Iron dissolution from volcanic ash in low-pH atmospheric water: a key control on volcanic iron input to the surface ocean?

A low concentration of dissolved iron (Fe) limits phytoplankton growth in approximately 30% of the ocean. The input of soluble Fe to these High-Nutrient Low-Chlorophyll (HNLC) regions has the potential to boost primary production and thereby enhance the drawdown of atmospheric carbon dioxide (CO₂). Over geological timescales, volcanic activity may alter the flux of Fe to the surface ocean and so contribute to modulating atmospheric CO₂ concentrations, ultimately impacting the global climate. Ocean Fe fertilisation has also recently been found to contribute to century-scale carbon sequestration via the export of biomass to the seafloor. Atmospherically deposited volcanic ash is now increasingly seen as an intermittent source of Fe to the surface ocean. Understanding the process of Fe release from ash in solution is key for assessing the potential for ash, particularly that produced by large but rare explosive eruptions or during sustained periods of intense volcanism, to fertilise the marine environment. Previous studies have measured the release of Fe from ash in near-neutral pH solution, but the influence of interaction between ash and acidic cloud- or rainwater during transport on Fe release is poorly understood. In this study, seven volcanic ash samples ranging from tephrite to rhyolite (49-74 wt.% SiO₂) were leached in pH 1 H₂SO₄ in batch reactors for 336 h, at a 1:500 ash-to-solution ratio, to investigate Fe release under acidic conditions. Major element concentrations were measured by inductively coupled plasma- atomic emission spectroscopy (ICP-AES) across a time series of ash leachates. Changes in ash surface composition induced by contact with acid solution were assessed by X-ray photoelectron spectroscopy (XPS). The Fe²⁺/Fe³⁺ ratio in ash leachates was also determined for the first time, using the Ferrozine method. The ash samples released 42 to 411 μmol m^-2 of Fe over 336 h of leaching. High initial Fe release rates (>1 μmol m^-2 h^-1) sustained for up to 6 h suggest that early Fe release is not due solely to the dissolution of surface salts, as has been suggested in previous ash leach studies. The initial preferential release of Al, Fe, Mg, Ca, Na and K relative to Si may indicate silicate leaching by proton exchange.The approach of leachate ratios to bulk ratios over time suggests progression towards congruent dissolution of the silicate network. Notably, the two samples which exhibited the highest Fe release were unique in displaying a preferential release of Fe²⁺ relative to Fe³⁺ (Fe²⁺/Fe³⁺_leachate = 4.3 and 2.1), suggesting that Fe speciation in the ash may act as a key control on ash Fe solubility. Remarkably, the ash from the second explosive phase of the 2010 Eyjafjallajökull eruption, Iceland, which exhibited a strong enrichment in soluble fluoride (F) inherited from gas-ash interaction within the eruption plume, displayed a total Fe release 5 to 10 times greater than that of the other ash samples. Calculations of silicate glass dissolution rates based on ash and leachate compositions suggest that the presence of soluble F significantly enhances Fe solubility in this sample. Therefore, plume processing of the ash is posited to exert a key control on the Fe release behaviour in solution of volcanic ash sourced from different eruptions.