This content will become publicly available on June 30, 2025
- PAR ID:
- 10539185
- Publisher / Repository:
- 2024 V.M. Goldschmidt Conference Abstracts
- Date Published:
- Format(s):
- Medium: X
- Location:
- Chicago, Illinois, USA
- Sponsoring Org:
- National Science Foundation
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The halogens (F, Cl, Br, I) are cycled into the crust via subduction. The presence of F and Cl in arc settings impacts melt viscosity, igneous phase relations, and thermodynamic properties of magma in the pluton-to-volcano system, whereas the systematics of Br and I in melt systems are poorly understood. Mass balance constraints show that more halogens are subducted with the slab than are released during volcanism and passive degassing, suggesting that a halogen sink may exist in the lithosphere. Despite this, the halogen content of the upper continental crust of arc systems and distribution of halogens between plutonic and volcanic arc rocks are poorly quantified. This study presents whole rock halogen (F, Cl, Br, I) concentrations for 22 unaltered, geospatially- and temporally-related Cretaceous granitoid, hypabyssal plutonic, and volcanic rocks from the Sierra Nevada, California. This sampling approach allows direct comparison of plutonic and volcanic counterparts to make inferences about the pluton-volcano relationship. Because F behaves more incompatibly than Cl, Br, and I, late-stage fluid exsolution from melts may concentrate F in plutonic rocks and Cl, Br, and I in volcanic rocks. These whole rock halogen data provide a first-order approximation of the proportion of subducted halogens that are stored in the upper continental crust, and where along the magmatic plumbing path they are stored with important implications for their role in primary igneous processes such as pluton crystallization and volcanism. Ultimately, the results from this work will serve as the preliminary data for a larger study, provide insight into the magnitude of the roles the halogens play during primary igneous processes, and add to the limited halogen data on arc rocks.more » « less
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Ongoing investigations of halogen element (F, Cl, Br, I) concentrations in rocks and minerals in the Cretaceous Sierra Nevada Batholith, CA, aim to elucidate the spatio-temporal distribution and budget of these important elements in a “typical” continental convergent margin arc. Using a 3.0 kW Axios (Panalytical) wavelength-dispersive X-ray fluorescence spectrometer (XRF) equipped with a Ge 111 crystal to eliminate second order interferences on Cl-Kα lines, the Pomona College XRF lab has undertaken a campaign-style study of Cl in pressed powder samples of metamorphic and metavolcanic rocks in the Sierra. This work complements pyrohydrolysis + ion chromatography (IC) and ICP-MS analyses the research team is undertaking at the University of Texas – Austin. Both labs quadruply wash powders to eliminate Cl contributions from decrepitated fluid inclusions or grain boundary deposits. Intercomparison between the two labs show correlation (r2 = 0.98) between analyses of the same unknown samples, but decreased accuracy of XRF (>30% relative) below 30 µg/g. Despite lower precision, XRF characterization is a relatively rapid and less labor intensive means to identify key Cl variations among rock types and to select samples for full analysis of all four halogen elements by pyrohydrolysis + IC (Cl,F) and ICP-MS (Br,I). Results thus far indicate that Mg- to Al-rich pelites ranging in metamorphic grade from phyllite to migmatite vary widely in Cl: 50–500 µg/g; cordierite-biotite hornfels are typically elevated in Cl (200–400 µg/g) and other lithologies such as skarns and amphibolite are highly varied (50–600 µg/g Cl); a localized study of a high temperature (650–750°C) migmatites surrounding a gabbro-diorite complex shows low and relatively uniform Cl (100 ± 50 µg/g) in the migmatites. This fundings suggests that Cl may have been mobilized into melts during biotite dehydration melting in the migmatites. Metavolcanic rocks vary from 20 to over 2000 µg/g Cl, suggesting post-eruptive exchange with exogenous fluids during hydrothermal alteration and metamorphism. Metavolcanic packages in different pendants, screens and septa show some localized patterns in Cl concentration that are being explored further.more » « less
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Subduction of oceanic plates releases large amounts of chlorine and fluorine into the mantle. These halogens are transported into the crust through hydrous melting, where they may be incorporated into minerals such as biotite, apatite, and amphibole. Halogen concentrations are measured in volcanic or plutonic material, while the concentration of Cl and F released from the subducting slab must be calculated based upon the amount of crystallized material and the partition coefficients of each mineral. As amphibole is the most common halogen bearing igneous mineral, it is commonly studied as a bearer of Cl and F. However, the partition coefficient of F between amphibole and a hydrous melt has not been agreed upon by previous studies. Here we show that F is moderately to highly compatible in amphibole, in agreement with other experiments performed at crustal conditions. As amphibole may be able to incorporate a large amount of F, cryptic amphibole crystallization may raise the Cl/F ratio of residual magma, which will then be transported to the surface bearing this geochemical signature, even with little crystallized amphibole present in erupted material. This provides further evidence for the occurrence of cryptic amphibole crystallization, previously predicted based on REE studies and phase equilibria. A better understanding of the halogen reservoirs present in the crust will allow for more accurate estimates of the amount of Cl and F released by subducting slabs.more » « less
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Abstract The conditions under which halogens partition in favor of an exsolved fluid relative to the coexisting melt are key for understanding many magmatic processes, including volcanic degassing, evolution of crustal melt bodies, and ore formation. We report new F, Cl, and Br fluid/melt partition coefficients for intermediate to silicic melts, for which F and Br data are particularly lacking; and for varying CO2-H2O contents to assess the effects of changing fluid composition (XH2O) on Br fluid/melt partitioning for the first time. The experiments were conducted at pressures 50–120 MPa, temperatures 800–1100 °C, and volatile compositions [molar XH2O = H2O/(H2O +CO2)] of 0.55 to 1, with redox conditions around the Nickel-Nickel Oxygen buffer (fO2 ≈ NNO). Experiments were not doped with Cl, Br, or F and were conducted on natural crystal-bearing volcanic products at conditions close to their respective pre-eruptive state. The experiments therefore provide realistic constraints on halogen partitioning at naturally occurring, brine-undersaturated conditions. Measurements of Br, Cl, and F were made by Secondary Ion Mass Spectrometry (SIMS) on 13 experimental glass products spanning andesite to rhyolitic compositions, together with their natural starting materials from Kelud volcano, Indonesia, and Quizapu volcano, Chile. Fluid compositions were constrained by mass balance. Average bulk halogen fluid/melt partition coefficients and standard deviations are: DClfluid/melt = 3.4 (±3.7 1 s.d.), DFfluid/melt = 1.7 (±1.7), and DBrfluid/melt = 7.1 (±6.4) for the Kelud starting material (bulk basaltic andesite), and DClfluid/melt = 11.1 (±3.5), DFfluid/melt = 0.8 (±0.8), and DBrfluid/melt = 31.3 (±20.9) for Quizapu starting material (bulk dacite). The large range in average partition coefficients is a product of changing XH2O, pressure and temperature. In agreement with studies on synthetic melts, our data show an exponential increase of halogen Dfluid/melt with increasing ionic radius, with partitioning behavior controlled by melt composition according to the nature of the complexes forming in the melt (e.g., SiF4, NaCl, KBr). The fundamental chemistry of the different halogens (differing ionic size and electronegativities) controls the way in which partitioning responds to changes in melt composition and other variables. Experimental results confirm that more Cl partitions into the fluid at higher bulk Cl contents, higher melt Na, higher fluid XH2O ratios, and lower temperatures. Bromine shows similar behavior, though it seems to be more sensitive to temperature and less sensitive to Na content and XH2O. In contrast, F partitioning into the fluid increases as the melt silica content decreases (from 72 to 56 wt% SiO2), which we attribute to the lower abundance of Si available to form F complexes in the melt. These new data provide more insights into the conditions and processes that control halogen degassing from magmas and may help to inform the collection and interpretation of melt inclusions and volcano gas data.
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Abstract Bromine is a key halogen element in the quantification of volcanic volatiles, but analytical difficulties in measuring its very low abundances have prevented progress in understanding its behavior and its role in volcanic emissions. We present a new data set of bromine, chlorine, and fluorine concentrations in melt inclusions and matrix glasses for two rhyolitic super-eruptions from the Toledo and Valles calderas, New Mexico, USA. We show that before eruption, Br and Cl were efficiently partitioned from the gas-saturated magma into a separate fluid phase, and we calculate the mass of halogens in the fluid phase. We further demonstrate that syn-eruptive magma degassing was negligible during the super-eruptions, so that the main source of halogen emissions must have been the fluid phase. If the fluid phase were erupted, the large mass of Br and Cl could have severely impacted the atmospheric chemistry upon eruption.more » « less