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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 of αnet = 0.99969 for diffusion and natural gas convection (low gas velocities) and αnet = 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. Plain Language Summary: Volcanic degassing is an important process for understanding emissions to the atmosphere of greenhouse gasses and toxic metals. Thallium (Tl) is a toxic metal that is highly volatile, which in recent years has been developed as a stable isotope system that can be applied to understand the transfer of material from the Earth surface to the deep mantle via measurements of volcanic lavas. However, degassing of Tl from volcanic lavas could potentially alter the isotope ratio of the residual lava and, thus, render applications of Tl isotopes in lavas difficult to relate to deep Earth material transfer. Here, we perform the first study of Tl isotopes in degassing experiments. These reveal that Tl isotope ratios progressively become enriched in the heavy isotope with loss of Tl. We also show that natural lavas from Kamchatka follow similar Tl depletion and isotope enrichment patterns as our experiments, which for the first time demonstrates that degassing in nature is associated with diffusion‐controlled loss of the light Tl isotope. Key Points: Degassing of Tl from experimental melts are associated with kinetic isotope fractionation limited by diffusion in the gas phaseBasaltic lavas from Kamchatka follow the same Tl depletion‐isotope fractionation pattern as experimental chargesThe majority of literature Tl isotope data for volcanic lavas reveal only limited effects from degassing [ABSTRACT FROM AUTHOR]

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 δ18OVSMOW (+8.6‰ to +23.5‰) correlates positively with δ13CVPDB (−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. Plain Language Summary: Most volcanoes on Earth are silica‐rich. Rare volcanoes that are composed of mostly carbonate minerals (referred to as carbonatite volcanoes) are not as well understood, but provide clues about carbon fluxes into and out of the mantle. To further our understanding of carbonatite genesis, we measured the thallium, oxygen, and carbon isotopes in rocks from a carbonatite volcano in Afghanistan. We discovered systematic variations in all three isotope systems caused by the massive release of carbon dioxide‐ and water‐rich fluids from the magmas prior to eruption. Interaction between these fluids and the surrounding rock—which we argue is fundamental to carbonatite genesis—appears to be largely responsible for magma evolution. As the first study of thallium isotopes in carbonatites, our results also have implications for the origins of carbonatite magmas: we infer that the magmas initially had thallium isotope compositions most similar to ocean crust, which implies that seafloor thallium cycles deep into the mantle and returns to the surface in carbonatitic magmas. Key Points: Thallium isotopes fractionate in carbonatite volcanic systemsThallium in carbonatites may derive from recycled ocean crustBrines cause potassic metasomatism during ascent and eruption of carbonatite magmas [ABSTRACT FROM AUTHOR]

It is generally accepted that subduction of the oceanic crust plays an important role in creation of mantle heterogeneity. HIMU (stands for high μ = ( 238 U/ 204 Pb)) is a rare and probably not volumetrically large mantle component, which is sampled at St. Helena in the Atlantic and in the Cook-Austral Islands in the South Pacific. Previous studies that used radiogenic isotopes have specifically invoked subducted hydrothermally altered oceanic crust (AOC) as a significant component in the source of HIMU. However, because radiogenic isotopes are affected by both parent-daughter fractionation and time that cannot be independently determined, it is difficult to unambiguously use these tracers to determine the source material of the HIMU reservoir. Thallium isotopes can be used to identify the involvement of sediments rich in Mn oxides or AOC, because these two components exhibit high Tl concentrations and highly fractionated Tl isotope compositons, whereas the upper mantle is depleted in Tl and homogenous with respect to Tl isotopes. Here we report Tl isotope data for a suite of St. Helena lavas previously characterized to investigate if the HIMU mantle reservoir can be linked to AOC. Samples show large Tl isotopic variation, from ε 205 Tl = − 9.8 to ε 205 Tl = + 3.9 and do not correlate with Sr, Nd, Hf or Pb isotopes. Eight samples have ε 205 Tl lighter than the mantle value (ε 205 T = − 2), with the lightest values similar to those observed for modern AOC. These features are consistent with the presence of different proportions of recycled oceanic crust in the source of St. Helena mantle source. Our results, therefore, support previous studies that inferred AOC as a significant component in the HIMU mantle reservoir and show that the Tl isotopic system can be used as a powerful tracer to detect contributions of AOC in the creation of mantle heterogeneities. [ABSTRACT FROM AUTHOR]

Abstract Thallium (Tl) isotope compositions of ocean island basalts (OIBs) have been proposed as a novel tracer of subducted oceanic crust and sediments in ocean island basalt sources, which could act as direct confirmation that deep mantle recycling eventually resurfaces through mantle upwelling to form ocean island basalt magmatism. However, it is unknown if oceanic crust that went through an active subduction zone would retain the Tl isotope compositions recorded in hydrothermally altered oceanic crust and authigenic marine sediments. In this study we present Tl isotope and concentration data for samples of subducted oceanic crust from five different locations: Zambezi Belt, Zambia; Cabo Ortegal complex, Iberian Massif, Spain; Raspas Complex, southwest Ecuador; Syros island, Cyclades, Greece; Tian Shan, northwest China. Thallium concentrations in most samples follow strong linear relationships with K, Rb, Cs and Ba, which strongly suggest that the mineral phengite is the primary control of Tl abundances in subducted oceanic crust. This conclusion is consistent with recent Tl data sets for arc lavas that imply residual phengite in the arc lava source regions as a strong control of Tl recycling. We find that Tl isotope compositions vary widely and systematically in each location depending on the protolith, metamorphic and metasomatic history of the samples. Samples from Cabo Ortegal and Raspas Complex reveal Tl isotope compositions similar to their protoliths, which were comprised of low-temperature altered oceanic crust. Tian Shan metamorphic rocks and Zambian eclogites reveal invariant Tl isotope values indistinguishable from average mantle, which is best explained by overprinting by metamorphic fluids that contained high concentrations of Tl and other alkali metals. Samples from Syros reveal a range of Tl isotope compositions from normal mantle towards values for pelagic clay sediments. The sediment-like values in Syros likely arose from fluids released from the surrounding mélange matrix that consists of serpentinite, metagabbros and metasediments. Each of the three Tl isotope ranges observed for subducted oceanic crust samples here are mirrored by individual OIB locations. Cabo Ortegal and Raspas Complex display Tl isotope compositions identical to St. Helena, suggesting that the HIMU component likely comprises subduction modified low-temperature altered oceanic crust. Thallium isotope ratios in Zambia and Tian Shan eclogites and blueschists are identical to lavas from Iceland, whereas Syros metamorphic rocks overlap almost exactly with lavas from Hawaii. Our data, therefore, show that Tl isotope compositions of oceanic crust and sediments can be traced through the subduction process and eventually is expressed largely unmodified in ocean island basalts. [ABSTRACT FROM AUTHOR]

Sediments are actively subducted in virtually every arc worldwide. However, quantifying their contributions to arc lavas and thereby establishing budgets of how sediments participate in slab-mantle interaction is challenging. In this contribution we use thallium (Tl) abundances and isotopic compositions of lavas from the Ryukyu arc (including south Kyushu) and its back-arc basin, Okinawa Trough, to investigate the influence of sediments from arc to back-arc. We also present extensive geochemical data for sediments and altered oceanic crust (AOC) outboard of the northern (DSDP Sites 296, 442B, 443 and 444) and central (DSDP Sites 294 and 295) part of the Ryukyu arc. The Tl isotopic compositions of sediments change systematically from lighter outboard of northern Ryukyu arc to heavier outboard of central Ryukyu arc. The feature reflects the dominance of terrigenous material and pelagic sedimentation outboard of the northern and central Ryukyu arc, respectively. Central and northern sections of Ryukyu arc and Okinawa Trough display larger range of Tl isotopic variation than southern section, which is consistent with more pelagic provenance for sediments outboard of central and northern Ryukyu arcs than that of expected sediments outboard of southern Ryukyu arc. Identical Tl, Sr, Nd and Pb isotope variations are found when comparing arc and back arc lavas, which indicates that sediments fluxes also account for the Tl isotopic variations in the Okinawa Trough lavas. Two-end-member mixing models of Tl with Pb, Sr and Nd isotopes require sediment inputs of< 1%, 0.1–1% and 0.3–2% by weight to the depleted mantle source to account for all these isotopic compositions of lavas from northern, central and southern portion of the Ryukyu arc and Okinawa Trough. Bulk mixing between mantle and sediment end members predict very similar sediment fluxes when using Tl, Sr, Nd and Pb isotopes, which indicates that fractionation of these elements must have happened after mixing between mantle and sediments. This conclusion is corroborated by model calculations of mixing between sediment melts with fractionated Sr/Nd ratios and mantle wedge, which show that no arc lava plot on such mixing lines. Thus bulk sediment mixing, rather than sediment melt, is required for the generation of the lavas from the Ryukyu arc and Okinawa Trough. The requirement of bulk sediment mixing occurring before trace element fractionation in the sub-arc mantle is consistent with models where mélange layers form at the top of the slab and are the principle source material for arc lavas. In addition, the fact that sediment components observed in the Ryukyu arc and Okinawa Trough lavas are similar, suggests that transport of mélange material to the source regions of the arc and back arc is equally efficient. This feature is most readily explained if mélange material is transported from the slab as diapirs. [ABSTRACT FROM AUTHOR]

Sediment transport from the subducted slab to the mantle wedge is an important process in understanding the chemical and physical conditions of arc magma generation. The Aleutian arc offers an excellent opportunity to study sediment transport processes because the subducted sediment flux varies systematically along strike (Kelemen et al., 2003) and many lavas exhibit unambiguous signatures of sediment addition to the sub-arc mantle (Morris et al., 1990). However, the exact sediment contribution to Aleutian lavas and how these sediments are transported from the slab to the surface are still debated. Thallium (Tl) isotope ratios have great potential to distinguish sediment fluxes in subduction zones because pelagic sediments and low-temperature altered oceanic crust are highly enriched in Tl and display heavy and light Tl isotope compositions, respectively, compared with the upper mantle and continental crust. Here, we investigate the Tl isotope composition of lavas covering almost the entire Aleutian arc a well as sediments outboard of both the eastern (DSDP Sites 178 and 183) and central (ODP Hole 886C) portions of the arc. Sediment Tl isotope compositions change systematically from lighter in the Eastern to heavier in the Central Aleutians reflecting a larger proportion of pelagic sediments when distal from the North American continent. Lavas in the Eastern and Central Aleutians mirror this systematic change to heavier Tl isotope compositions to the west, which shows that the subducted sediment composition is directly translated to the arc east of Kanaga Island. Moreover, quantitative mixing models of Tl and Pb, Sr and Nd isotopes reveal that bulk sediment transfer of ∼0.6–1.0% by weight in the Eastern Aleutians and ∼0.2–0.6% by weight in the Central Aleutians can account for all four isotope systems. Bulk mixing models, however, require that fractionation of trace element ratios like Ce/Pb, Cs/Tl, and Sr/Nd in the Central and Eastern Aleutians occurs after the sediment component was mixed with the mantle wedge. Models of Sr and Nd isotopes that involve sediment melting require either high degrees of sediment melting (>50%), in which case trace element ratios like Ce/Pb, Cs/Tl, and Sr/Nd of Aleutian lavas need to be produced after mixing with the mantle, or significant fluid additions from the underlying oceanic crust with Sr and Nd isotope compositions indistinguishable from the mantle wedge as well as high Sr/Nd ratios similar to that of low (<20%) degree sediment melts. Thallium isotope data from Western Aleutian lavas exhibit compositions slightly lighter than the upper mantle, which implies a negligible sediment flux at this location and probably involvement of low-temperature altered oceanic crust in the generation of these lavas. In general, the lightest Tl isotope compositions are observed for the highest Sr/Y ratios and most unradiogenic Sr and Pb isotope compositions, which is broadly consistent with derivation of these lavas via melting of eclogitized altered oceanic crust. [ABSTRACT FROM AUTHOR]

Fluids driven off the subducting Pacific plate infiltrate the shallow Mariana forearc and lead to extensive serpentinization of mantle peridotite. However, the sources, pathways, and chemical modifications of ascending, slab-derived fluids remain poorly constrained and controversial. In this study, we use thallium (Tl) concentrations and isotopic ratios of serpentinized peridotite and rodingitized diabase from the South Chamorro and Conical Seamounts to discriminate between potential fluid sources with distinct Tl isotope compositions. Serpentinite samples from the Mariana forearc all display ε 205 Tl > − 0.5 (where ε 205 Tl = 10 , 000 × ( Tl 205 / Tl sample 203 − Tl 205 / Tl SRM 997 203 ) / ( Tl 205 / Tl SRM 997 203 ) ), which is significantly enriched in 205 Tl compared to the normal mantle ( ε 205 Tl = − 2 ). Given that high temperature hydrothermal processes do not impart significant Tl isotope fractionation, the isotope compositions of the serpentinites must reflect that of the serpentinizing fluid. Pelagic sediments are the only known slab component that consistently displays ε 205 Tl > − 0.5 and, therefore, we interpret the heavy Tl isotope signatures as signifying that the serpentinizing fluids were derived from subducting pelagic sediments. A rodingitized diabase from Conical Seamount was found to have an ε 205 Tl of 0.8, suggesting that sediment-sourced serpentinization fluids could also affect diabase and other mafic lithologies in the shallow Mariana forearc. Forearc rodingitization of diabase led to a strong depletion in Tl content and a virtually complete loss of K, Na and Rb. The chemical composition of hybrid fluids resulting from serpentinization of harzburgite with concomitant rodingitization of diabase can be highly alkaline, depleted in Si, yet enriched in Ca, Na, K, and Rb, which is consistent with the composition of fluids emanating from mud volcanoes in the Mariana forearc. Our study suggests that fluid–rock interactions between sedimentary, mafic, and ultramafic lithologies are strongly interconnected even in the shallowest parts of subduction zones. We conclude that transfer of fluids and dissolved elements at temperatures and pressures below 400 °C and 1 GPa, respectively, must be taken into account when elemental budgets and mass transfer between the subducting plate, the forearc, the deep mantle and the ocean are evaluated. [ABSTRACT FROM AUTHOR]

Dehydration of the subducted slab is a crucial process in the generation of arc magmas. However, the mineralogical controls of slab dehydration remain uncertain. Thallium (Tl) isotopes have emerged as tracers of subducted slab components, but the Tl isotope characteristics of slab fluids are not known. High-pressure metamorphic veins and host eclogites in the Dabie terrane (China) provide important information on the composition and evolution of subduction zone fluids. In this study, we present the first Tl concentration and Tl isotope data for two high-pressure metamorphic epidote-rich veins formed through breakdown of lawsonite, as well as host eclogites and phengite separates, from the Ganghe and Hualiangting areas. The high Tl concentrations in phengite separates and identical Tl isotope compositions between phengites and their host bulk eclogites demonstrate that phengite controls the overall inventory of Tl in the host eclogites. Generally, the vein samples from both areas have much lower Tl concentrations than their host eclogites, suggesting that the fluids from which the veins precipitated were derived from phengite-bearing eclogites that retained Tl in the residue. The Ganghe eclogites display similar Tl isotope compositions compared with Ganghe omphacite-epidote vein. This similarity indicates that the vein-forming fluid was likely derived from the host eclogites, and that Tl isotopes did not fractionate during fluid-release. Three generations of veins in the Hualiangting area record variable Tl isotope values and were likely derived from multi-stage dehydration of heterogeneous host eclogites, some of which may have contained a sediment component. We argue that fluids derived from eclogite dehydration are likely characterized by higher Cs/Tl ratios compared to their host eclogites. Arc magmas that display high Cs/Tl (i.e. >15) that cannot be caused by variations in slab source composition, coupled with relatively low Ba/Th ratios, are likely to directly record the presence of residual phengite at subarc depths. • Thallium isotope compositions of high-pressure veins and host eclogites were investigated to provide first constraints on the thallium isotope characteristics of fluids produced during eclogite dehydration. • Thallium concentration and isotope compositions of phengites separated from host eclogites are reported. When present, phengite is the dominant host of thallium in subducted slabs. • Fluids released from the subducted slab in the presence of phengite may carry high Cs/Tl ratios, potentially tracing residual phengite in the source of some arc lavas. [ABSTRACT FROM AUTHOR]