Diffuse emission of organic trace gases from the flank and crater of a quiescent active volcano (Vulcano, Aeolian Islands, Italy)

Abstract

<jats:p>Volcanoes discharge a range of inorganic major gas species (e.g., H<jats:sub>2</jats:sub>O, CO<jats:sub>2</jats:sub>, SO<jats:sub>2</jats:sub>, and CO) not only during eruptions but also during quiescent phases through fumarolic and diffuse degassing in their craters and on their flanks. The emission of organic trace gases from volcanoes is similarly not expected to be restricted to discrete fumarolic gas discharges alone. To test this hypothesis, we have sampled soil gas emissions for organic compounds and determined CO<jats:sub>2</jats:sub> fluxes along a profile extending from the vegetated base of the active La Fossa cone (Vulcano Island, Italy) over the unvegetated volcanic flank and up into the crater rim and base and then continuing over fumarolic areas. The results indicate that the majority of volatile organic compounds in the soil gas show significant increases in concentration toward the crater and fumaroles and that diffuse emissions contribute significantly to the volcanic halocarbon source strength. Emissions of the halocarbon CFC‐11 (CCl<jats:sub>3</jats:sub>F) correlate well with soil CO<jats:sub>2</jats:sub> fluxes measured on site (R<jats:sup>2</jats:sup> = 0.89, slope = 1.42 ± 0.1) and both increase toward the crater and fumaroles. Other ozone‐depleting substances were found in concentrations significantly above those found in field and system blanks, including CH<jats:sub>3</jats:sub>Br, CH<jats:sub>3</jats:sub>Cl, CH<jats:sub>3</jats:sub>I, C<jats:sub>2</jats:sub>H<jats:sub>5</jats:sub>Br, and chlorinated benzenes. Abundances ranged from upper pptv to ppmv; for example, the maximum observed CFC‐11 concentrations were 1200 pptv in diffuse emissions and 3700 pptv in dry fumarolic gas (average dry air is 268 pptv). On the basis of these results the natural volcanic source strength of halocarbon emissions to the atmosphere requires reevaluation, and in some cases, correction to higher values. Global average fumarolic and diffuse halocarbon source strengths were estimated and scaled to known global volcanic fumarolic and diffuse CO<jats:sub>2</jats:sub> flux data. Among these were CFC‐11 (8.56 ± 4.7 × 10<jats:sup>−6</jats:sup> Tg y<jats:sup>−1</jats:sup>), CH<jats:sub>3</jats:sub>Br (0.98 ± 0.47 × 10<jats:sup>−6</jats:sup> Tg y<jats:sup>−1</jats:sup>), CHCl<jats:sub>3</jats:sub> (94.9 ± 27.6 × 10<jats:sup>−6</jats:sup> Tg y<jats:sup>−1</jats:sup>), and CCl<jats:sub>4</jats:sub> (3.41 ± 1.0 × 10<jats:sup>−6</jats:sup> Tg y<jats:sup>−1</jats:sup>).</jats:p>