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.
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Experimentally derived F, Cl, and Br fluid/melt partitioning of intermediate to silicic melts in shallow magmatic systems
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.
more » « less- PAR ID:
- 10515988
- Publisher / Repository:
- Mineralogical Society of America
- Date Published:
- Journal Name:
- American Mineralogist
- Volume:
- 107
- Issue:
- 10
- ISSN:
- 0003-004X/22/0010-1825$05.00
- Page Range / eLocation ID:
- 1825 to 1839
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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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
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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.2014.03.006more » « 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 Many lines of evidence from high P–T experiments, thermodynamic models, and natural observations suggest that slab-derived aqueous fluids, which flux mantle wedges contain variable amounts of dissolved carbon. However, constraints on the effects of H2O–CO2 fluids on mantle melting, particularly at mantle wedge P–T conditions, are limited. Here, we present new piston cylinder experiments on fertile and depleted peridotite compositions with 3.5 wt.% H2O and XCO2 [= molar CO2 / (CO2 + H2O)] of 0.04–0.17. Experiments were performed at 2–3 GPa and 1350°C to assess how temperature, peridotite fertility, and XCO2 of slab-derived fluid affects partial melting in mantle wedges. All experiments produce olivine + orthopyroxene +7 to 41 wt.% partial melt. Our new data, along with previous lower temperature data, show that as mantle wedge temperature increases, primary melts become richer in SiO2, FeO*, and MgO and poorer CaO, Al2O3, and alkalis when influenced by H2O–CO2 fluids. At constant P–T and bulk H2O content, the extent of melting in the mantle wedge is largely controlled by peridotite fertility and XCO2 of slab-fluid. High XCO2 depleted compositions generate ~7 wt.% melt, whereas, at identical P–T, low XCO2 fertile compositions generate ~30 to 40 wt.% melt. Additionally, peridotite fertility and XCO2 have significant effects on peridotite partial melt compositions. At a constant P–T–XCO2, fertile peridotites generate melts richer in CaO and Al2O3 and poorer in SiO2, MgO + FeO, and alkalis. Similar to previous experimental studies, at a constant P–T fertility condition, as XCO2 increases, SiO2 and CaO of melts systematically decrease and increase, respectively. Such distinctive effects of oxidized form of dissolved carbon on peridotite partial melt compositions are not observed if the carbon-bearing fluid is reduced, such as CH4-bearing. Considering the large effect of XCO2 on melt SiO2 and CaO concentrations and the relatively oxidized nature of arc magmas, we compare the SiO2/CaO of our experimental melts and melts from previous peridotite + H2O ± CO2 studies to the SiO2/CaO systematics of primitive arc basalts and ultra-calcic, silica-undersaturated arc melt inclusions. From this comparison, we demonstrate that across most P–T–fertility conditions predicted for mantle wedges, partial melts from bulk compositions with XCO2 ≥ 0.11 have lower SiO2/CaO than all primitive arc melts found globally, even when correcting for olivine fractionation, whereas partial melts from bulk compositions with XCO2 = 0.04 overlap the lower end of the SiO2/CaO field defined by natural data. These results suggest that the upper XCO2 limit of slab-fluids influencing primary arc magma formation is 0.04 < XCO2 < 0.11, and this upper limit is likely to apply globally. Lastly, we show that the anomalous SiO2/CaO and CaO/Al2O3 signatures observed in ultra-calcic arc melt inclusions can be reproduced by partial melting of either CO2-bearing hydrous fertile and depleted peridotites with 0 < XCO2 < 0.11 at 2–3 GPa, or from nominally CO2-free hydrous fertile peridotites at P > 3 GPa.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.2138/am-2022-8109
