Experimental characterization of heavy halogens behavior in alkaline magmas
Résumé
Halogens are minor volatile species emitted during volcanic
eruptions, whose injection into the atmosphere contributes to the
diminution of the stratospheric ozone layer and causes major
climatic impacts. However, the lack of detailed understanding
concerning halogens behavior in magmas – especially bromine
and iodine - and their degassing during magma ascent, prevents a
full assessment of halogen cycling in the Earth’s system.
Previous studies on iron-free synthetic systems have shown that
the partitioning of Cl, Br and I between fluids and silicate melts
increasingly favors the former as the ionic radii of the halogenide
ions increases [1]. These results suggest that bromine and iodine
fluxes to the atmosphere are probably underestimated. To
evaluate this phenomenon, additional experimental constraints on
Br and I behavior in natural magmas are urgently needed. In this
study, the Br partitioning between fluids and natural silicate
melts has been investigated experimentally as a function of melt
composition, pressure, temperature and oxygen fugacity.
Composition investigated and corresponding geodynamic
settings are representative of alkaline/hyperalkaline magmatic
systems worldwide. Experiments were performed in internally
heated pressure vessels (IHPV) under controlled oxygen fugacity
and allowing drop quench. Bromine abundances were
determined by μ-XRF, LA-ICP-MS or nanoSIMS, while fluid
composition was estimated by mass balance calculations. Our
results confirm the preference of bromine for the fluid phase,
whatever the experimental conditions investigated, being in
agreement with previous studies on metaluminous compositions
[2], DBr
f/m increasing with melt silica content. Due to its very low
concentration in magmas, iodine behavior remains particularly
poorly known. To address this issue, we have carried out HP-HT
solubility experiments to synthesize a series of reference glasses,
in order to test several sensitive analytical techniques for iodine
quantification, such as LA-ICP-MS, nanoSIMS or neutron
irradiation noble gas mass spectrometric technique. Data
acquired in this study will enrich a still fragmentary knowledge
of deep halogens geochemistry and therefore constitute part of
the essential basis to develop the first physically-based
quantitative framework for volcanic heavy halogen emissions.
[1] Bureau et al., (2000), Earth And Planetary Science Letters
183, 51-60.
[2] Cadoux et al., (2018), Earth And Planetary Science Letters
498, 450–463.