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Fluids mediate the transport of subducted slab material and play a crucial role in the generation of arc magmas. However, the source of subduction-derived fluids remains debated. The Kamchatka arc is an ideal subduction zone to identify the source of fluids because the arc magmas are comparably mafic, their source appears to be essentially free of subducted sediment-derived components, and subducted Hawaii-Emperor Seamount Chain (HESC) is thought to contribute a substantial fluid flux to the Kamchatka magmas. Here we show that Tl isotope ratios are unique tracers of HESC contribution to Kamchatka arc magma sources. In conjunction with trace element ratios and literature data, we trace the progressive dehydration and melting of subducted HESC across the Kamchatka arc. In succession, serpentine (<100 km depth), lawsonite (100–250 km depth) and phengite (>250 km depth) break down and produce fluids that contribute to arc magmatism at the Eastern Volcanic Front (EVF), Central Kamchatka Depression (CKD), and Sredinny Ridge (SR), respectively. However, given the Tl-poor nature of serpentine and lawsonite fluids, simultaneous melting of subducted HESC is required to explain the HESC-like Tl isotope signatures observed in EVF and CKD lavas. In the absence of eclogitic crust melting processes in this region of the Kamchatka arc, we propose that progressive dehydration and melting of a HESC-dominated mélange offers the most compelling interpretation of the combined isotope and trace element data.

Carbonatite volcanism remains poorly understood compared to silicic volcanism due to the scarcity of carbonatite volcanoes worldwide and because volcanic H₂O and CO₂—major components in carbonatite volcanic systems—are not well preserved in the rock record. To further our understanding of carbonatite genesis, we utilize the non‐traditional thallium (Tl) isotope system in Khanneshin carbonatites in Afghanistan. These carbonatites contain 250–30,000 ng/g Tl and have ε²⁰⁵Tl values (−4.6 to +4.6) that span much of the terrestrial igneous range. We observe that δ¹⁸O_VSMOW(+8.6‰ to +23.5‰) correlates positively with δ¹³C_VPDB(−4.6‰ to +3.5‰) and ε²⁰⁵Tl up to δ¹⁸O = 15‰. Rayleigh fractionation of calcite from an immiscible CO₂‐H₂O fluid with a mantle‐like starting composition can explain the δ¹⁸O and δ¹³C—but not ε²⁰⁵Tl—trends. Biotite fractionates Tl isotopes in other magmatic settings, so we hypothesize that a Tl‐rich hydrous brine caused potassic metasomatism (i.e., biotite fenitization) of wall rock that increased the ε²⁰⁵Tl of the residual magma‐fluid reservoir. Our results imply that, in carbonatitic volcanic systems, simultaneous igneous differentiation and potassic metasomatism increase ε²⁰⁵Tl, δ¹⁸O, δ¹³C, and light rare earth element concentrations in residual fluids. Our fractionation models suggest that the Tl isotopic compositions of the primary magmas were among the isotopically lightest (less than or equal to ε²⁰⁵Tl = −4.6) material derived from the mantle for which Tl isotopic constraints exist. If so, the ultimate source of Tl in Khanneshin lavas—and perhaps carbonatites elsewhere—may be recycled ocean crust.

Thallium (Tl) isotope ratios are an emerging tool that can be used to trace crustal recycling processes in arc lavas and ocean island basalts (OIBs). Thallium is a highly volatile metal that is enriched in volcanic fumaroles, but it is unknown whether degassing of Tl from subaerial lavas has a significant effect on their residual Tl isotope compositions. Here, we present Tl isotope and concentration data from degassing experiments that are best explained by Rayleigh kinetic isotope fractionation during Tl loss. Our data closely follow predicted isotope fractionation models in which TlCl is the primary degassed species and where Tl loss is controlled by diffusion and natural convection, consistent with the slow gas advection velocity utilized during our experiments. We calculate that degassing into air should be associated with a net Tl isotope fractionation factor ofα_net = 0.99969 for diffusion and natural gas convection (low gas velocities) andα_net = 0.99955 for diffusion and forced gas convection (high gas velocities). We also show that lavas from three volcanoes in the Kamchatka arc exhibit Tl isotope and concentration patterns that plot in between the two different gas convection regimes, implying that degassing played an important role in controlling the observed Tl isotope compositions in these three volcanoes. Literature inspection of Tl isotope data for subaerial lavas reveals that the majority of these appear only minorly affected by degassing, although a few samples from both OIBs and arc volcanoes can be identified that likely experienced some Tl degassing.