Seafloor Alteration Research Articles

Fore-arc metasomatism by hybrid slab fluids during subduction initiation: Sr–Mg–Ca isotopes of rodingite, western Yarlung Zangbo suture zone

Subduction zone metasomatism is critical for Earth's material exchanges, yet the details of slab dehydration, particularly deserpentinization beneath fore-arcs, remain poorly understood. Here, we present Sr–Mg–Ca isotopic data for Purang rodingites from the western Yarlung Zangbo suture zone (YZSZ), a remnant of the Neo-Tethys Ocean that was subducted during the collision between the Indian and Eurasian Plates. The rodingites, occurring as centimeter- to meter-sized veins and blocks in serpentinized harburgite, are dominated by amphibolite- to greenschist-facies minerals like tremolite, magnesiohornblende, and chlorite. Their cumulate textures and rare earth element patterns resemble troctolite or gabbronorite, presumably formed beneath a seafloor spreading center. The rodingites are enriched in large ion lithophile elements and depleted in high field strength elements, with higher Sr/Nb and Ba/La and lower Nb/U and Ce/Pb ratios than mid-ocean ridge basalts (MORB) and rodingites formed through seawater or serpentinizing fluid alteration of MORB-like protoliths. They also exhibit higher initial 87Sr/86Sr ratios (0.7067–0.7075) and elevated δ26Mg values (−0.22 ± 0.07 ‰ to −0.13 ± 0.02 ‰) compared to unaltered oceanic basalts, while their δ44/40Ca values (0.72 ± 0.02 ‰ to 0.87 ± 0.03 ‰) remain similar to MORB. These signatures point to a metasomatic process beyond seafloor alteration, suggesting modification of a MOR-derived protolith in the fore-arc mantle at slab depths of <40 km, driven by Sr- and Mg-rich fluids from clay-rich sediments and serpentinitized mantle. The measured Sr, Mg and Ca isotope compositions can be reproduced by mixing a MORB-like protolith with hybrid fluids derived from varying proportions of sedimentary clays and serpentinitized peridotite. Combined with previous studies on YZSZ metamorphic soles, we propose that this fore-arc metasomatism occurred during the early Cretaceous, concurrent with the incipient subduction of the Neo-Tethys oceanic rocks. These results highlight the significance of deserpentinization at shallow fore-arc mantle settings during subduction initiation, suggesting that slab dehydration is more complex than previously recognized.

The use of combined C[sbnd]Mg isotope compositions of carbonates from orogenic Sb[sbnd]Au deposits as a tracer of fluid interaction with sea-floor altered crust

The Mesoarchaean Murchison Greenstone Belt is composed of a strongly deformed volcano-sedimentary succession metamorphosed up to amphibolite facies and surrounded by metaluminous and peraluminous granitoids in the north of the Kaapvaal Craton of southern Africa. A circa 40 km-long shear-zone of strongly carbonatised rocks (the Antimony Line, or Sb-Line) oriented along the main trend of the greenstone belt (WSW–ENE) hosts important Sb deposits with accessory Au. These commodities mostly occur as stibnite and native gold hosted by quartz‑carbonate rocks at the centre of the Sb-Line, underlining the importance of CO2-rich fluid flow for mineralisation during deformation and metamorphism.In this study, we compare the elemental and stable isotope (C-O-Mg) composition of carbonates from the Sb-Line with regionally distributed carbonates hosted by the volcano-sedimentary succession distal to mineralisation. The carbonates of the Sb-Line and regional rocks have overlapping major element compositions. Both magnesite and dolomite in most Sb-Line samples have marked light-REE-depleted patterns with variable positive Eu anomalies. Carbon isotope ratios define two clusters, with marked δ13C peaks at ca. -5 ‰ for Sb-Line rocks and ca. -2 ‰ for regional rocks, implying separate C-sources. The peak at ca. -2 ‰ likely represents early carbonatisation through sea-floor alteration, whereas the first peak at ca. -5 ‰ is indicative of deep CO2 (mantle, or magma-derived) introduced during tectonic activity of the Sb-Line. Magnesium isotope ratios of regional rocks reveal limited fractionation (bulk δ26Mg = −0.27 ± 0.10 ‰) that overlap with mantle values, but some carbonate-bearing veins present 26Mg-depleted compositions (bulk δ26Mg = −1.91 to −0.40 ‰). Sb-Line carbonated rocks have more fractionated Mg isotope compositions (bulk δ26Mg = −0.8 to 0.0 ‰) and carbonates display marked negative 26Mg values (δ26Mg from −1.46 to −0.31 ‰). We interpret these results in terms of preferential remobilisation of isotopically light Mg during fluid-rock interaction and dissolution of carbonate in the host-rocks. The lack of correlation between δ13C and δ26Mg indicates decoupling of these isotopic systems, implying contribution from isotopically distinct sources of C and Mg to the mineralised zone.Similar to other structurally controlled AuSb mineralisation in Archaean greenstone belts, metal transport and ore deposition in the Murchison Greenstone Belt was closely related to the deep cycle of carbon, linking C-draw-down during sea-floor alteration, carbonate re-mobilisation during metamorphism and CO2 degassing from deep sources along major crustal discontinuities. In contrast to models for orogenic AuSb deposits invoking a purely intra-crustal, metamorphic origin of mineralising fluids, our results underline the importance of deep-sourced fluids originating from an external source from the volcano-sedimentary succession.

The Fate of “Immobile” Ti in Hyaloclastites: An Evidence from Silica–Iron-Rich Sedimentary Rocks of the Urals Paleozoic Massive Sulfide Deposits

The formation of Paleozoic silica–iron-rich sedimentary rocks in the Urals volcanic-hosted massive sulfide (VHMS) deposits is considered a result of seafloor alteration of hyaloclastites mixed with calcareous/organic or sulfide material. These rocks host various Ti mineral phases pointing to the transformation of precursor metacolloidal TiO2 phases to disordered anatase during seafloor alteration of hyaloclastites, which was later converted to globules and clusters and further to diagenetic rutile. The LA-ICP-MS analysis showed that the Ti content of hyaloclasts partly replaced by finely dispersed Si–Fe aggregates increases to 540–2950 ppm and decreases (&lt;5 ppm) in full Si–Fe pseudomorphs after hyaloclasts. LA-ICP-MS element mapping reveals the enrichment in V, U, Cr, W, Nb, Pb, and Th of the anatase globules and the local accumulation of Zr, Y, and REE on their periphery. Corrosive biogenic textures in the outer zones of some hyaloclasts and biomorphic aggregates in rocks contain anatase particles in assemblage with apatite indicating the biophilic properties of Ti. This work fills the knowledge gaps about Ti mobilization during low-temperature seafloor alteration of hyaloclastites in VHMS deposits.

Lithium isotopic composition of low-temperature altered oceanic crust and its implications for Li cycling

To investigate the Li fluxes and its isotopic fractionation during low-temperature seafloor alteration, we present the Li isotope compositions of fifty fresh and altered basalts drilled from the Integrated Ocean Drilling Program (IODP) 329 Expedition Sites U1365 and U1368, which show different low-temperature (<150 °C) alteration styles and intensities (i.e., total volume of secondary minerals and degrees of elemental enrichment) with meager sedimentation rates (0.71 and 1.1 m/Myr, respectively). The fresh basalts (δ7Li vary from +2.7 to +6.4) show Li isotope compositions consistent with the published N-MORB (+3.5 ± 1.0‰), whereas the altered basalts exhibit considerably higher δ7Li values (+1.7‰ to +11.6‰). Furthermore, their δ7Li values show positive correlations with alkali elements and loss on ignition and follow a mixing trend between a MORB-like endmember and a Li-rich seawater-derived endmember (+9.2 ± 0.2‰), which indicates the effects of low-temperature seafloor alteration on Li isotopic compositions. Based on previously reconstructed paleo-seawater Li isotope compositions, the Li isotopic fractionation scale between seawater and altered basalts is estimated (+12.6‰ and +18.0‰ for Sites U1365 and U1368, respectively), which further supports previous conclusions that the scale of Li isotope fractionation changes over time. A mass calculation suggests the upper limits of the Li-uptake fluxes during low-temperature seafloor alteration are 14.9 ± 2.2 × 109 mol/year and 3.6 ± 1.3 × 109 mol/year for Sites U1365 and U1368, respectively. In addition, our estimation shows the Li-uptake flux during low-temperature seafloor alteration in the Cretaceous is comparable to the total Li-input flux, whereas, in the Neogene, the Li-uptake flux during low-temperature seafloor alteration is much lower than that of the Li-input flux, which suggests a large diagenetic Li sink may be necessary to maintain the seawater Li budget balance if we assume the seawater Li concentration is roughly constant.

Subseafloor hydrothermal mineralization in a non-transform offset: Mineralogy and LA-ICP-MS study of sulfide from the Taiji-2 hydrothermal field, Southern Mid-Atlantic Ridge

In modern seafloor hydrothermal mineralization systems, subseafloor deposits are crucial alongside seafloor massive sulfides, consisting mainly of stockwork at the periphery and semi-massive sulfides at the central of subseafloor ore bodies. These two ore types exhibit contrasting mineralogical and elemental compositions, and the difference between their formation processes are unclear due to sampling challenges. The mafic-hosted Taiji-2 hydrothermal field, located on the Southern Mid-Atlantic Ridge, presents pyrite-enriched subseafloor sulfides on the seafloor, providing a good research opportunity. Our study included comprehensive analyses of mineralogy, pyrite chemistry, and in-situ sulfur isotopes through LA-MC-ICP-MS method on Taiji-2 subseafloor samples. Our findings suggest: (1) a hybrid source of ore-forming materials, (2) increased seawater involvement and decreased temperature and sulfur fugacity from the periphery to the central of subseafloor deposits, and (3) multistage of subseafloor ore-forming activities. Additionally, we characterized the seafloor alteration of Taiji-2 subseafloor sulfides. These results enhance our understanding of subseafloor mineralization in seafloor hydrothermal field.

Progressive lawsonite eclogitization of the oceanic crust: Implications for deep mass transfer in subduction zones

Abstract Lawsonite eclogites are major hosts of H2O and trace elements and thus key for long-term deep element cycling in subduction zones. Existing cycling models suggest that the subducting oceanic crust transforms to lawsonite-eclogite assemblages; yet the scarcity of lawsonite eclogites in the rock record questions to what extent the oceanic crust transforms to lawsonite-eclogite assemblages during subduction. Here, we use petrological modeling coupled with geodynamic calculations for a typical subduction zone to show that the occurrence of lawsonite eclogites is controlled by the maturation of the subduction zone. We find that lawsonite eclogite does not form in infant subduction zones; with time, the oceanic crust forms lawsonite assemblages, but prograde heating obliterates lawsonite except in rocks exhumed prior to such heating. Lawsonite-eclogite assemblages in the oceanic crust form and survive prograde metamorphism only in mature and cold subduction zones but still necessitate specific characteristics during exhumation to preserve lawsonite. We show that the stability of lawsonite in mature subduction zones is hindered by hybridization between the mafic crust and the overlaying mantle wedge material; by contrast, lawsonite proportion increases with intense seafloor alteration and Ca-Al metasomatism. These latter processes are thus key for enhancing recycling. We argue that lawsonite-driven mass cycling to the deep mantle is important in mature subduction zones, but the role of lawsonite eclogite in carrying mass deep into Earth in the infant stage of a subduction zone is minor.

Architectural and Compositional Diversity of Early Earth Ocean Floor Evidenced by the Paleoarchean Nondweni Greenstone Belt, South Africa

Abstract The nature of the early Archean ocean floor remains a topic of important debate. There are relatively few well-preserved occurrences worldwide where such terrains may be studied in detail because of structural dismemberment, metamorphic overprinting and pervasive early stage hydrothermal alteration to recent weathering. The 3.41-Ga dominantly mafic formations of the Nondweni Greenstone Belt (NGB) covering 270 km2 in the south-eastern Kaapvaal Craton comprise submarine volcanics that exhibit a wide range of textural features, including pillows, chill zones and brecciated flow tops, and various spinifex textures, including the rare platy pyroxene type, cumulate layers, and tuffs. Channelized subaqueous lava lakes that underwent fractionation are capped by thick spinifex-textured units and pillows. Early stage seafloor alteration is regionally variable, ranging from intense to minimal, with preservation of original mineralogy in many areas. Mafic volcanic rocks of the NGB contrast with those of the Barberton Greenstone Belt both in the style of volcanism and in the associated compositional range of komatiitic basalt to basalt with a complete absence of high-Mg komatiites. Olivine-phyric rocks, or derivatives thereof, are largely absent and pyroxene is the main controlling phase with orthopyroxene in the most primitive komatiitic basalts and clinopyroxene in the evolved lava lake sequences. The abundance of orthopyroxene typifies the long-standing silica-enriched character of the Kaapvaal Craton. Three exceptionally well-preserved and well-exposed sequences were studied utilizing hand-drilled samples and deep coring providing unprecedented stratigraphic and textural detail and field controls for more than 400 samples. A unifying feature of the mafic volcanics of the NGB is the range of compositions and ratios of incompatible elements most clearly illustrated by a series of high- and low-Ti compositional lineages reflecting differing sources or degrees of mantle partial melting. Sharp boundaries between high- and low-Ti flow successions indicate sudden changes in the melting regimes or the interaction of flow sequences from different volcanic centres. Th/Nb ranges from 0.1 to 0.2 and reveals crustal contamination of primitive lavas. The primary magma that gave rise to the most primitive komatiitic basalts with 19.5% MgO was derived from partial melting of a mantle plume source in the garnet stability field. Trace element modeling shows that the sequences studied in detail have been modified by fractionation and crustal contamination with the most likely contaminant being the Ancient Gneiss Complex (3.43–3.66 Ga), which is extensively exposed in Eswatini and probably underlies the Paleoarchean terrains in the southern Kaapvaal Craton. The geotectonic setting was likely that of a submerged felsic crustal platform as enclaves within an oceanic plateau.

Sulfur in Archean komatiite implies early subduction of oceanic lithosphere

Komatiite is a magnesium-rich volcanic rock that erupted almost exclusively during the Archean era, requiring high partial melting of Earth's upper mantle to form. Archean komatiites, therefore, provide the most reliable information on the mantle geochemistry of the early Earth. However, it remains unclear whether komatiite compositions reflect only remnants of an early deep mantle or may provide evidence of recycling of subducted components. Sulfur mass-independent fractionation (S-MIF) could be useful to distinguish the two scenarios because S-MIF is produced only by photochemistry in anoxic atmospheres. We report here multiple sulfur isotope analyses of the 2.7 Ga Belingwe komatiites and related volcanics. Some Belingwe komatiites show clear S-MIF signatures (Δ33S from −0.20‰ to −0.12‰). Petrology, trace element chemistry, and Sr-Nd-Pb isotope compositions demonstrate that the samples contain Ni-poor pristine igneous sulfides and crustal contamination is minimal. The observed S and initial Nd isotope covariation can be reconciled if the komatiite source involved an early depleted shallow mantle which acquired S-MIF from seawater (Δ33S < 0‰) via seafloor alteration. We suggest that the Belingwe komatiites were derived at least partly from a past subducted oceanic lithosphere that stagnated in the mantle from the Archean era to the present. Therefore, the sulfur isotopes in Archean komatiite provide new constraints on the history of subduction and the recycling of crustal material.

Favorable P–T–ƒO2 conditions for abiotic CH4 production in subducted oceanic crusts: A comparison between CH4-bearing ultrahigh- and CO2-bearing high-pressure eclogite

Subduction is a key element in the carbon cycle between the Earth’s surface and deep interior. In addition to pressure (P) and temperature (T), oxygen fugacity (ƒO2) is an intensive variable that can change the speciation, stability, and mobility of carbon-bearing phases in subduction zones. However, tracking redox evolution and associated carbon speciation in high-pressure metamorphic rocks from subduction zones remains challenging. In this study, we identified CH4-rich fluid inclusions in ultra-high-pressure (UHP; i.e., coesite-bearing) eclogites (the UHP-CH4 eclogite) and CO2-rich fluid inclusions in high-pressure (HP; i.e., quartz-bearing) eclogites (the HP-CO2 eclogite) from the Chinese southwestern (SW) Tianshan palaeosubduction zone, respectively. Combining the garnet-clinopyroxene oxybarometry and comprehensive thermodynamic calculations, we revealed that the ƒO2 of the UHP-CH4 eclogite decreases to a minimum of ∼FMQ − 3 at peak P–T conditions (2.8 GPa, 525 °C) and CH4 is expected to form in graphite-saturated CHO fluids. Whereas during the early-exhumation stage (2.5 GPa, 600 °C), the UHP-CH4 eclogite is predicted to buffer higher ƒO2 conditions of ∼FMQ − 0.9. In contrast, the HP-CO2 eclogite, which has a higher bulk CO2 content (∼10 wt%) and elevated Fe3+/ΣFe ratio (0.24) than the UHP-CH4 eclogite, suggesting a stronger oxidative seafloor alteration of the HP-CO2 eclogite protolith before subduction, stabilizes graphite and CO2-rich fluids at peak ƒO2 conditions between FMQ and FMQ + 1 (2.6 GPa, 500 °C). These data demonstrate that the thermal structure (P–T conditions) of the subduction zone and the composition of the slab are first-order controls on the redox evolution of subducting slabs and the changing speciation of carbon in slab fluids buffered by the metamorphic rock system. Therefore, we propose that the cold subduction of a weakly altered oceanic crust (e.g., UHP-CH4 eclogites from the SW Tianshan) provides ideal conditions for the formation of ultra-deep abiotic CH4.

Early accretion and prolonged carbonation of the Pacific Ocean's oldest crust

Abstract Newly formed oceanic crust is altered by seawater and carbonated at low temperatures over poorly defined periods of time. We applied in situ U-Pb dating to investigate 28 carbonate veins from Ocean Drilling Program Hole 801C, which is situated in the oldest Jurassic-age oceanic crust preserved in the western Pacific Ocean. Our results indicate that Pacific Ocean crust began accreting at 192 ± 6 Ma, which is ~25 m.y. earlier than previously recognized. Carbonation peaked at 171 ± 5 Ma and continued at a low rate for more than ~65 m.y. after accretion. Jurassic carbonation rates varied over ~10 m.y. timescales but encompassed a range similar to that observed today. These data suggest that carbonation rates are relatively insensitive to changes in atmospheric CO2, but confirm the longevity of seafloor alteration as a critical control in global volatile cycling.

Multi-mode chemical exchange in seafloor alteration revealed by lithium and potassium isotopes

Elemental exchange during seafloor alteration exerts substantial control on the chemical compositions of seawater and oceanic crust, as well as the global elemental cycling. However, detailed processes and mechanisms for element transport and isotopic exchange remain unclear. Here, we report Li and K isotopic compositions across an altered MORB-like pillow basalt from Mariana Trench. We find large and systematic isotopic variations on a centimeter scale, with δ7Li decreasing from +9.07‰ to +6.21‰ and δ41K increasing from −0.12‰ to +0.33‰ from the rim to the core. The heavier-than-mantle Li and K isotopic compositions in the core likely inherit from an enriched mantle source rather than post-magmatic alteration processes. The low K and high Li isotopic compositions at the outmost rims result from adsorption during seawater-rock interactions. The basin-shaped elemental and isotopic variations were subsequently formed by chemical diffusion and spontaneous seawater penetration from the weathered rind to the interior of pillow basalt sample. This study uses a small-scale sampling approach and provides the first evidence for multi-mode chemical exchange in oceanic basalts and improves our understanding of the seafloor alteration processes.

Iron isotope compositions of subduction-derived rocks: Insights from eclogites and metasediments of the Münchberg Massif (Germany)

The Fe isotope systematics of subducted lithologies are crucial for the understanding of redox-dependent mass transfer in subducting slabs, with consequences for the compositions of arc magmas and of the deep mantle. We investigated eclogites, metagabbros, and paragneisses from the Variscan Münchberg Massif to unravel whether their Fe isotope compositions are dominated by the igneous/sedimentary protolith signature, by low-temperature seawater alteration, or by later fluid-rock interactions during the subduction-exhumation cycle. Although the eclogites are thought to be derived from a continental rather than oceanic setting (possibly a rift-drift transition stage), they have mid-ocean ridge basalt (MORB)-like major and trace element compositions. They are often moderately oxidized compared to MORB (Fe3+/ΣFe = 0.06 to 0.30). Their δ56Fe values (+0.00 to +0.17‰; mean + 0.08 ± 0.01‰) mostly resemble those of MORB (+0.07 to +0.17‰). The metagabbros, which are derived from a more enriched mantle source than the eclogites, yielded heavier δ56Fe values (+0.09 to +0.22‰) similar to ocean island basalts, whereas those of the paragneisses (+0.03 to +0.10‰) are typical for pelitic sediments.It appears that the Fe isotope compositions of the igneous protoliths are largely preserved and little if any Fe was mobilized during the diverse fluid-rock interaction stages. The parental magma of the eclogites was probably somewhat isotopically lighter than similarly differentiated MORB magmas, perhaps due to the presence of metasomatized, isotopically light peridotites in the subcontinental lithospheric mantle (SCLM) source. Although it is possible that δ56Fe values were slightly modified during seawater alteration and/or metamorphic fluid-rock interactions in some of the eclogites, the impact of fluid-rock interactions on the major element compositions of the eclogites appears to be small. Furthermore, the scarcity of metamorphic veins in the Münchberg Massif argues against significant Fe mobilization in the slab. We suggest that continental eclogites tend to retain their magmatic δ56Fe values throughout the subduction-exhumation cycle, whereas δ56Fe values of oceanic eclogites may often be dominated by seafloor alteration with potential local modifications in the slab close to fluid channels. The remarkable robustness of the Fe isotope compositions of continental eclogites suggests that they may be used to reconstruct protolith mantle source properties despite the complex post-magmatic history.

The origin of early continental crust: New clues from coupling Ge/Si ratios with silicon isotopes

The recent discovery of heavy Si isotopic compositions in both high-Na Tonalite-Trondhjemite-Granodiorite (TTG) and High-K Granite-Monzonite-Syenite (GMS) suites of early continental crust requires that a notable seawater-derived silica-rich component had been added to their respective protoliths prior to melting. Here we use the Ge/Si ratio as a complementary tracer to δ30Si in order to delineate the exact role of modal quartz and silicified basalts from the Archean seafloor among the primary controls of the early appearance of felsic melts on Earth. We have approached the question by (1) specifying the Ge/Si signatures of various Archean and post-Archean rock types by compiling the Ge-SiO2 data stored within the GEOROC database; (2) coupling Ge/Si investigation to silicon isotopes on a large selection of silicified and unsilicified altered mafic and ultramafic greenstones, felsic volcanics, TTG and GMS granitoids and mineral separates from TTGs of the Barberton Greenstone Belt (BGB) of South Africa. The GEOROC compilation demonstrates that Archean TTGs and granites display much lower Ge/Si (1.15±0.10 and 1.13±0.11 μmol/mol, respectively) than post-Archean adakites, granites, tonalites and granodiorites (with average Ge/Si in the range of 1.64 to 1.85 μmol/mol). This result is corroborated by the Ge/Si ratios we report from BGB rocks that formed prior to Kaapvaal craton stabilisation, including 3.5 Ga Theespruit Formation felsic volcanic rocks, 3.5-3.2 Ga TTGs and 3.2-3.1 Ga GMSs, all of which exhibit low ratios (0.68±0.23; 0.92±0.17; 1.05±0.19 μmol/mol, respectively). Based on their low TTG-like Ge/Si, pre-cratonic GMSs are dismissed as being derived from melting of both TTG and metasedimentary sources. Instead, TTGs and GMSs originated from similar Ge-depleted sources. Low Ge/Si ratios, coupled to heavy Si isotopic signatures (−0.14‰<δ30Si<+0.27‰) are also a characteristic feature of mafic and ultramafic BGB greenstones subjected to low-temperature hydrothermal seafloor alteration, especially at the interface between silicified (0.2<Ge/Si<1.2 μmol/mol) and unsilicified (1.8<Ge/Si<3.1 μmol/mol) portions of the altered Archean seafloor. We infer that both Na-rich and K-rich Archean felsic melts are derived from a unique class of protoliths: Ge-depleted metabasalts containing a significant modal proportion of supracrustal quartz generated by the silicification of the Eo-Paleoarchean basaltic seafloors. The transition from Na-rich to K-rich felsic melts in the BGB is assumed to be connected to a gradual increase of potassium as a key element associated with seafloor silicification. In contrast, younger (3.07-2.69 Ga), post-cratonic BGB granites have higher Ge/Si (1.93±0.23 μmol/mol) and were generated through the reworking of a TTG-like basement, by incongruent melting of biotite and hornblende (1.79<Ge/Si<2.97 μmol/mol) leaving an oligoclase-rich (0.64<Ge/Si<0.72) residue. The Earth changed from a prevalent Ge-depleted felsic crust in early-middle Archean times to a widespread Ge-enriched post-Archean crust, which emphasizes the importance of late Archean changes in the Earth dynamics. In particular, our data suggest the likelihood of generating primitive felsic continents by rather shallow melting processes, without the need for inducing high pressures by subduction, as long as Archean ocean floors were silicified.

Copper Isotopic Fractionation During Seafloor Alteration: Insights From Altered Basalts in the Mariana and Yap Trenches

AbstractTo further investigate copper (Cu) isotopic fractionation during seawater‐oceanic crust interactions, 13 subsamples across a basalt altering section and 12 bulk‐rock basalts from the southern Mariana and Yap trenches, western Pacific Ocean, were studied. We find that the δ65Cu values of the basalt section roughly increase from mid‐ocean ridge basalt‐like values (0.04% – 0.10%) in the core to higher values (up to 0.20%) near the core‐rim interface, and then lower values (down to −0.17%) at the rims. Isotopically light rims reflect the initial dissolution of Cu‐bearing sulfides releasing isotopically heavy Cu into ambient seawater, consistent with both lower Cu and sulfide contents in the altered rims. The elevated δ65Cu values reveal that sulfide dissolution induced a concentration‐driven diffusion from the core to rims, controlling the rim‐core‐rim Cu content and isotopic variations on centimeter scale. By contrast, the δ65Cu values of bulk‐rock basalts show a wide range (0.02% – 0.56%) with most samples enriched in heavy isotopes, and negatively correlate with Cu concentrations, indicating preferential adsorption of isotopically heavy Cu from seawater. We propose that chemical diffusion occurred prior to any adsorption processes, suggesting that a three‐stage process involving sulfide dissolution, chemical diffusion and adsorption controls Cu isotopic fractionation during seafloor basalt alteration.

Latest Miocene (Kapitean/Messinian) glauconite and the central Chatham Rise greensand: an enigmatic, highly condensed, relict/palimpsest deposit on the modern seafloor

ABSTRACT A unique 10–140 cm thick veneer of greensand and glauconite-rich deposits (10–80 wt% glauconite) presently sits atop central Chatham Rise (CR) in water depths of 200-500 m. The glauconite is dominated by chemically mature, polished ovoidal and lobate pellets, with a 10–12 Å phyllosilicate structure and K-Ar ages of 7–5 Ma, indicating that the glauconite pellets are predominantly allogenic (i.e. derived/reworked) grains, and not of in situ authigenic origin. Glauconite possibly evolved from seafloor alteration of detrital and/or volcanogenic smectitic clays, likely concentrated within organic-rich faecal pellets under unique paleoceanographic conditions (nutrient cycling, upwelling, carbon isotope gradients) within the latest Miocene Subtropical Front. The distribution of glauconite abundance suggests a ‘glauconite factory’ existed at this time about Reserve Bank on western central CR. The pellets were dispersed eastwards along the crest by intensified bottom currents within the dynamic Subtropical Frontal zone, perhaps during the numerous glacial periods of lowered sea level throughout the Plio-Quaternary. The bioturbated greensand veneer, and its mix of other reworked Neogene and Quaternary skeletal, phosphatic and siliciclastic components, rest unconformably on mainly Early Oligocene chalks, forming a highly condensed, relict/palimpsest deposit that alone embodies the last up to 30 My of sedimentation history atop central CR.

The Paleoarchean Northern Mundo Novo Greenstone Belt, São Francisco Craton: Geochemistry, U–Pb–Hf–O in zircon and pyrite δ34S-Δ33S-Δ36S signatures

Greenstone belts contain several clues about the evolutionary history of primitive Earth. Here, we describe the volcano-sedimentary rock association exposed along the eastern margin of the Gavião Block, named the Northern Mundo Novo Greenstone Belt (N-MNGB), and present data collected with different techniques, including U–Pb–Hf–O isotopes of zircon and multiple sulfur isotopes (32S, 33S, 34S, and 36S) of pyrite from this supracrustal sequence. A pillowed metabasalt situated in the upper section of the N-MNGB is 3337 ± 25 Ma old and has zircon with εHf(t) = −2.47 to −1.40, Hf model ages between 3.75 Ga and 3.82 Ga, and δ18O = +3.6‰ to +7.3‰. These isotopic data, together with compiled whole-rock trace element data, suggest that the mafic metavolcanic rocks formed in a subduction-related setting, likely a back-arc basin juxtaposed to a continental arc. In this context, the magma interacted with older Eoarchean crustal components from the Gavião Block. Detrital zircons from the overlying quartzites of the Jacobina Group are sourced from Paleoarchean rocks, in accordance with previous studies, yielding a maximum depositional age of 3353 ± 22 Ma. These detrital zircons have εHf(t) = −5.40 to −0.84, Hf model ages between 3.66 Ga and 4.30 Ga, and δ18O = +4.8‰ to +6.4‰. The pyrite multiple sulfur isotope investigation of the 3.3 Ga supracrustal rocks from the N-MNGB enabled a further understanding of Paleoarchean sulfur cycling. The samples have diverse isotopic compositions that indicate sulfur sourced from distinct reservoirs. Significantly, they preserve the signal of the anoxic Archean atmosphere, expressed by MIF-S signatures (Δ33S between −1.3‰ to +1.4‰) and a Δ36S/Δ33S slope of −0.81 that is indistinguishable from the so-called Archean array. A BIF sample has a magmatic origin of sulfur, as indicated by the limited δ34S range (0 to +2‰), Δ33S ~ 0‰, and Δ36S ~ 0‰. A carbonaceous schist shows positive δ34S (2.1‰–3.5‰) and elevated Δ33S (1.2‰–1.4‰) values, with corresponding negative Δ36S between −1.2‰ to −0.2‰, which resemble the isotopic composition of Archean black shales and suggest a source from the photolytic reduction of elemental sulfur. The pillowed metabasalt displays heterogeneous δ34S, Δ33S, and Δ36S signatures that reflect assimilation of both magmatic sulfur and photolytic sulfate during hydrothermal seafloor alteration. Lastly, pyrite in a massive sulfide lens is isotopically similar to barite of several Paleoarchean deposits worldwide, which might indicate mass dependent sulfur processing from a global and well-mixed sulfate reservoir at this time.

The Molybdenum isotope subduction recycling conundrum: A case study from the Tongan subduction zone, Western Alps and Alpine Corsica

Molybdenum isotopes have emerged as novel tracers for high-temperature igneous and metamorphic processes. The debate remains to what extent different subducted slab lithologies, such as oceanic crust and marine sediments, contribute to the Mo isotope signature of arc magmas and, hence, exert different controls on the terrestrial Mo cycle. Here we investigate Mo isotope systematics from input to output at the Tongan subduction zone: Arc lavas from different Tongan islands, pelagic sediments and altered oceanic crust (AOC) samples from DSDP site 595/596 on the subducting Pacific plate. For complementary insights into the fate of Mo and its isotopic signatures during prograde subduction metamorphism, we also present data of metasediments and variably altered AOC-type eclogites from the Zermatt-Saas ophiolite, Switzerland and Italy, and the Schistes Lustrés Complex in Alpine Corsica.Manganese oxide-rich pelagic sediments from DSDP site 595/596 show variable, depth-dependent Mo/Mn ratios and Mo isotope compositions controlled by diagenetic reactions. As subducted equivalents, Mn-rich eclogitic metapelites display lower Mo contents and δ98/95Mo ratios compared to their non-subducted protolith. This indicates prominent loss of Mo along with isotope fractionation during early subduction metamorphism. In comparison to unaltered MORB, low temperature seafloor alteration has shifted Mo/Ce and δ98/95Mo in studied AOC samples towards lower ratios, in the range of most mafic eclogites published so far. However, some mafic eclogites show even lower Mo/Ce and δ98/95Mo ratios compared to AOC, likely due to fluid-related Mo loss upon early subduction and preferential incorporation of light Mo into residual rutile.Our data document a prominent loss of isotopically heavy Mo before and upon early subduction metamorphism at shallow depths in the forearc region. Moreover, when prograde rutile crystallizes at ~30 km depth, it fixes the largest fraction of Mo in the subducting material. This creates an “arc Mo-conundrum” as devolatization of the slab at subarc depths is not able to account for the fluid-mobile Mo source responsible for observed higher Mo/Ce and δ98/95Mo in Tongan arc lavas compared to the mantle. As an alternative scenario, Mo mobilization by slab-derived aqueous fluids during the early stages of subduction into the forearc mantle produces serpentinites enriched in Mo with a possible heavy Mo isotopic signature. Mechanical transport and devolatization of forearc serpentinites at subarc regions is a plausible alternative recycling process accounting for the observed Mo systematics in Tongan arc lavas. This is supported by positive covariations of Mo/Ce and δ98/95Mo with elements such as As, Sb, and Cs, which are thought to be mostly released from the subducting material during early stages of subduction. We propose that a multi-stage recycling of metasomatized forearc mantle can be an important process in recycling of Mo and possibly other elements.

Multiple sulfur isotopes constraints on origin and evolution of the Neoarchean and Paleoproterozoic Cu-Au systems from the Carajás Domain, Amazonian Craton, Brazil

Multiple sulfur isotopes in sulfides were measured by in situ Secondary Ion Mass Spectrometry in order to constrain sulfur sources and pathways, as well as explore atmosphere–ore genesis implications on the metallogeny of the Neoarchean and Paleoproterozoic Cu-Au systems of the Carajás Domain, southeast Amazonian Craton, Brazil. All of the investigated Neoarchean (2.70–2.57 Ga; i.e., Salobo, Igarapé Bahia, Castanha and Sequeirinho) and Paleoproterozoic IOCG (ca 1.88 Ga; i.e., Alvo 118 and Sossego) deposits show Δ33S < 0‰ (-0.17‰ to + 0.02‰). The Paleoproterozoic Cu-Au(W-Sn-Bi) Breves deposit reveals Δ33S > 0‰ (+0.08‰ to + 0.27‰), implying that sulfur underwent mass-independent fractionation (MIF). In addition, three distinct δ34S ranges are defined: −3.07‰ to + 3.01‰ and + 2.17‰ to + 4.68‰ for the Neoarchean and Paleoproterozoic IOCG deposits, respectively, and −0.46‰ to + 3.81‰ for the Paleoproterozoic Breves deposit.In the Neoarchean IOCG deposits, sulfur is most likely of mantle/magmatic origin. However, a subtle but detectable MIF-S signature reflects the inheritance of a minor sulfur component transported to the atmosphere, experienced photolytic reactions and returned to the hydrosphere. The interaction between highly saline, hot, and deep-seated metalliferous fluids with the host rocks, including sulfate-bearing volcanic rocks that underwent seafloor alteration, may account for the small negative Δ33S values in the IOCG deposits. The similarity between the negative Δ33S signatures of the Neoarchean and the Paleoproterozoic IOCG deposits (i.e., Sossego and Alvo 118) suggest that the MIF signatures recorded by the latter most likely reflect inheritance of Neoarchean sulfur with MIF signatures acquired by large scale fluid-rock interaction triggered by the ca 1.88 Ga A-type granitic magmatism.The positive Δ33S values of sulfides from the Paleoproterozoic Breves deposit, in contrast, were probably generated by reduced sulfur species sourced from crustal sources (e.g., Archean pyrite-bearing sedimentary units) in addition to magmatic sulfur related to ca. 1.88 Ga A-type granite emplacement.

The role of the antigorite\u2009+\u2009brucite to olivine reaction in subducted serpentinites (Zermatt, Switzerland)

Metamorphic olivine formed by the reaction of antigorite + brucite is widespread in serpentinites that crop out in glacier-polished outcrops at the Unterer Theodulglacier, Zermatt. Olivine overgrows a relic magnetite mesh texture formed during ocean floor serpentinization. Serpentinization is associated with rodingitisation of mafic dykes. Metamorphic olivine coexists with magnetite, shows high Mg# of 94–97 and low trace element contents. A notable exception is 4 µg/g Boron (> 10 times primitive mantle), introduced during seafloor alteration and retained in metamorphic olivine. Olivine incorporated 100–140 µg/g H2O in Si-vacancies, providing evidence for low SiO2-activity imposed by brucite during olivine growth. No signs for hydrogen loss or major and minor element diffusional equilibration are observed. The occurrence of olivine in patches within the serpentinite mimics the former heterogeneous distribution of brucite, whereas the network of olivine-bearing veins and shear zones document the pathways of the escaping fluid produced by the olivine forming reaction. Relic Cr-spinels have a high Cr# of 0.5 and the serpentinites display little or no clinopyroxene, indicating that they derive from hydrated harzburgitic mantle that underwent significant melt depletion. The enrichment of Mg and depletion of Si results in the formation of brucite during seafloor alteration, a pre-requisite for later subduction-related olivine formation and fluid liberation. The comparison of calculated bulk rock brucite contents in the Zermatt-Saas with average IODP serpentinites suggests a large variation in fluid release during olivine formation. Between 3.4 and 7.2 wt% H2O is released depending on the magnetite content in fully serpentinized harzburgites (average oceanic serpentinites). Thermodynamic modelling indicates that the fluid release in Zermatt occurred between 480 °C and 550 °C at 2–2.5 GPa with the Mg# of olivine varying from 68 to 95. However, the majority of the fluid released from this reaction was produced within a narrow temperature field of < 30 °C, at higher pressures 2.5 GPa and temperatures 550–600 °C than commonly thought. Fluids derived from the antigorite + brucite reaction might thus trigger eclogite facies equilibration in associated metabasalts, meta-gabbros, meta-rodingites and meta-sediments in the area. This focused fluid release has the potential to trigger intermediate depths earthquakes at 60–80 km in subducted oceanic lithosphere.

Serpentine alteration as source of high dissolved silicon and elevated \u03b430Si values to the marine Si cycle

Serpentine alteration is recognized as an important process for element cycling, however, related silicon fluxes are unknown. Pore fluids from serpentinite seamounts sampled in the Mariana forearc region during IODP Expedition 366 were investigated for their Si, B, and Sr isotope signatures (δ30Si, δ11B, and 87Sr/86Sr, respectively) to study serpentinization in the mantle wedge and shallow serpentine alteration to authigenic clays by seawater. While serpentinization in the mantle wedge caused no significant Si isotope fractionation, implying closed system conditions, serpentine alteration by seawater led to the formation of authigenic phyllosilicates, causing the highest natural fluid δ30Si values measured to date (up to +5.2 ± 0.2‰). Here we show that seafloor alteration of serpentinites is a source of Si to the ocean with extremely high fluid δ30Si values, which can explain anomalies in the marine Si budget like in the Cascadia Basin and which has to be considered in future investigations of the global marine Si cycle.