Real-time quadrupole mass spectrometry of hydrothermal gases from the unstable Pisciarelli fumaroles (Campi Flegrei): Trends, challenges and processes

•QMS-based monitoring comparable with discrete sampling and other in situ techniques.•Measured ratios shed light on minor fluctuations about subtle hydrothermal changes.•QMS-based geochemical monitoring unravels short-term variations in safe conditions.•QMS is suitable for monitoring of harsh environments at a reasonable price.•High-frequency QMS monitoring can be made compatible with geophysical acquisition.

Volcanic gas sampling and post-collection chemical determination in a laboratory may preclude any real-time continuous monitoring of volcanic activity. We describe the development, and show the advantages, of a system used for the continuous monitoring of fumarolic gases discharged from the Pisciarelli site (Campi Flegrei, Southern Italy) based on a commercial quadrupole mass spectrometer (QMS-301 Omnistar™). Although numerous technical problems were addressed due to the ephemeral nature of the emission point and the harsh environment, we also report measurements of the chemical composition of the major gas species emitted from the fumarole for two different periods (in 2009 and 2012). The CO2/H2S, H2S/H2, He/CO2 and CH4/CO2 molar ratios were investigated in order to detect magmatic and/or hydrothermal components in the system, while the N2/O2 ratio was adopted to infer other non-volcanic processes, such as air contamination and mixing with polluted surface waters. The presented methodology allows continuous gas sampling and provides the first evidence of short-term gas variations not available by direct sampling, which is often impractical and hazardous. Compared to the current techniques that are used worldwide for the full characterization of gaseous emissions, i.e. chemical analysis of traditional soda-filled under-vacuum bottles and MultiGAS surveys (laboratory-based and in situ, respectively), QMS-based monitoring is complementary and, in prospect, an alternative. With our method, the geochemical monitoring benefits of the real-time analysis for high sampling rates that can be made comparable to the continuous measurements of geophysical networks. This allows a better understanding of hydrothermal features, particularly of chemical fluctuations occurring on the very short-term, which is fundamental for the evaluation of the evolution of unrest episodes at Campi Flegrei, one of the most hazardous volcanic areas in the world.

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