-1.00024-1
Calvert, S. E., Piper, D. Z., & Baedecker, P. A. (1987). Geochemistry of the rare earth elements in ferromanganese nodules from DOMES Site A, northern equatorial Pacific. Geochimica et Cosmochimica Acta, 51(9), 2331–2338. https://doi.org/10.1016/0016-7037(87)90287-0
Cammack, J. N., Spicuzza, M. J., Cavosie, A. J., Van Kranendonk, M. J., Hickman, A. H., Kozdon, R., Orland, I. J., Kitajima, K., & Valley, J. W. (2018). SIMS microanalysis of the Strelley Pool Formation cherts and the implications for the secular-temporal oxygen-isotope trend of cherts. Precambrian Research, 304, 125–139. https://doi.org/10.1016/j.precamres.2017.11.005
Chacko, T., & Deines, P. (2008). Theoretical calculation of oxygen isotope fractionation factors in carbonate systems. Geochimica et Cosmochimica Acta, 72(15), 3642–3660. https://doi.org/10.1016/j.gca.2008.06.001
Chavagnac, V. (2004). A geochemical and Nd isotopic study of Barberton komatiites (South Africa): implication for the Archean mantle. Lithos, 75(3–4), 253–281. https://doi.org/10.1016/j.lithos.2004.03.001
Clayton, R. N., O’Neil, J. R., & Mayeda, T. K. (1972). Oxygen isotope exchange between quartz and water. Journal of Geophysical Research, 77(17), 3057–3067. https://doi.org/10.1029/jb077i017p03057
Condie, K. C., Viljoen, M. J., & Kable, E. J. D. (1977). Effects of alteration on element distributions in archean tholeiites from the Barberton greenstone belt, South Africa. Contributions to Mineralogy and Petrology, 64(1), 75–89. https://doi.org/10.1007/bf00375286
Coogan, L. A., & Gillis, K. M. (2018). Temperature dependence of chemical exchange during seafloor weathering: Insights from the Troodos ophiolite. Geochimica et Cosmochimica Acta, 243, 24–41. https://doi.org/10.1016/j.gca.2018.09.025
Cutts, K. A., Stevens, G., Hoffmann, J. E., Buick, I. S., Frei, D., & Münker, C. (2014). Paleo- to Mesoarchean polymetamorphism in the Barberton Granite-Greenstone Belt, South Africa: Constraints from U-Pb monazite and Lu-Hf garnet geochronology on the tectonic processes that shaped the belt. Geological Society of America Bulletin, 126(3–4), 251–270. https://doi.org/10.1130/b30807.1
Cutts, K. A., Stevens, G., & Kisters, A. (2015). Reply to “Paleo- to Mesoarchean polymetamorphism in the Barberton granite-greenstone belt, South Africa: Constraints from U-Pb monazite and Lu-Hf garnet geochronology on the tectonic processes that shaped the belt: Discussion” by M. Brown. Geological Society of America Bulletin, 127(11–12), 1558–1563. https://doi.org/10.1130/b31304.1
de Wit, M. J., & Furnes, H. (2016). 3.5-Ga hydrothermal fields and diamictites in the Barberton Greenstone Belt—Paleoarchean crust in cold environments. Science Advances, 2(2), 1–12. https://doi.org/10.1126/sciadv.1500368
Decker, N. B., Byerly, G. R., Thompson Stiegler, M., Lowe, D. R., & Stefurak, E. (2015). High resolution tephra and U/Pb chronology of the 3.33–3.26 Ga Mendon Formation, Barberton Greenstone Belt, South Africa. Precambrian Research, 261, 54–74. https://doi.org/10.1016/j.precamres.2015.02.003
Deng, Z., Chaussidon, M., Guitreau, M., Puchtel, I. S., Dauphas, N., & Moynier, F. (2019). An oceanic subduction origin for Archaean granitoids revealed by silicon isotopes. Nature Geoscience, 12(9), 774–778. https://doi.org/10.1038/s41561-019-0407-6
Dhuime, B., Hawkesworth, C. J., Cawood, P. A., & Storey, C. D. (2012). A Change in the Geodynamics of Continental Growth 3 Billion Years Ago. Science, 335(6074), 1334–1336. https://doi.org/10.1126/science.1216066
Diener, J. F. A., Stevens, G., Kisters, A. F. M., & Poujol, M. (2005). Metamorphism and exhumation of the basal parts of the Barberton greenstone belt, South Africa: Constraining the rates of Mesoarchaean tectonism. Precambrian Research, 143(1–4), 87–112. https://doi.org/10.1016/j.precamres.2005.10.001
Djokic, T., Bolhar, R., Brengman, L. A., Havig, J. R., & Van Kranendonk, M. J. (2024). Trace elements (REE + Y) reveal marine, subaerial, and hydrothermal controls on an early Archean habitat for life: The 3.48Ga volcanic-caldera system of the dresser formation, Pilbara Craton. Chemical Geology, 644, 121865. https://doi.org/10.1016/j.chemgeo.2023.121865
Drabon, N., & Lowe, D. R. (2021). Progressive accretion recorded in sedimentary rocks of the 3.28–3.23 Ga Fig Tree Group, Barberton Greenstone Belt. GSA Bulletin, 134(5–6), 1258–1276. https://doi.org/10.1130/b35973.1
Duchac, K. C., & Hanor, J. S. (1987). Origin and timing of the metasomatic silicification of an early archean komatiite sequence, barberton mountain land, South Africa. Precambrian Research, 37(2), 125–146. https://doi.org/10.1016/0301-9268(87)90075-1
Dziggel, A., Stevens, G., Poujol, M., Anhaeusser, C. R., & Armstrong, R. A. (2002). Metamorphism of the granite–greenstone terrane south of the Barberton greenstone belt, South Africa: an insight into the tectono-thermal evolution of the ‘lower’ portions of the Onverwacht Group. Precambrian Research, 114(3–4), 221–247. https://doi.org/10.1016/s0301-9268(01)00225-x
Falcone, E. E., Federico, C., & Boudoire, G. (2022). Geochemistry of trace metals and Rare Earth Elements in shallow marine water affected by hydrothermal fluids at Vulcano (Aeolian Islands, Italy). Chemical Geology, 593, 120756. https://doi.org/10.1016/j.chemgeo.2022.120756
Furnes, H., Robins, B., & de Wit, M. J. (2012). Geochemistry and petrology of lavas in the Upper Onverwacht Suite, Barberton Mountain Land, South Africa. South African Journal of Geology, 115(2), 171–210. https://doi.org/10.2113/gssajg.115.2.171
Garçon, M. (2021). Episodic growth of felsic continents in the past 3.7 Ga. Science Advances, 7(39). https://doi.org/10.1126/sciadv.abj1807
Garçon, M., Boyet, M., Carlson, R. W., Horan, M. F., Auclair, D., & Mock, T. D. (2018). Factors influencing the precision and accuracy of Nd isotope measurements by thermal ionization mass spectrometry. Chemical Geology, 476, 493–514. https://doi.org/10.1016/j.chemgeo.2017.12.003
Geilert, S., Vroon, P. Z., & van Bergen, M. J. (2014). Silicon isotopes and trace elements in chert record early Archean basin evolution. Chemical Geology, 386, 133–142. https://doi.org/10.1016/j.chemgeo.2014.07.027
Gillis, K. M., & Robinson, P. T. (1990). Patterns and processes of alteration in the lavas and dykes of the Troodos Ophiolite, Cyprus. Journal of Geophysical Research: Solid Earth, 95(B13), 21523–21548. https://doi.org/10.1029/jb095ib13p21523
Grosch, E. G. (2018). Metamorphic processes preserved in early Archean supracrustal rocks of the Barberton Greenstone Belt, South Africa. Geological Society, London, Special Publications, 478(1), 315–334. https://doi.org/10.1144/sp478.15
Halevy, I., & Bachan, A. (2018). The geologic history of seawater pH. Science, 355(6329), 1069–1071. https://doi.org/10.1126/science.aal4151
Hanor, J. S., & Duchač, K. C. (1990). Isovolumetric Silicification of Early Archean Komatiites: Geochemical Mass Balances and Constraints on Origin. The Journal of Geology, 98(6), 863–877. https://doi.org/10.1086/629458
Hart, S. R., & Staudigel, H. (1982). The control of alkalies and uranium in seawater by ocean crust alteration. Earth and Planetary Science Letters, 58(2), 202–212. https://doi.org/10.1016/0012-821x(82)90194-7
Hauff, F., Hoernle, K., & Schmidt, A. (2003). Sr‐Nd‐Pb composition of Mesozoic Pacific oceanic crust (Site 1149 and 801, ODP Leg 185): Implications for alteration of ocean crust and the input into the Izu‐Bonin‐Mariana subduction system. Geochemistry, Geophysics, Geosystems, 4(8). https://doi.org/10.1029/2002gc000421
Hayashi, T., Tanimizu, M., & Tanaka, T. (2004). Origin of negative Ce anomalies in Barberton sedimentary rocks, deduced from La–Ce and Sm–Nd isotope systematics. Precambrian Research, 135(4), 345–357. https://doi.org/10.1016/j.precamres.2004.09.004
Heck, P. R., Huberty, J. M., Kita, N. T., Ushikubo, T., Kozdon, R., & Valley, J. W. (2011). SIMS analyses of silicon and oxygen isotope ratios for quartz from Archean and Paleoproterozoic banded iron formations. Geochimica et Cosmochimica Acta, 75(20), 5879–5891. https://doi.org/10.1016/j.gca.2011.07.023
Heinrichs, T. (1984). The Umsoli chert, turbidite testament for a major phreatoplinian event at the onverwacht/fig tree transition (Swaziland supergroup, Archaean, South Africa). Precambrian Research, 24(3–4), 237–283. https://doi.org/10.1016/0301-9268(84)90061-5
Heubeck, C. (2019). The Moodies Group—a High-Resolution Archive of Archaean Surface Processes and Basin-Forming Mechanisms. In The Archaean Geology of the Kaapvaal Craton, Southern Africa (pp. 133–169). Springer International Publishing. https://doi.org/10.1007/978-3-319-78652-0_6
Heubeck, C., & Lowe, D. R. (1994). Depositional and tectonic setting of the Archean Moodies Group, Barberton Greenstone Belt, South Africa. Precambrian Research, 68(3–4), 257–290. https://doi.org/10.1016/0301-9268(94)90033-7
Hofmann, A., Bolhar, R., Orberger, B., & Foucher, F. (2013). Cherts of the Barberton Greenstone Belt, South Africa: Petrology and Trace-Element Geochemistry of 3.5 To 3.3 Ga Old Silicified Volcaniclastic Sediments. South African Journal of Geology, 116(2), 297–322. https://doi.org/10.2113/gssajg.116.2.297
Hofmann, A., & Harris, C. (2008). Silica alteration zones in the Barberton greenstone belt: A window into subseafloor processes 3.5–3.3 Ga ago. Chemical Geology, 257(3–4), 221–239. https://doi.org/10.1016/j.chemgeo.2008.09.015
Hofmann, A., & Wilson, A. H. (2007). Chapter 5.5 Silicified Basalts, Bedded Cherts and Other Sea Floor Alteration Phenomena of the 3.4 Ga Nondweni Greenstone Belt, South Africa. In Earth’s Oldest Rocks (Vol. 15, pp. 571–605). Elsevier. https://doi.org/10.1016/s0166-2635(07)15055-6
Hongo, Y., Obata, H., Sotto Alibo, D., & Nozaki, Y. (2006). Spatial variations of rare earth elements in North Pacific surface water. Journal of Oceanography, 62(4), 441–455. https://doi.org/10.1007/s10872-006-0067-1
Hyslop, E. V., Valley, J. W., Johnson, C. M., & Beard, B. L. (2008). The effects of metamorphism on O and Fe isotope compositions in the Biwabik Iron Formation, northern Minnesota. Contributions to Mineralogy and Petrology, 155(3), 313–328. https://doi.org/10.1007/s00410-007-0244-2
Israel, C., Boyet, M., Doucelance, R., Bonnand, P., Frossard, P., Auclair, D., & Bouvier, A. (2020). Formation of the Ce-Nd mantle array: Crustal extraction vs. recycling by subduction. Earth and Planetary Science Letters, 530, 115941. https://doi.org/10.1016/j.epsl.2019.115941
Jaffrés, J. B. D., Shields, G. A., & Wallmann, K. (2007). The oxygen isotope evolution of seawater: A critical review of a long-standing controversy and an improved geological water cycle model for the past 3.4 billion years. Earth-Science Reviews, 83(1–2), 83–122. https://doi.org/10.1016/j.earscirev.2007.04.002
Johnson, B. W., & Wing, B. A. (2020). Limited Archaean continental emergence reflected in an early Archaean 18O-enriched ocean. Nature Geoscience, 13(3), 243–248. https://doi.org/10.1038/s41561-020-0538-9
Kasting, J. F., Howard, M. T., Wallmann, K., Veizer, J., Shields, G., & Jaffrés, J. (2006). Paleoclimates, ocean depth, and the oxygen isotopic composition of seawater. Earth and Planetary Science Letters, 252(1–2), 82–93. https://doi.org/10.1016/j.epsl.2006.09.029
Kelley, K. A., Plank, T., Ludden, J., & Staudigel, H. (2003). Composition of altered oceanic crust at ODP Sites 801 and 1149. Geochemistry, Geophysics, Geosystems, 4(6). https://doi.org/10.1029/2002gc000435
Kisters, A. F. M., Stevens, G., Dziggel, A., & Armstrong, R. A. (2003). Extensional detachment faulting and core-complex formation in the southern Barberton granite–greenstone terrain, South Africa: evidence for a 3.2 Ga orogenic collapse. Precambrian Research, 127(4), 355–378. https://doi.org/10.1016/j.precamres.2003.08.002
Kitoga, L. S., Moyen, J.-F., Boyet, M., Marin-Carbonne, J., Olivier, N., Garçon, M., & Stevens, G. (2025). Drone images and geochemical compositions of reference materials and silicified lavas and cherts from the Paleoarchean Barberton Greenstone Belt [dataset]. OPGC, LMV. https://doi.org/10.25519/QXR1-9Y88
Kitoga, L. S., Zakharov, D., Marin-Carbonne, J., Boyet, M., Moyen, J.-F., Di Rocco, T., Pack, A., Olivier, N., & Stevens, G. (2024). Oxygen and silicon isotopic compositions of Archean silicified lava and cherts of the Onverwacht Group: Implication for seafloor hydrothermalism and the nature of recycled components in the source of granitoids. Chemical Geology, 670, 122407. https://doi.org/10.1016/j.chemgeo.2024.122407
Knauth, L. P., & Lowe, D. R. (1978). Oxygen isotope geochemistry of cherts from the Onverwacht Group (3.4 billion years), Transvaal, South Africa, with implications for secular variations in the isotopic composition of cherts. Earth and Planetary Science Letters, 41(2), 209–222. https://doi.org/10.1016/0012-821x(78)90011-0
Knauth, L. P., & Lowe, D. R. (2003). High Archean climatic temperature inferred from oxygen isotope geochemistry of cherts in the 3.5 Ga Swaziland Supergroup, South Africa. Geological Society of America Bulletin, 115, 566–580. https://doi.org/10.1130/0016-7606(2003)115<0566:hactif>2.0.co;2
Konhauser, K. O., Planavsky, N. J., Hardisty, D. S., Robbins, L. J., Warchola, T. J., Haugaard, R., Lalonde, S. V., Partin, C. A., Oonk, P. B. H., Tsikos, H., Lyons, T. W., Bekker, A., & Johnson, C. M. (2017). Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history. Earth-Science Reviews, 172, 140–177. https://doi.org/10.1016/j.earscirev.2017.06.012
Krissansen-Totton, J., Arney, G. N., & Catling, D. C. (2018). Constraining the climate and ocean pH of the early Earth with a geological carbon cycle model. Proceedings of the National Academy of Sciences of the United States of America, 115(16), 4105–4110. https://doi.org/10.1073/pnas.1721296115
Kröner, A., Anhaeusser, C. R., Hoffmann, J. E., Wong, J., Geng, H., Hegner, E., Xie, H., Yang, J., & Liu, D. (2016). Chronology of the oldest supracrustal sequences in the Palaeoarchaean Barberton Greenstone Belt, South Africa and Swaziland. Precambrian Research, 279, 123–143. https://doi.org/10.1016/j.precamres.2016.04.007
Kutyrev, A., Bindeman, I. N., O’Neil, J., & Rizo, H. (2024). Seawater-oceanic crust interaction constrained by triple oxygen and hydrogen isotopes in rocks from the Saglek-Hebron complex, NE Canada: Implications for moderately low-δ18O Eoarchean Ocean. Chemical Geology, 670, 122378. https://doi.org/10.1016/j.chemgeo.2024.122378
Lahaye, Y., Arndt, N., Byerly, G., Chauvel, C., Fourcade, S., & Gruau, G. (1995). The influence of alteration on the trace-element and Nd isotopic compositions of komatiites. Chemical Geology, 126(1), 43–64. https://doi.org/10.1016/0009-2541(95)00102-1
Lanari, P., Vidal, O., De Andrade, V., Dubacq, B., Lewin, E., Grosch, E. G., & Schwartz, S. (2014). XMapTools: A MATLAB©-based program for electron microprobe X-ray image processing and geothermobarometry. Computers and Geosciences, 62, 227–240. https://doi.org/10.1016/j.cageo.2013.08.010
Lanier, W. P., & Lowe, D. R. (1982). Sedimentology of the Middle Marker (3.4 Ga), Onverwacht Group, Transvaal, South Africa. Precambrian Research, 18(3), 237–260. https://doi.org/10.1016/0301-9268(82)90012-2
Lécuyer, C., Gruau, G., Anhaeusser, C. R., & Fourcade, S. (1994). The origin of fluids and the effects of metamorphism on the primary chemical compositions of Barberton komatiites: New evidence from geochemical (REE) and isotopic (Nd, O, H, 30Ar40Ar) data. Geochimica et Cosmochimica Acta, 58(2), 969–984. https://doi.org/10.1016/0016-7037(94)90519-3
Ledevin, M., Arndt, N., Chauvel, C., Jaillard, E., & Simionovici, A. (2019). The Sedimentary Origin of Black and White Banded Cherts of the Buck Reef, Barberton, South Africa. Geosciences, 9(10). https://doi.org/10.3390/geosciences9100424
Ledevin, M., Arndt, N., Davaille, A., Ledevin, R., & Simionovici, A. (2015). The rheological behaviour of fracture-filling cherts: example of Barite Valley dikes, Barberton Greenstone Belt, South Africa. Solid Earth, 6(1), 253–269. https://doi.org/10.5194/se-6-253-2015
Ledevin, M., Arndt, N., Simionovici, A., Jaillard, E., & Ulrich, M. (2014). Silica precipitation triggered by clastic sedimentation in the Archean: New petrographic evidence from cherts of the Kromberg type section, South Africa. Precambrian Research, 255, 316–334. https://doi.org/10.1016/j.precamres.2014.10.009
Lei, K., Wang, H., Wang, X., Zhang, Q., & Li, X. (2023). Decoupled Zircon Si–O Isotopes Tracing the Supracrustal Silicification and Komatiitic‐Derived Fluids in the Source of TTGs. Geophysical Research Letters, 50(16), 1–9. https://doi.org/10.1029/2023gl104002
Li, C.-F., Li, X.-H., Li, Q.-L., Guo, J.-H., Li, X.-H., & Yang, Y.-H. (2012). Rapid and precise determination of Sr and Nd isotopic ratios in geological samples from the same filament loading by thermal ionization mass spectrometry employing a single-step separation scheme. Analytica Chimica Acta, 727, 54–60. https://doi.org/10.1016/j.aca.2012.03.040
Lowe, D. R., & Byerly, G. R. (1986). Archaean flow-top alteration zones formed initially in a low-temperature sulphate-rich environment. Nature, 324(6094), 245–248. https://doi.org/10.1038/324245a0
Lowe, D. R., & Byerly, G. R. (1999). Geologic evolution of the Barberton Grenstone Belt. Geological Society of America. https://doi.org/10.1130/0-8137-2329-9
Lowe, D. R., & Byerly, G. R. (2007a). Chapter 5.3 An Overview of the Geology of the Barberton Greenstone Belt and Vicinity: Implications for Early Crustal Development. In Earth’s Oldest Rocks (Vol. 15, pp. 481–526). Elsevier. https://doi.org/10.1016/s0166-2635(07)15053-2
Lowe, D. R., & Byerly, G. R. (2007b). Ironstone bodies of the Barberton greenstone belt, South Africa: Products of a Cenozoic hydrological system, not Archean hydrothermal vents! Geological Society of America Bulletin, 119(1–2), 65–87. https://doi.org/10.1130/b25997.1
Lowe, D. R., & Byerly, G. R. (2020). The non-glacial and non-cratonic origin of an early Archean felsic volcaniclastic unit, Barberton Greenstone Belt, South Africa. Precambrian Research, 341, 105647. https://doi.org/10.1016/j.precamres.2020.105647
Lowe, D. R., Ibarra, D. E., Drabon, N., & Chamberlain, C. P. (2020). Constraints on surface temperature 3.4 billion years ago based on triple oxygen isotopes of cherts from the Barberton Greenstone Belt, South Africa, and the problem of sample selection. American Journal of Science, 320(9), 790–814. https://doi.org/10.2475/11.2020.02
Makishima, A., Shimizu, H., & Masuda, A. (1986). Precise measurement of cerium and lanthanum isotope ratios. Journal of the Mass Spectrometry Society of Japan, 35(2), 64–72. https://doi.org/10.5702/massspec.35.64
Marin, J., Chaussidon, M., & Robert, F. (2010). Microscale oxygen isotope variations in 1.9 Ga Gunflint cherts: Assessments of diagenesis effects and implications for oceanic paleotemperature reconstructions. Geochimica et Cosmochimica Acta, 74(1), 116–130. https://doi.org/10.1016/j.gca.2009.09.016
Marin-Carbonne, J., Chaussidon, M., Boiron, M.-C., & Robert, F. (2011). A combined in situ oxygen, silicon isotopic and fluid inclusion study of a chert sample from Onverwacht Group (3.35Ga, South Africa): New constraints on fluid circulation. Chemical Geology, 286(3–4), 59–71. https://doi.org/10.1016/j.chemgeo.2011.02.025
Moyen, J.-F., Stevens, G., Kisters, A. F. M., Belcher, R. W., & Lemirre, B. (2019). TTG Plutons of the Barberton Granitoid-Greenstone Terrain, South Africa. In Earth’s Oldest Rocks (pp. 615–653). Elsevier. https://doi.org/10.1016/b978-0-444-63901-1.00025-3
Olivier, N., & Boyet, M. (2006). Rare earth and trace elements of microbialites in Upper Jurassic coral- and sponge-microbialite reefs. Chemical Geology, 230(1–2), 105–123. https://doi.org/10.1016/j.chemgeo.2005.12.002
Paris, I., Stanistreet, I. G., & Hughes, M. J. (1985). Cherts of the Barberton Greenstone Belt Interpreted as Products of Submarine Exhalative Activity. The Journal of Geology, 93(2), 111–129. https://doi.org/10.1086/628935
Parman, S. W., Grove, T. L., & Dann, J. C. (2001). The production of Barberton komatiites in an Archean Subduction Zone. Geophysical Research Letters, 28(13), 2513–2516. https://doi.org/10.1029/2000gl012713
Perry, E. C., & Lefticariu, L. (2007). Formation and Geochemistry of Precambrian Cherts. In Treatise on Geochemistry (pp. 1–21). Elsevier. https://doi.org/10.1016/b0-08-043751-6/07138-3
Pfennig, M. L., Pakulla, J. J., Hasenstab-Dübeler, E., Wombacher, F., Jodder, J., Hofmann, A., & Münker, C. (2025). Young oxygenation of the Archean Keonjhar Palaeosol, India, from 138La-138Ce chronometry. Geochemical Perspectives Letters, 33(51–55), 51–55. https://doi.org/10.7185/geochemlet.2503
Planavsky, N. J., McGoldrick, P., Scott, C. T., Li, C., Reinhard, C. T., Kelly, A. E., Chu, X., Bekker, A., Love, G. D., & Lyons, T. W. (2011). Widespread iron-rich conditions in the mid-Proterozoic ocean. Nature, 477(7365), 448–451. https://doi.org/10.1038/nature10327
Planavsky, N. J., Robbins, L. J., Kamber, B. S., & Schoenberg, R. (2020). Weathering, alteration and reconstructing Earth’s oxygenation. Interface Focus, 10(4), 20190140. https://doi.org/10.1098/rsfs.2019.0140
Puchtel, I. S., Blichert-Toft, J., Touboul, M., Walker, R. J., Byerly, G. R., Nisbet, E. G., & Anhaeusser, C. R. (2013). Insights into early Earth from Barberton komatiites: Evidence from lithophile isotope and trace element systematics. Geochimica et Cosmochimica Acta, 108, 63–90. https://doi.org/10.1016/j.gca.2013.01.016
Quinn, K. A., Byrne, R. H., & Schijf, J. (2006). Sorption of yttrium and rare earth elements by amorphous ferric hydroxide: Influence of solution complexation with carbonate. Geochimica et Cosmochimica Acta, 70(16), 4151–4165. https://doi.org/10.1016/j.gca.2006.06.014
Reimann, S., Heubeck, C. E., Fugmann, P., Janse van Rensburg, D. J., Zametzer, A., Serre, S. H., & Thomsen, T. B. (2021). Syndepositional hydrothermalism selectively preserves records of one of the earliest benthic ecosystems, Moodies Group (3.22 Ga), Barberton Greenstone Belt, South Africa. South African Journal of Geology, 124(1), 253–278. https://doi.org/10.25131/sajg.124.0012
Robert, F., & Chaussidon, M. (2006). A palaeotemperature curve for the Precambrian oceans based on silicon isotopes in cherts. Nature, 443(7114), 969–972. https://doi.org/10.1038/nature05239
Roberts, N. M. W., & Santosh, M. (2018). Capturing the Mesoarchean Emergence of Continental Crust in the Coorg Block, Southern India. Geophysical Research Letters, 45(15), 7444–7453. https://doi.org/10.1029/2018gl078114
Rollion-Bard, C., & Marin-Carbonne, J. (2011). Determination of SIMS matrix effects on oxygen isotopic compositions in carbonates. Journal of Analytical Atomic Spectrometry, 26(6), 1285–1289. https://doi.org/10.1039/c0ja00213e
Rouchon, V., & Orberger, B. (2008). Origin and mechanisms of K–Si-metasomatism of ca. 3.4–3.3 Ga volcaniclastic deposits and implications for Archean seawater evolution: Examples from cherts of Kittys Gap (Pilbara craton, Australia) and Msauli (Barberton Greenstone Belt, South Africa). Precambrian Research, 165(3–4), 169–189. https://doi.org/10.1016/j.precamres.2008.06.003
Rouchon, V., Orberger, B., Hofmann, A., & Pinti, D. L. (2009). Diagenetic Fe-carbonates in Paleoarchean felsic sedimentary rocks (Hooggenoeg Formation, Barberton greenstone belt, South Africa): Implications for CO2 sequestration and the chemical budget of seawater. Precambrian Research, 172(3–4), 255–278. https://doi.org/10.1016/j.precamres.2009.04.010
Saitoh, M., Olivier, N., Garçon, M., Boyet, M., Thomazo, C., Alleon, J., Moyen, J.-F., Motto-Ros, V., & Marin-Carbonne, J. (2021). Metamorphic origin of anastomosing and wavy laminas overprinting putative microbial deposits from the 3.22 Ga Moodies Group (Barberton Greenstone Belt). Precambrian Research, 362, 106306. https://doi.org/10.1016/j.precamres.2021.106306
Schmidt, K., Bau, M., Hein, J. R., & Koschinsky, A. (2014). Fractionation of the geochemical twins Zr–Hf and Nb–Ta during scavenging from seawater by hydrogenetic ferromanganese crusts. Geochimica et Cosmochimica Acta, 140, 468–487. https://doi.org/10.1016/j.gca.2014.05.036
Schnabel, C., Münker, C., & Strub, E. (2017). La–Ce isotope measurements by multicollector-ICPMS. Journal of Analytical Atomic Spectrometry, 32(12), 2360–2370. https://doi.org/10.1039/c7ja00256d
Schneider, K. P., Hoffmann, J. E., Münker, C., Patyniak, M., Sprung, P., Roerdink, D., Garbe-Schönberg, D., & Kröner, A. (2019). Petrogenetic evolution of metabasalts and metakomatiites of the lower Onverwacht Group, Barberton Greenstone Belt (South Africa). Chemical Geology, 511, 152–177. https://doi.org/10.1016/j.chemgeo.2019.02.020
Sharp, Z. D., & Kirschner, D. L. (1994). Quartz-calcite oxygen isotope thermometry: A calibration based on natural isotopic variations. Geochimica et Cosmochimica Acta, 58(20), 4491–4501. https://doi.org/10.1016/0016-7037(94)90350-6
Shibuya, T., Komiya, T., Nakamura, K., Takai, K., & Maruyama, S. (2010). Highly alkaline, high-temperature hydrothermal fluids in the early Archean ocean. Precambrian Research, 182(3), 230–238. https://doi.org/10.1016/j.precamres.2010.08.011
Shibuya, T., Tahata, M., Kitajima, K., Ueno, Y., Komiya, T., Yamamoto, S., Igisu, M., Terabayashi, M., Sawaki, Y., Takai, K., Yoshida, N., & Maruyama, S. (2012). Depth variation of carbon and oxygen isotopes of calcites in Archean altered upperoceanic crust: Implications for the CO2 flux from ocean to oceanic crust in the Archean. Earth and Planetary Science Letters, 321–322, 64–73. https://doi.org/10.1016/j.epsl.2011.12.034
Siever, R. (1992). The silica cycle in the Precambrian. Geochimica et Cosmochimica Acta, 56(8), 3265–3272. https://doi.org/10.1016/0016-7037(92)90303-z
Śliwiński, M. G., Kitajima, K., Spicuzza, M. J., Orland, I. J., Ishida, A., Fournelle, J. H., & Valley, J. W. (2018). SIMS Bias on Isotope Ratios in Ca‐Mg‐Fe Carbonates (Part III): δ18O and δ13C Matrix Effects Along the Magnesite–Siderite Solid‐Solution Series. Geostandards and Geoanalytical Research, 42(1), 49–76. https://doi.org/10.1111/ggr.12194
Stanistreet, I. G., de Wit, M. J., & Fripp, R. E. P. (1981). Do graded units of accretionary spheroids in the Barberton Greenstone Belt indicate Archaean deep water environment? Nature, 293, 280–284. https://doi.org/10.1038/293280a0
Stefurak, E. J. T., Fischer, W. W., & Lowe, D. R. (2015). Texture-specific Si isotope variations in Barberton Greenstone Belt cherts record low temperature fractionations in early Archean seawater. Geochimica et Cosmochimica Acta, 150, 26–52. https://doi.org/10.1016/j.gca.2014.11.014
Stevens, G., & Moyen, J.-F. (2007). Chapter 5.7 Metamorphism in the Barberton Granite Greenstone Terrain: A Record of Paleoarchean Accretion. In Earth’s Oldest Rocks (pp. 669–698). Elsevier. https://doi.org/10.1016/s0166-2635(07)15057-x
Sugahara, H., Sugitani, K., Mimura, K., Yamashita, F., & Yamamoto, K. (2010). A systematic rare-earth elements and yttrium study of Archean cherts at the Mount Goldsworthy greenstone belt in the Pilbara Craton: Implications for the origin of microfossil-bearing black cherts. Precambrian Research, 177(1–2), 73–87. https://doi.org/10.1016/j.precamres.2009.10.005
Tanner, P. W. G., & Miller, R. G. (1980). Geochemical evidence for loss of Na and K from Moinian calc-silicate pods during prograde metamorphism. Geological Magazine, 117(3), 267–275. https://doi.org/10.1017/s001675680003048x
Tatzel, M., Frings, P. J., Oelze, M., Herwartz, D., Lünsdorf, N. K., & Wiedenbeck, M. (2022). Chert oxygen isotope ratios are driven by Earth’s thermal evolution. Proceedings of the National Academy of Sciences of the United States of America, 120. https://doi.org/10.1073/pnas.2213076119
Tatzel, M., Oelze, M., Frick, D. A., Di Rocco, T., Liesegang, M., Stuff, M., & Wiedenbeck, M. (2024). Silicon and oxygen isotope fractionation in a silicified carbonate rock. Chemical Geology, 658, 122120. https://doi.org/10.1016/j.chemgeo.2024.122120
Taylor, S. R., & McLennan, S. (1985). The continental crust: its composition and evolution. In Planetary Crusts (pp. 301–324). Cambridge University Press. https://doi.org/10.1017/cbo9780511575358.014
Tice, M. M., Bostick, B. C., & Lowe, D. R. (2004). Thermal history of the 3.5–3.2 Ga Onverwacht and Fig Tree Groups, Barberton greenstone belt, South Africa, inferred by Raman microspectroscopy of carbonaceous material. Geology, 32(1), 37. https://doi.org/10.1130/g19915.1
Tice, M. M., & Lowe, D. R. (2006). The origin of carbonaceous matter in pre-3.0 Ga greenstone terrains: A review and new evidence from the 3.42 Ga Buck Reef Chert. Earth Science Reviews, 76(3–4), 259–300. https://doi.org/10.1016/j.earscirev.2006.03.003
Toulkeridis, T., Goldstein, S. L., Clauer, N., Kröner, A., Todt, W., & Schidlowski, M. (1998). Sm–Nd, Rb–Sr and Pb–Pb dating of silicic carbonates from the early Archaean Barberton Greenstone Belt, South Africa: Evidence for post-depositional isotopic resetting at low temperature. Precambrian Research, 92(2), 129–144. https://doi.org/10.1016/s0301-9268(98)00071-0
Trail, D., Boehnke, P., Savage, P. S., Liu, M.-C., Miller, M. L., & Bindeman, I. (2018). Origin and significance of Si and O isotope heterogeneities in Phanerozoic, Archean, and Hadean zircon. Proceedings of the National Academy of Sciences of the United States of America, 115(41), 10287–10292. https://doi.org/10.1073/pnas.1808335115
Trower, E. J., & Lowe, D. R. (2016). Sedimentology of the sim3.3 Ga upper Mendon Formation, Barberton Greenstone Belt, South Africa. Precambrian Research, 281, 473–494. https://doi.org/10.1016/j.precamres.2016.06.003
van den Boorn, S. H. J. M., van Bergen, M. J., Nijman, W., & Vroon, P. Z. (2007). Dual role of seawater and hydrothermal fluids in Early Archean chert formation: Evidence from silicon isotopes. Geology, 35(10), 939–942. https://doi.org/10.1130/g24096a.1
van den Boorn, S. H. J. M., van Bergen, M. J., Vroon, P. Z., de Vries, S. T., & Nijman, W. (2010). Silicon isotope and trace element constraints on the origin of sim3.5 Ga cherts: Implications for Early Archaean marine environments. Geochimica et Cosmochimica Acta, 74(3), 1077–1103. https://doi.org/10.1016/j.gca.2009.09.009
van Zuilen, M. A., Chaussidon, M., Rollion-Bard, C., & Marty, B. (2007). Carbonaceous cherts of the Barberton Greenstone Belt, South Africa: Isotopic, chemical and structural characteristics of individual microstructures. Geochimica et Cosmochimica Acta, 71(3), 655–669. https://doi.org/10.1016/j.gca.2006.09.029
Vezinet, A., Pearson, D. G., Thomassot, E., Stern, R. A., Sarkar, C., Luo, Y., & Fisher, C. M. (2018). Hydrothermally-altered mafic crust as source for early Earth TTG: Pb/Hf/O isotope and trace element evidence in zircon from TTG of the Eoarchean Saglek Block, N. Labrador. Earth and Planetary Science Letters, 503, 95–107. https://doi.org/10.1016/j.epsl.2018.09.015
Vidal, O., Lanari, P., Munoz, M., Bourdelle, F., & De Andrade, V. (2016). Deciphering temperature, pressure and oxygen-activity conditions of chlorite formation. Clay Minerals, 51(4), 615–633. https://doi.org/10.1180/claymin.2016.051.4.06
Viehmann, S., Bau, M., Hoffmann, J. E., & Münker, C. (2018). Decoupled Hf and Nd isotopes in suspended particles and in the dissolved load of Late Archean seawater. Chemical Geology, 483, 111–118. https://doi.org/10.1016/j.chemgeo.2018.01.017
Viehmann, S., Reitner, J., Tepe, N., Hohl, S. V., Van Kranendonk, M., Hofmann, T., Koeberl, C., & Meister, P. (2020). Carbonates and cherts as archives of seawater chemistry and habitability on a carbonate platform 3.35 Ga ago: Insights from Sm/Nd dating and trace element analysis from the Strelley Pool Formation, Western Australia. Precambrian Research, 344, 105742. https://doi.org/10.1016/j.precamres.2020.105742
Villemant, B. (1988). Trace element evolution in the Phlegrean Fields (Central Italy): fractional crystallization and selective enrichment. Contributions to Mineralogy and Petrology, 98(2), 169–183. https://doi.org/10.1007/bf00402110
Weis, D., & Wasserburg, G. J. (1987a). Rb-Sr and Sm-Nd isotope geochemistry and chronology of cherts from the Onverwacht Group (3.5 AE), South Africa. Geochimica et Cosmochimica Acta, 51(4), 973–984. https://doi.org/10.1016/0016-7037(87)90109-8
Weis, D., & Wasserburg, G. J. (1987b). Rb-Sr and Sm-Nd systematics of cherts and other siliceous deposits. Geochimica et Cosmochimica Acta, 51(4), 959–972. https://doi.org/10.1016/0016-7037(87)90108-6
Xie, X., Byerly, G. R., & Ferrell Jr., R. E. (1997). IIb trioctahedral chlorite from the Barberton greenstone belt: crystal structure and rock composition constraints with implications to geothermometry. Contributions to Mineralogy and Petrology, 126(3), 275–291. https://doi.org/10.1007/s004100050250
Yoshida, S., Ueda, H., Asanuma, H., & Sawaki, Y. (2024). Y-Ho fractionation during basalt alteration in hydrothermal system: An implication for superchondritic Y/Ho signature recorded in Precambrian banded iron formations. Chemical Geology, 670, 122421. https://doi.org/10.1016/j.chemgeo.2024.122421
Zakharov, D. O., Marin-Carbonne, J., Alleon, J., & Bindeman, I. N. (2021). Triple Oxygen Isotope Trend Recorded by Precambrian Cherts: A Perspective from Combined Bulk and in situ Secondary Ion Probe Measurements. Reviews in Mineralogy and Geochemistry, 86(1), 323–365. https://doi.org/10.2138/rmg.2021.86.10

This work is licensed under a Creative Commons Attribution 4.0 International License.
Copyright (c) 2026 Lungele Steve Kitoga, Jean-François Moyen, Maud Boyet, Johanna Marin-Carbonne, Nicolas Olivier, Marion Garçon, Gary Stevens

