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We present geochemical data from gas samples from ~1200 km of arc in the Central Volcanic Zone of the Andes (CVZA), the volcanic arc with the thickest (~70 km) continental crust globally. The primary goals of this study are to characterize and understand how magmatic gases interact with hydrothermal systems, assess the origins of the major gas species, and constrain gas emission rates. To this end, we use gas chemistry, isotope compositions of H, O, He, C, and S, and SO2 fluxes from the CVZA. Gas and isotope ratios (CO2/ST, CO2/CH4, H2O/ST, δ13C, δ34S, 3He/4He) vary dramatically as magmatic gases are progressively affected by hydrothermal processes, reflecting removal and crustal sequestration of reactive species (e.g., S) and addition of less reactive meteoric and crustal components (e.g., He). The observed variations are similar in magnitude to those expected during the magmatic reactivation of volcanoes with hydrothermal systems. Carbon and sulfur isotope compositions of the highest temperature emissions (97–408 ◦C) are typical of arc magmatic gases. Helium isotope compositions reach values similar to upper mantle in some volcanic gases indicating that transcustal magma systems are effective conduits for volatiles, even through very thick continental crust. However, He isotopes are highly sensitive to even low degrees of hydrothermal interaction and radiogenic overprinting. Previous work has significantly underestimated volatile fluxes from the CVZA; however, emission rates from this study also appear to be lower than typical arcs, which may be related to crustal thickness. 

Halogens (F, Cl, Br, I) are primary components of volcanic gas emissions and play an essential role in continental arc magmatic environments due to their solubility in fluids that generate metallic ore deposits. Despite their ubiquity, the behavior and budget of halogens in continental arc environments are poorly constrained. We investigated the plutonic and volcanic halogen budgets in intermediate-to-felsic igneous rocks (56–77 wt% SiO2) from the Sierra Nevada (California) - a Mesozoic continental arc where plutonic and volcanic outcrops can be correlated via their geographic, compositional, and geochronologic framework. We measured the halogen concentrations of bulk rock powders and their leachates via ion chromatography (F, Cl) and ICP-MS (Br, I). Halogen concentrations in our rock powders range between 107–727 μg/g F, 13–316 μg/g Cl, 2–323 ng/g Br, and 1–69 ng/g I. In contrast, leachates yielded 3–4 orders of magnitude less Cl and F, one order of magnitude less I, and similar amounts of Br compared to their corresponding bulk rocks. Preliminary data show no significant differences between volcanic and plutonic samples, suggesting that halogen concentrations in these rocks are insensitive to shallow fractionation. Although F and I exhibit no correlation with major element compositions, Cl and Br display negative trends with increasing SiO2 and K2O, and positive trends with increasing Fe2O3T, MnO, MgO, CaO, and TiO2, suggesting mafic minerals as important hosts of structurally bound halogens. Overall, Sierran plutonic rocks display low halogen contents (max. F, Cl = 727, 315 μg/g), consistent with biotite- and apatite-bearing granitoids reported in [1]. This work suggests that halogens do not preferentially enrich in shallow plutonic or volcanic portions of a continental arc system and that mafic mineral phases likely serve as primary reservoirs of these elements in intermediate-to-felsic igneous rocks. These hypotheses will be further investigated in future work through in-situ analysis of halogen concentrations in crystals. [1] Teiber, Marks, Wenzel, Siebel, Altherr & Markl (2014), Chemical Geology, vol. 374–375, pp. 92–109, doi: 10.1016/j.chemgeo.2014.03.006 

Spring waters from across the Costa Rica margin were analyzed for their Li and He isotope compositions to determine the utility of Li isotopes as a tracer of volatile sources in subduction zones. Li isotope ratios systematically decrease with increasing depth to the subducting slab: averaging +15.0‰ ± 9.2‰ in the outer forearc (<40 km to the slab), +9.3‰ ± 4.3‰ in the forearc (40–80 km to the slab), and +5.8‰ ± 2.8‰ in the arc (>80 km to the slab). In contrast, air-corrected 3He/4He values (reported relative to the ratio in air, RA) range from 0.4 to 7.5 RA and increase from predominantly crustal values near the trench to mantle values in the arc. Together, these data support progressive devolatilization of the subducting plate with slab-derived Li components sourced from shallowly expelled pore fluids in the outer forearc, sedimentary and/or altered oceanic crust contributing to the forearc, and limited slab input beneath the arc. 

Abstract. Retrograde metamorphic rocks provide key insights into the pressure–temperature (P–T) evolution of exhumed material, and resultant P–T constraints have direct implications for the mechanical and thermal conditions of subduction interfaces. However, constraining P–T conditions of retrograde metamorphic rocks has historically been challenging and has resulted in debate about the conditions experienced by these rocks. In this work, we combine elastic thermobarometry with oxygen isotope thermometry to quantify the P–T evolution of retrograde metamorphic rocks of the Cycladic Blueschist Unit (CBU), an exhumed subduction complex exposed on Syros, Greece. We employ quartz-in-garnet and quartz-in-epidote barometry to constrain pressures of garnet and epidote growth near peak subduction conditions and during exhumation, respectively. Oxygen isotope thermometry of quartz and calcite within boudin necks was used to estimate temperatures during exhumation and to refine pressure estimates. Three distinct pressure groups are related to different metamorphic events and fabrics: high-pressure garnet growth at ∼1.4–1.7 GPa between 500–550 ∘C, retrograde epidote growth at ∼1.3–1.5 GPa between 400–500 ∘C, and a second stage of retrograde epidote growth at ∼1.0 GPa and 400 ∘C. These results are consistent with different stages of deformation inferred from field and microstructural observations, recording prograde subduction to blueschist–eclogite facies and subsequent retrogression under blueschist–greenschist facies conditions. Our new results indicate that the CBU experienced cooling during decompression after reaching maximum high-pressure–low-temperature conditions. These P–T conditions and structural observations are consistent with exhumation and cooling within the subduction channel in proximity to the refrigerating subducting plate, prior to Miocene core-complex formation. This study also illustrates the potential of using elastic thermobarometry in combination with structural and microstructural constraints, to better understand the P–T-deformation conditions of retrograde mineral growth in high-pressure–low-temperature (HP/LT) metamorphic terranes. 

Abstract Exhumed high‐pressure/low‐temperature (HP/LT) metamorphic rocks provide insights into deep (∼20–70 km) subduction interface dynamics. On Syros Island (Cyclades, Greece), the Cycladic Blueschist Unit preserves blueschist‐to‐eclogite facies oceanic‐ and continental‐affinity rocks that record the structural and thermal evolution linked to Eocene subduction. Despite decades of research, the metamorphic and deformation history (P‐T‐D) and timing of subduction and exhumation are matters of ongoing discussion. We suggest that Syros comprises three coherent tectonic slices and that each slice underwent subduction, underplating, and syn‐subduction return flow along similar P‐T trajectories, but at progressively younger times. Subduction and exhumation are distinguished by lineations and ductile fold axis orientations, and are kinematically consistent with previous studies that document top‐to‐the‐S‐SW shear (prograde‐to‐peak subduction), top‐to‐the‐NE shear (blueschist facies exhumation), and then E‐W coaxial stretching (greenschist facies exhumation). Amphibole zonations record cooling during decompression, indicating return flow above a cold slab. Multi‐mineral Rb‐Sr isochrons and compiled metamorphic geochronology show that the three slices record distinct stages of peak subduction (53–52, ∼50, and 45 Ma) that young with structural depth. Retrograde blueschist and greenschist facies fabrics span ∼50–40 and ∼43–20 Ma, respectively, and also young with structural depth. Synthesized data sets support a revised tectonic framework for Syros, involving subduction of structurally distinct coherent slices and simultaneous return flow of previously accreted tectonic slices in the subduction channel shear zone. Distributed, ductile, dominantly coaxial return flow in an Eocene‐Oligocene subduction channel proceeded at rates of ∼1.5–5 mm/yr and accommodated ∼80% of the total exhumation of this HP/LT complex.