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Holes CM1A and CM2B of the International Continental Scientific Drilling Program (ICDP) Oman Drilling Project (OmanDP, https://www.omandrilling.ac.uk/) drilled through the Moho Transition Zone (MTZ). CM1A is composed of layered gabbro (0–160 meters below surface, mbs), dunite (160–310 mbs), and harzburgites (310–405 mbs), whereas CM2B contains dunite (20–120 mbs) and harzburgites (120–300 mbs). The drillholes provided an unprecedented opportunity to study the behavior of metals in the MTZ, where arriving primitive MORB melts extensively react with the mantle. Here, melts, typically enriched with sulfur and chalcophile elements, are supposed to enrich the mantle and lower crust with sulfides (Gonzalez-Jimenez et al., 2020 – Ore Geol. Rev.; Ciążela et al., 2018 - GCA). Modal sulfide content increases downwards the gabbro sequence from ~0.004 vol.‰ to ~1.0 vol.‰ but decreases again from 0.8 vol.‰ to 0.01 vol.‰ in the lower part of the MTZ and in the harzburgite of the upper mantle. This is reflected in the S concentration increasing from 341 ± 17 ppm, 2sd (standard deviation = σ) to 832 ± 37 ppm, 2sd, in the gabbro section and decreasing downwards from the middle part of Moho into harzburgites from 475 ± 21, 2sd ppm to 63 ± 3 ppm, 2σ. The sulfides in olivine gabbro from MTZ are mostly (56–87% of all sulfides) pyrrhotite-pentlandite-chalcopyrite assemblages indicating the magmatic origin. Sulfides in layered gabbro sequence are consisted of similar magmatic assemblages (36-100%) with minor chalcopyrite, bornite, heazlewoodite, chalcocite, millerite, siegenite and sphalerite with secondary origin. In dunite and harzburgite sequences sulfides are exclusively hydrothermal.Based on EMPA and LA-ICPMS measurements, Zn, Co and Cu seem to reach their maximum concentrations in magmatic sulfides from the MTZ. Although, no significant differences are observed between the Fe isotope signatures in magmatic pyrrhotites from the lower crust (–0.73 to –0.24, 2sd [‰] of δ56Fe) and the MTZ (–0.73 to –0.53, [‰] of δ56Fe), we found different δ56Fe for pyrrhotite (–0.24‰) and chalcopyrite +0.36‰ within the same sulfide grain. The bulk signature of δ56Fe for this grain is –0,12‰ being in accordance with the mass balance calculated δ56Fe 0.025‰ ± 0.025‰ of the mantle (Craddock et al., 2013 – Earth Planet. Sci. Lett). The enrichment in sulfides and selected metals (Zn, Co, Cu) towards the MTZ might result from melt-mantle reaction as we proposed previously for the slow-spread oceanic lithosphere based on the Kane Megamullion Ocean Core Complex (Ciążela et al., 2018 - GCA). In the CM1A/2B ultramafic rocks: dunites and harzburgites, most sulfides are, however, secondary, formed by the same secondary fluids which caused the pervasive serpentinization. To verify whether these sulfides replaced the primary magmatic sulfides or were brought from late-stage seawater-derived fluids, we plan to measure sulfur in whole-rocks and in situ and more iron isotopes in sulfides in situ. Preliminary δ56Fe signature isotope data give us evidence for magmatic origin of the sulfides from upper part of the MTZ section.

The study of the oldest surviving rock suites is crucial for understanding the processes that shaped the early Earth and formed an environment suitable for life. The metasedimentary and metavolcanic rocks of the early Archean Isua supracrustal belt contain abundant apatite, the geochemical signatures of which may help decipher ancient environmental conditions. However, previous research has shown that secondary processes, including amphibolite-facies metamorphism, have reset the original hydrogen isotope composition (&delta, D) of apatite from the Isua belt, therefore, &delta, D values are not indicative of primary conditions in the Archean. Here, we report the first in situ chlorine isotope (&delta, 37Cl) analyses by Secondary Ion Mass Spectrometry (SIMS) from Isua apatite, which we combine with information from transmission electron microscopy, cathodoluminescence imaging, and spectroscopy, documenting the micron-scale internal features of apatite crystals. The determined &delta, 37ClSMOC values (chlorine isotope ratios vs. standard mean ocean chloride) fall within a range from &minus, 0.8&permil, to 1.6&permil, with the most extreme values recorded by two banded iron formation samples. Our results show that &delta, 37Cl values cannot uniquely document primary signatures of apatite crystals, but the results are nonetheless helpful for assessing the extent of secondary overprint.

Here we report on a set of six apatite reference materials (chlorapatites MGMH#133648, TUBAF#38 and fluorapatites MGMH#128441A, TUBAF#37, 40, 50) which we have characterised for their chlorine isotope ratios; these RMs span a range of Cl mass fractions within the apatite Ca10(PO4)6(F,Cl,OH)2 solid solution series. Numerous apatite specimens, obtained from mineralogical collections, were initially screened for 37Cl/35Cl homogeneity using SIMS followed by δ37Cl characterisation by gas source mass spectrometry using both dual‐inlet and continuous‐flow modes. We also report major and key trace element compositions as determined by EPMA. The repeatability of our SIMS results was better than ± 0.10% (1s) for the five samples with > 0.5% m/m Cl and ± 0.19% (1s) for the low Cl abundance material (0.27% m/m). We also observed a small, but significant crystal orientation effect of 0.38% between the mean 37Cl/35Cl ratios measured on three oriented apatite fragments. Furthermore, the results of GS‐IRMS analyses show small but systematic offset of δ37ClSMOC values between the three laboratories. Nonetheless, all studied samples have comparable chlorine isotope compositions, with mean 103δ37ClSMOC values between +0.09 and +0.42 and in all cases with 1s ≤ ± 0.25., Key Points: Six apatite reference materials having various Cl mass fractions were characterised for chlorine isotope ratios by SIMS and three GS‐IRMS laboratories. A small, but significant, crystal orientation effect was recorded by SIMS analyses. Correlation of instrumental mass fractionation factor with Cl mass fraction is visible along the apatite solid solution series., Narodowe Centrum Nauki, Deutscher Akademischer Austauschdienst, Helmholtz Recruiting Initiative, Institute of Geological Sciences, Polish Academy of Sciences

Here we report on a set of six apatite reference materials (chlorapatites MGMH#133648, TUBAF#38 and fluorapatites MGMH#128441A, TUBAF#37, 40, 50) which we have characterised for their chlorine isotope ratios; these RMs span a range of Cl mass fractions within the apatite Ca10(PO4)6(F,Cl,OH)2 solid solution series. Numerous apatite specimens, obtained from mineralogical collections, were initially screened for 37Cl/35Cl homogeneity using SIMS followed by δ37Cl characterisation by gas source mass spectrometry using both dual‐inlet and continuous‐flow modes. We also report major and key trace element compositions as determined by EPMA. The repeatability of our SIMS results was better than ± 0.10% (1s) for the five samples with > 0.5% m/m Cl and ± 0.19% (1s) for the low Cl abundance material (0.27% m/m). We also observed a small, but significant crystal orientation effect of 0.38% between the mean 37Cl/35Cl ratios measured on three oriented apatite fragments. Furthermore, the results of GS‐IRMS analyses show small but systematic offset of δ37ClSMOC values between the three laboratories. Nonetheless, all studied samples have comparable chlorine isotope compositions, with mean 103δ37ClSMOC values between +0.09 and +0.42 and in all cases with 1s ≤ ± 0.25., Key Points: Six apatite reference materials having various Cl mass fractions were characterised for chlorine isotope ratios by SIMS and three GS‐IRMS laboratories. A small, but significant, crystal orientation effect was recorded by SIMS analyses. Correlation of instrumental mass fractionation factor with Cl mass fraction is visible along the apatite solid solution series., Narodowe Centrum Nauki, Deutscher Akademischer Austauschdienst, Helmholtz Recruiting Initiative, Institute of Geological Sciences, Polish Academy of Sciences