Elena Maters

Atmospheric Processing of Volcanic Glass: Effects on Iron Solubility and Redox Speciation

Volcanic ash from explosive eruptions can provide iron (Fe) to oceanic regions where this micronutrient limits primary production. Controls on the soluble Fe fraction in ash remain poorly understood but Fe solubility is likely influenced during atmospheric transport by condensation-evaporation cycles which induce large pH fluctuations. Using glass powder as surrogate for ash, we experimentally simulate its atmospheric processing via cycles of pH 2 and 5 exposure. Glass fractional Fe solubility (maximum 0.4%) is governed by the pH 2 exposure duration rather than by the pH fluctuations, however; pH 5 exposure induces precipitation of Fe-bearing nanoparticles which (re)dissolve at pH 2. Glass leaching/dissolution release Fe(II) and Fe(III) which are differentially affected by changes in pH; the average dissolved Fe(II)/Fetot ratio is ∼0.09 at pH 2 versus ∼0.18 at pH 5. Iron release at pH 2 from glass with a relatively high bulk Fe(II)/Fetot ratio (0.5), limited aqueous Fe(II) oxidation at pH 5, and possibly glass-mediated aqueous Fe(III) reduction may render atmospherically processed ash a significant source of Fe(II) for phytoplankton. By providing new insight into the form(s) of Fe associated with ash as wet aerosol versus cloud droplet, we improve knowledge of atmospheric controls on volcanogenic Fe delivery to the ocean.

Volcanic influence on the Carbon, Sulfur, and Halogen Biogeochemical cycles

Volcanism manifests itself at the Earths surface in various guises ranging from violent explosive injection of ash and gases into the atmosphere to sustained outpouring of lava onto vast land areas, or quiescent release of gas plumes that gently sweep the landscape downwind. By adding various amounts of carbon, sulfur and halogen gases, and silicate materials into the atmosphere and terrestrial and ocean environments, these volcanic phenomena have the potential to affect biogeochemical cycles over different spatial and temporal scales. While recognition of such interaction is not new, notably in relation to large ancient volcanic eruptions, quantitative data that can shed light on the interlinked mechanisms underpinning biogeochemical disturbances have only recently begun. This chapter provides an updated overview of the volcanic contributions to and effects upon the carbon, sulfur, and halogen biogeochemical cycles.

Reactive Uptake of Sulfur Dioxide and Ozone on Volcanic Glass and Ash at Ambient Temperature

Abstract The atmospheric impacts of volcanic ash from explosive eruptions are rarely considered alongside those of volcanogenic gases/aerosols. While airborne particles provide solid surfaces for chemical reactions with trace gases in the atmosphere, the reactivity of airborne ash has seldom been investigated. Here we determine the total uptake capacity (NiM) and initial uptake coefficient (γM) for sulfur dioxide (SO2) and ozone (O3) on a compositional array of volcanic ash and glass powders at ~25 °C in a Knudsen flow reactor. The measured ranges of NiSO2 and γSO2 (1011-1013 molecules cm-2 and 10-3-10-2) and NiO3 and γO3 (1012-1013 molecules cm-2 and 10-3-10-2) are comparable to values reported for mineral dust. Differences in ash and glass reactivity towards SO2 and O3 may relate to varying abundances of, respectively, basic and reducing sites on these materials. The typically lower SO2 and O3 uptake on ash compared to glass likely results from prior exposure of ash surfaces to acidic and oxidizing conditions within the volcanic eruption plume/cloud. While sequential uptake experiments overall suggest that these gases do not compete for reactive surface sites, SO2 uptake forming adsorbed S(IV) species may enhance the capacity for subsequent O3 uptake via redox reaction forming adsorbed S(VI) species. Our findings imply that ash emissions may represent a hitherto neglected sink for atmospheric SO2 and O3.