Distinguishing contributions to diffuse CO2 emissions in volcanic areas from magmatic degassing and thermal decarbonation using soil gas 222Rn-δ13C systematics: Application to Santorini volcano, Greece

- 222Rn-δ13C systematics can quantify magmatic and crustal sources of CO2.
- The pattern of soil CO2 degassing changed during the period of volcanic unrest.
- (Rn222)/CO2 ratios indicate the gas has a significant magmatic component.
- Our results confirm that the unrest is the result of a new intrusion of melt.

Between January 2011 and April 2012, Santorini volcano (Greece) experienced a period of unrest characterised by the onset of detectable seismicity and caldera-wide uplift. This episode of inflation represented the first sizeable intrusion of magma beneath Santorini in the past 50 years. We employ a new approach using 222Rn-δ13C systematics to identify and quantify the source of diffuse degassing at Santorini during the period of renewed activity. Soil CO2 flux measurements were made across a network of sites on Nea Kameni between September 2010 and January 2012. Gas samples were collected in April and September 2011 for isotopic analysis of CO2 (δ13C), and radon detectors were deployed during September 2011 to measure (222Rn). Our results reveal a change in the pattern of degassing from the summit of the volcano (Nea Kameni) and suggest an increase in diffuse CO2 emissions between September 2010 and January 2012. High-CO2-flux soil gas samples have δ13C∼0‰. Using this value and other evidence from the literature we conclude that these CO2 emissions from Santorini were a mixture between CO2 sourced from magma, and CO2 released by the thermal or metamorphic breakdown of crustal limestone. We suggest that this mixing of magmatic and crustal carbonate sources may account more broadly for the typical range of δ13C values of CO2 (from ∼−4‰ to ∼+1‰) in diffuse volcanic and fumarole gas emissions around the Mediterranean, without the need to invoke unusual mantle source compositions. At Santorini a mixing model involving magmatic CO2 (with δ13C of −3±2‰ and elevated (222Rn)/CO2 ratios ∼105-106 Bqkg−1) and CO2 released from decarbonation of crustal limestone (with (222Rn)/CO2 ∼ 30-300 Bq kg−1, and δ13C of +5‰) can account for the δ13C and (222Rn)/CO2 characteristics of the 'high flux' gas source. This model suggests ∼60% of the carbon in the high flux deep CO2 end member is of magmatic origin. This combination of δ13C and (222Rn) measurements has potential to quantify magmatic and crustal contributions to the diffuse outgassing of CO2 in volcanic areas, especially those where breakdown of crustal limestone is likely to contribute significantly to the CO2 flux.