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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Efficient release of bromine by super-eruptions
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.
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- Award ID(s):
- 1664308
- PAR ID:
- 10312559
- Date Published:
- Journal Name:
- Geology
- Volume:
- 49
- Issue:
- 12
- ISSN:
- 0091-7613
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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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 Volcanic super-eruptions have been theorized to cause severe global cooling, with the 74 kya Toba eruption purported to have driven humanity to near-extinction. However, this eruption left little physical evidence of its severity and models diverge greatly on the magnitude of post-eruption cooling. A key factor controlling the super-eruption climate response is the size of volcanic sulfate aerosol, a quantity that left no physical record and is poorly constrained by models. Here we show that this knowledge gap severely limits confidence in model-based estimates of super-volcanic cooling, and accounts for much of the disagreement among prior studies. By simulating super-eruptions over a range of aerosol sizes, we obtain global mean responses varying from extreme cooling all the way to the previously unexplored scenario of widespread warming. We also use an interactive aerosol model to evaluate the scaling between injected sulfur mass and aerosol size. Combining our model results with the available paleoclimate constraints applicable to large eruptions, we estimate that global volcanic cooling is unlikely to exceed 1.5°C no matter how massive the stratospheric injection. Super-eruptions, we conclude, may be incapable of altering global temperatures substantially more than the largest Common Era eruptions. This lack of exceptional cooling could explain why no single super-eruption event has resulted in firm evidence of widespread catastrophe for humans or ecosystems.
Significance Statement Whether volcanic super-eruptions pose a threat to humanity remains a subject of debate, with climate models disagreeing on the magnitude of global post-eruption cooling. We demonstrate that this disagreement primarily stems from a lack of constraint on the size of volcanic sulfate aerosol particles. By evaluating the range of aerosol size scenarios, we demonstrate that eruptions may be incapable of causing more than 1.5°C cooling no matter how much sulfur they inject into the stratosphere. This could explain why archaeological records provide no evidence of increased human mortality following the Toba super-eruption. Further, we raise the unexplored possibility that the largest super-eruptions could cause global-scale warming.
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The role of hydroxyl radicals (OH) as a daytime oxidant is well established on a global scale. In specific source regions, such as the marine boundary layer and polluted coastal cities, other daytime oxidants, such as chlorine atoms (Cl) and even bromine atoms (Br), may compete with OH for the oxidation of volatile organic compounds (VOCs) and/or enhance the overall oxidation capacity of the atmosphere. However, the number of studies investigating halogen-initiated secondary organic aerosol (SOA) formation is extremely limited, resulting in large uncertainties in these oxidative aging processes. Here, we characterized the chemical composition and yield of laboratory SOA generated in an oxidation flow reactor (OFR) from the OH and Cl oxidation of n -dodecane ( n -C 12 ) and toluene, and the OH, Cl, and Br oxidation of isoprene and α-pinene. In the OFR, precursors were oxidized using integrated OH, Cl, and Br exposures ranging from 3.1 × 10 10 to 2.3 × 10 12 , 6.1 × 10 9 to 1.3× 10 12 and 3.2 × 10 10 to 9.7 × 10 12 molecules cm −3 s −1 , respectively. Like OH, Cl facilitated multistep SOA oxidative aging over the range of OFR conditions that were studied. In contrast, the extent of Br-initiated SOA oxidative aging was limited. SOA elemental ratios and mass yields obtained in the OFR studies were comparable to those obtained from OH and Cl oxidation of the same precursors in environmental chamber studies. Overall, our results suggest that alkane, aromatic, and terpenoid SOA precursors are characterized by distinct OH- and halogen-initiated SOA yields, and that while Cl may enhance the SOA formation potential in regions influenced by biogenic and anthropogenic emissions, Br may have the opposite effect.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
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1130/G49114.1
