Chalcophile elements track the fate of sulfur at Kīlauea Volcano, Hawai'i

© 2020 Elsevier Ltd Chalcophile element concentrations in melt inclusions and matrix glasses may be used to investigate low pressure degassing processes, as well as sulfide saturation during crustal fractionation, and mantle melting. Erupted products from Kīlauea Volcano, Hawaiʻi, record three stages of sulfide saturation (in the mantle, crust, and within lava lakes), separated by episodes of sulfide resorption (i.e., sulfide undersaturation) during ascent through the thick Hawaiian lithosphere, and during syn-eruptive degassing. The presence of residual sulfides in the mantle source throughout the melting interval accounts for the high S concentrations of Kīlauean primary melts (1387–1600 ppm). Residual sulfides retain chalcophile elements during melting, decoupling the variability of these elements in high MgO melts from that of lithophile elements. Decompression associated with magma ascent through the thick Hawaiian lithosphere drives an increase in the sulfide concentration at sulfide saturation (SCSS2−), resulting in shallow storage reservoirs (∼1–5 km depth) being supplied with sulfide-undersaturated melts. A drop in temperature, coupled with major element changes during the fractionation of olivine, causes the SCSS2− to decrease. Combined with an increase in melt S contents during fractionation, this initiates a second stage of sulfide saturation at relatively high MgO contents (∼12 wt%). Syn-eruptive degassing of S drives the resorption of sulfides in contact with the carrier liquid. The covariance structure of Cu, MgO and Ni contents in melt inclusions and matrix glasses indicates that the dissolution of sulfides effectively liberates sulfide-hosted Cu and Ni back into the melt, rather than the vapour phase. The contrasting behaviour of Cu, Ni, Se and S during sulfide resorption indicates that the chalcophile element signature of the Kīlauean plume is largely controlled by silicate melt-vapour partitioning, rather than sulfide-vapour partitioning. The participation of dense sulfide liquids in shallow degassing processes may result from their direct attachment to buoyant vapour bubbles, or olivine crystals which were remobilized prior to eruption. Sulfide resorption obscures the textural and chemical record of sulfide saturation in matrix glasses, but not in melt inclusions, which are isolated from this late-stage release of chalcophile elements. The partitioning of S between the dissolving sulfide, melt and the vapour phase accounts for approximately 20% of the total S release into the atmosphere

New constraints from Central Chile on the origins of enriched continental compositions in thick-crusted arc magmas

Magmas from continental arcs built on thick crust have elevated incompatible element abundances and “enriched” radiogenic isotope ratios compared to magmas erupted in island and continental arcs overlying thinner crust. The relative influence of the slab, mantle, and upper plate on this variability is heavily debated. The Andean Southern Volcanic Zone (SVZ; 33-46° S) is an ideal setting to investigate the production of enriched continental arc compositions, because both crustal thickness and magma chemistry vary coherently along strike. However, the scarcity of primitive magmas in the thick-crusted northern SVZ has hindered previous regional studies. To better address the origin of enriched continental compositions, we investigate the geochemistry (major and trace element abundances, 87Sr/86Sr and 143Nd/144Nd ratios) of new mafic samples from Don Casimiro and Maipo volcanoes in Diamante-Maipo Caldera Complex of the northern SVZ. While evolved Diamante-Maipo samples show evidence for crustal assimilation, the trace element and isotopic enrichment of the most mafic samples cannot result from crustal processing, as no known regional or global basement lithologies are enriched in all of the necessary incompatible trace elements. Subduction erosion models similarly fail to account for the enriched isotopic and trace element signature of these samples. Instead, we suggest that the enrichment of northern SVZ magmas is derived from an enriched ambient mantle component (similar to EM1-type ocean island basalts), superimposed on a northward decline in melt extent. A substantial, but nearly uniform contribution of melts from subducting sediment and altered oceanic crust are required at all latitudes. The EM1-like enrichment may arise from recycling of metasomatized subcontinental lithospheric mantle (M-SCLM), as the isotopic trajectory of primitive rear-arc monogenetic cones trend towards the compositions of SCLM melts sampled across South America. Isotopic data from spatially distributed rear-arc centres demonstrate that the arc-parallel variations in the degree of EM1-type enrichment observed in arc-front samples are also present up to 600 km behind the trench in the rear-arc. Rear-arc trace element systematics require significant but variable quantities of slab melts to be transported to the mantle wedge at these large trench distances. Overall, we show that a unified model incorporating variable mantle enrichment, slab additions, and melt extents can account for along and acrossarc trends within the SVZ. The recognition that mantle enrichment plays a key role in the production of enriched continental compositions in the SVZ has important implications for our understanding of the chemical evolution of the Earth. If ambient mantle enrichment is not taken into account, petrogenetic models of evolved lavas may overestimate the role of crustal assimilation, which, in turn, may lead models of continental crust growth to overestimate the amount of continental material that has been recycled back into the mantle

To sink, swim, twin, or nucleate: A critical appraisal of crystal aggregation processes

Abstract Crystal aggregates in igneous rocks have been variously ascribed to growth processes (e.g., twinning, heterogeneous nucleation, epitaxial growth, dendritic growth), or dynamical processes (e.g., synneusis, accumulation during settling). We tested these hypotheses by quantifying the relative orientation of adjacent crystals using electron backscatter diffraction. Both olivine aggregates from Kīlauea volcano (Hawaiʻi, USA) and chromite aggregates from the Bushveld Complex (South Africa) show diverse attachment geometries inconsistent with growth processes. Near-random attachments in chromite aggregates are consistent with accumulation by settling of individual crystals. Attachment geometries and prominent geochemical differences across grain boundaries in olivine aggregates are indicative of synneusis.</jats:p

VESIcal: 2. A Critical Approach to Volatile Solubility Modeling Using an Open-Source Python3 Engine

Abstract: Accurate models of H2O and CO2 solubility in silicate melts are vital for understanding volcanic plumbing systems. These models are used to estimate the depths of magma storage regions from melt inclusion volatile contents, investigate the role of volatile exsolution as a driver of volcanic eruptions, and track the degassing path followed by a magma ascending to the surface. However, despite the large increase in the number of experimental constraints over the last two decades, many recent studies still utilize an earlier generation of models which were calibrated on experimental datasets with restricted compositional ranges. This may be because many of the available tools for more recent models require large numbers of input parameters to be hand‐typed (e.g., temperature, concentrations of H2O, CO2, and 8–14 oxides), making them difficult to implement on large datasets. Here, we use a new open‐source Python3 tool, VESIcal, to critically evaluate the behaviors and sensitivities of different solubility models for a range of melt compositions. Using literature datasets of andesitic‐dacitic experimental products and melt inclusions as case studies, we illustrate the importance of evaluating the calibration dataset of each model. Finally, we highlight the limitations of particular data presentation methods, such as isobar diagrams, and provide suggestions for alternatives, and best practices regarding the presentation and archiving of data. This review will aid the selection of the most applicable solubility model for different melt compositions, and identifies areas where additional experimental constraints on volatile solubility are required

VESIcal Part I: An Open-Source Thermodynamic Model Engine for Mixed Volatile (H<inf>2</inf>O-CO<inf>2</inf>) Solubility in Silicate Melts

Abstract: Thermodynamics has been fundamental to the interpretation of geologic data and modeling of geologic systems for decades. However, more recent advancements in computational capabilities and a marked increase in researchers' accessibility to computing tools has outpaced the functionality and extensibility of currently available modeling tools. Here, we present VESIcal (Volatile Equilibria and Saturation Identification calculator): the first comprehensive modeling tool for H 2 O, C O 2 , and mixed ( H 2 O‐ C O 2 ) solubility in silicate melts that: (a) allows users access to seven of the most popular models, plus easy inter‐comparison between models; (b) provides universal functionality for all models (e.g., functions for calculating saturation pressures, degassing paths, etc.); (c) can process large datasets (1,000s of samples) automatically; (d) can output computed data into an Excel spreadsheet or CSV file for simple post‐modeling analysis; (e) integrates plotting capabilities directly within the tool; and (f) provides all of these within the framework of a python library, making the tool extensible by the user and allowing any of the model functions to be incorporated into any other code capable of calling python. The tool is presented within this manuscript, which may be read as a static PDF but is better experienced via the Jupyter Notebook version of this manuscript. Here, we present worked examples accessible to python users with a range of skill levels. The basic functions of VESIcal can also be accessed via a web app (https://vesical.anvil.app). The VESIcal python library is open‐source and available for download at https://github.com/kaylai/VESIcal, or it can be installed using pip. It is recommended to read and interact with this manuscript as an executable Jupyter Notebook, available at https://mybinder.org/v2/gh/kaylai/vesical-binder/HEAD?filepath=Manuscript.ipynb

Explosive Activity on Kīlauea's Lower East Rift Zone Fueled by a Volatile-Rich, Dacitic Melt

Abstract: Magmas with matrix glass compositions ranging from basalt to dacite erupted from a series of 24 fissures in the first 2 weeks of the 2018 Lower East Rift Zone (LERZ) eruption of Kīlauea Volcano. Eruption styles ranged from low spattering and fountaining to strombolian activity. Major element trajectories in matrix glasses and melt inclusions hosted by olivine, pyroxene and plagioclase are consistent with variable amounts of fractional crystallization, with incompatible elements (e.g., Cl, F, and H2O) becoming enriched by 4–5 times as melt MgO contents evolve from 6 to 0.5 wt%. The high viscosity and high H2O contents (∼2 wt%) of the dacitic melts erupting at Fissure 17 account for the explosive Strombolian behavior exhibited by this fissure, in contrast to the low fountaining and spattering observed at fissures erupting basaltic to basaltic‐andesite melts. Saturation pressures calculated from melt inclusion CO2‐H2O contents indicate that the magma reservoir(s) supplying these fissures was located at ∼2–3 km depth, which is in agreement with the depth of a dacitic magma body intercepted during drilling in 2005 (∼2.5 km) and a seismically imaged low Vp/Vs anomaly (∼2 km depth). Nb/Y ratios in erupted products are similar to lavas erupted between 1955 and 1960, indicating that melts were stored and underwent variable amounts of crystallization in the LERZ for >60 years before being remobilized by a dike intrusion in 2018. We demonstrate that extensive fractional crystallization generates viscous and volatile‐rich magma with potential for hazardous explosive eruptions, which may be lurking undetected at many ocean island volcanoes

Spatial and Temporal Variations in SO₂ and PM₂.₅ Levels Around Kīlauea Volcano, Hawai'i During 2007–2018

Among the hazards posed by volcanoes are the emissions of gases and particles that can affect air quality and damage agriculture and infrastructure. A recent intense episode of volcanic degassing associated with severe impacts on air quality accompanied the 2018 lower East Rift Zone (LERZ) eruption of Kīlauea volcano, Hawai'i. This resulted in a major increase in gas emission rates with respect to usual emission values for this volcano, along with a shift in the source of the dominant plume to a populated area on the lower flank of the volcano. This led to reduced air quality in downwind communities. We analyse open-access data from the permanent air quality monitoring networks operated by the Hawai'i Department of Health (HDOH) and National Park Service (NPS), and report on measurements of atmospheric sulfur dioxide (SO2) between 2007 and 2018 and PM2.5 (aerosol particulate matter with diameter <2.5 μm) between 2010 and 2018. Additional air quality data were collected through a community-operated network of low-cost PM2.5 sensors during the 2018 LERZ eruption. From 2007 to 2018 the two most significant escalations in Kīlauea's volcanic emissions were: the summit eruption that began in 2008 (Kīlauea emissions averaged 5–6 kt/day SO2 from 2008 until summit activity decreased in May 2018) and the LERZ eruption in 2018 when SO2 emission rates reached a monthly average of 200 kt/day during June. In this paper we focus on characterizing the airborne pollutants arising from the 2018 LERZ eruption and the spatial distribution and severity of volcanic air pollution events across the Island of Hawai'i. The LERZ eruption caused the most frequent and severe exceedances of the Environmental Protection Agency (EPA) PM2.5 air quality threshold (35 μg/m3 as a daily average) in Hawai'i in the period 2010–2018. In Kona, for example, the maximum 24-h-mean mass concentration of PM2.5 was recorded as 59 μg/m3 on the twenty-ninth of May 2018, which was one of eight recorded exceedances of the EPA air quality threshold during the 2018 LERZ eruption, where there had been no exceedances in the previous 8 years as measured by the HDOH and NPS networks. SO2 air pollution during the LERZ eruption was most severe in communities in the south and west of the island, as measured by selected HDOH and NPS stations in this study, with a maximum 24-h-mean mass concentration of 728 μg/m3 recorded in Ocean View (100 km west of the LERZ emission source) in May 2018. Data from the low-cost sensor network correlated well with data from the HDOH PM2.5 instruments, confirming that these low-cost sensors provide a robust means to augment reference-grade instrument networks

Rapid metal pollutant deposition from the volcanic plume of Kīlauea, Hawai’i

AbstractLong-lived basaltic volcanic eruptions are a globally important source of environmentally reactive, volatile metal pollutant elements such as selenium, cadmium and lead. The 2018 eruption of Kīlauea, Hawai’i produced exceptionally high discharge of metal pollutants, and was an unprecedented opportunity to track them from vent to deposition. Here we show, through geochemical sampling of the plume that volatile metal pollutants were depleted in the plume up to 100 times faster than refractory species, such as magnesium and iron. We propose that this rapid wet deposition of complexes containing reactive and potentially toxic volatile metal pollutants may disproportionately impact localised areas close to the vent. We infer that the relationship between volatility and solubility is an important control on the atmospheric behaviour of elements. We suggest that assessment of hazards from volcanic emissions should account for heterogeneous plume depletion of metal pollutants.</jats:p