Abstract

Formation of soluble sulfate and halide salts on volcanic ash particles via syn-eruptive interactions between ash surfaces and magmatic gases is a ubiquitous phenomenon in explosive eruptions. Surficial salts may be rapidly mobilized into their depositional environment undermining the quality of drinking water, harming aquatic life, and damaging soil and vegetation. Assessment of the potential for salt formation on ash and related environmental impacts have been based almost exclusively on bulk mineralogical or chemical analyses of ash; similarly, quantification of surficial salts has been made via leachate analysis only. However, it is the ash surface state and salt crystal properties that exert the predominant control on its reactivity, thus in determining their immediate environmental impact. Here, using scanning electron microscope (SEM) images, we present a novel image analysis protocol for the quantitative characterization of surficial salts, together with chemical analyses of resulting leachates. As volcanic ash proxies, we used synthetic rhyolitic glass particles (with systematic variations in FeOT and CaO content) and a crushed obsidian. Using an ash-gas reactor, we artificially surface-loaded samples with CaSO4 and NaCl crystals, the most common crystal phases found on volcanic ash surfaces. Analogous variations were found using both methods: for CaSO4 crystals, higher temperature treatments or increasing FeOT content at the same temperature led to higher concentrations of salt leachate and higher salt volumes; unexpectedly, increasing the CaO content caused only a minor increase in salt formation. In addition to bulk salt formation, morphometric results provided insight into formation processes, nucleation and growth rates, and limiting factors for salt formation. Higher temperatures increased CaSO4 crystal size and surface coverage which we infer to result from higher element mobility in the glasses driving crystal growth. Increasing FeOT content of the glasses yielded increased salt surface coverage and leachate concentrations, but decreased crystal size (i.e., the salt number density increased). This latter effect likely relates to the role of iron as an electron-donor to charge balance salt-forming cation migration to the ash surface, indicating the importance of iron in determining surface reaction site density and, consequently, environmental reactivity. The controlling roles of ash composition and temperature on salt formation observed here can improve estimations for surface salt formation, volatile scavenging, and environmental impact for eruptions producing glass-rich ash. Our characterization protocol can therefore become a useful tool for the investigation of solid–gas reactions for terrestrial and planetary processes, and it also appears to be a powerful complement to research into atmospheric processes mediated by ash surfaces, such as ash aggregation and nucleation of water or ice on ash.

Highlights

  • Chemical and physical characterization of volcanic ash has long provided volcanologists with data, which upon careful interpretation, can give insights into the conditions of a given eruption, such as magma composition, duration of the episode, and gas chemistry (Le Maitre et al 2002; Armienta et al 1998; Rose 1977)

  • This becomes evident for the treated HPG8 samples (Fig. 2a–r), where salts formed on Fe-free samples (HPG8 0 wt.% F­ eOT) doped with 1 and 2 wt.% CaO (Fig. 2a–c and j–l, respectively) seem to be smaller (< 0.5 μm) and display more variable aspect ratio, when compared to those formed on Fe-bearing samples

  • Surficial salts formed on Krafla rhyolite particles after S­ O2-exposure (Fig. 2s–u), appear to be generally larger (≤ 1 μm), and have a higher surface coverage than those observed for the HPG8 set of samples

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Summary

Introduction

Chemical and physical characterization of volcanic ash (pyroclasts of ≤ 2 mm) has long provided volcanologists with data, which upon careful interpretation, can give insights into the conditions of a given eruption, such as magma composition, duration of the episode, and gas chemistry (Le Maitre et al 2002; Armienta et al 1998; Rose 1977). The chemical analysis of ash leachates (fluid obtained by the dissolution of soluble material from ash surfaces) has been useful to estimate the composition of volatiles in the gas phase of eruptive plumes (Rose et al 1973). This is because, during explosive eruptions, silicate ash and a hot mixture of gases (mainly H­ 2O, ­CO2, ­SO2, HCl, and HF) are turbulently ejected above the magma-fragmentation level, where solid–gas interactions result in formation of sulfateand halide-bearing salts on ash surfaces (Taylor and Stoiber 1973), the salt-composition can be expected to represent the gas chemistry of an eruptive plume.

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