- Award ID(s):
- 2211243
- PAR ID:
- 10514006
- Publisher / Repository:
- Geological Society of America
- Date Published:
- Journal Name:
- Geological Society of America Abstracts with Programs
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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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 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 Halogens are primarily located within surface reservoirs of the Earth; as such they have proven to be effective tracers for the identification of subducted volatiles within the mantle. Subducting lithologies exhibit a wide variety of halogen compositions, yet the mantle maintains a fairly uniform signature, suggesting halogens may be homogenized during subduction to the mantle or during eruption. Here we present halogen (Cl, Br, and I), K, noble gas, and major and trace element data on olivines from three seamounts along the Hawaiian‐Emperor seamount chain to determine if the deep mantle source has retained evidence of halogen heterogeneities introduced through subduction. High Ni contents indicate that the Hawaiian‐Emperor mantle source contains a recycled oceanic crust component in the form of pyroxenite, which increases from the 46% in the oldest (Detroit) to 70% in the younger seamount (Koko). Detroit seamount retains mid‐ocean ridge basalts (MORB)‐like Br/Cl and I/Cl, while the Br/Cl and I/Cl of Suiko and Koko seamounts are higher than MORB and similar to altered oceanic crust and dehydrated serpentinite. Helium isotopes show a similar evolution, from MORB‐like values at Detroit seamount toward higher values at Suiko and Koko seamounts. The correlation between pyroxenite contributions, Br/Cl, I/Cl, and3He/4He indicates that subducted material has been incorporated into the primordial undegassed Hawaiian mantle plume source. The identification of recycled oceanic crustal signatures in both the trace elements and halogens indicates that subduction and dehydration of altered oceanic crust may exert control on the cycling of volatile elements to the deep mantle.
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Abstract We present microbeam major- and trace-element data from 14 monzodiorites collected from the Malaspina Pluton (Fiordland, New Zealand) with the goal of evaluating processes involved in the production of andesites in lower arc crust. We focus on relict igneous assemblages consisting of plagioclase and amphibole with lesser amounts of clinopyroxene, orthopyroxene, biotite and quartz. These relict igneous assemblages are heterogeneously preserved in the lower crust within sheeted intrusions that display hypersolidus fabrics defined by alignment of unstrained plagioclase and amphibole. Trace-element data from relict igneous amphiboles in these rocks reveal two distinct groups: one relatively enriched in high field strength element concentrations and one relatively depleted. The enriched amphibole group has Zr values in the range of ∼25–110 ppm, Nb values of ∼5–32 ppm, and Th values up to 2·4 ppm. The depleted group, in contrast, shows Zr values <35 ppm and Nb values <0·25 ppm, and Th is generally below the level of detection. Amphibole crystallization temperatures calculated from major elements range from ∼960 to 830 °C for all samples in the pluton; however, we do not observe significant differences in the range of crystallization temperatures between enriched (∼960–840 °C) and depleted groups (∼940–830 °C). Bulk-rock Sr and Nd isotopes are also remarkably homogeneous and show no apparent difference between enriched (εNdi = 0·1 to –0·1; 87Sr/86Sri = 0·70420–0·70413) and depleted groups (εNdi = 0·3 to –0·4; 87Sr/86Sri = 0·70424–0·70411). Calculated amphibole-equilibrium melt compositions using chemometric equations indicate that melts were highly fractionated (molar Mg# <50), andesitic to dacitic in composition, and were much more evolved than bulk lower continental crust or primitive basalts and andesites predicted to have formed from hydrous melting of mantle-wedge peridotite beneath an arc. We suggest that melts originated from a common, isotopically homogeneous source beneath the Malaspina Pluton, and differences between enriched and depleted trace-element groups reflect varying contributions from subducted sediment-derived melt and sediment-derived fluid, respectively. Our data demonstrate that andesites and dacites were the dominant melts that intruded the lower crust, and their compositions mirror middle and upper bulk-continental crust estimates. Continental crust-like geochemical signatures were acquired in the source region from interaction between hydrous mantle-wedge melts and recycled subducted sediment rather than assimilation and/or remelting of pre-existing lower continental crust.more » « less