As magma rises through the crust, decreasing pressure conditions allow volatiles to exsolve from the magma. These volatiles then migrate upward through the crust, where they can be stored at shallower levels or escape to the atmosphere. Rising magma also heats rock masses beneath volcanic centers, causing water in shallow aquifers and hydrothermal systems to boil and release additional gases and steam (see chapter F, this volume; Ingebritsen and Hurwitz, 2024). The chemistry and quantity of gases that reach the surface during periods of quiescence or volcanic unrest can reveal that gas-rich magma is ascending, crystallizing, or alternatively stalling, with important implications for volcanic hazard (for example, Sutton and others, 1992; Aiuppa and others, 2007, 2021; Werner and others, 2009, 2011, 2012; Moretti and others, 2013; de Moor and others, 2016; Lewicki and others, 2019; Edmonds and others, 2022; Kern and others, 2022; Kunrat and others, 2022).

Most volcanoes in Alaska and the western United States are characterized by weak degassing, with one or more low-temperature fumaroles (typically near the local boiling temperature of water) and connect to a deeper and sometimes extensive hydrothermal system (for example, McGee and others, 2001; Symonds and others, 2003a, b). Hydrothermal systems will affect the chemistry of rising gases exsolved from deeper magma (Symonds and others, 2001), including sulfur dioxide (SO₂), hydrogen chloride (HCl), and water vapor (for example, Doukas and Gerlach, 1995; Gerlach and others, 1998, 2008; Symonds and others, 2001; Werner and others, 2013). As an example, depending on factors such as temperature, pressure, and oxidation state, rising SO₂ will react with groundwater to form hydrogen sulfide (H₂S) gas, dissolved sulfate (SO₄²⁻), or elemental sulfur (Christenson, 2000; Symonds and others, 2001; Werner and others, 2008). The reaction and dissolution of SO₂ into shallow groundwater is commonly referred to as scrubbing, and can reduce the likelihood that ascending, degassing magma can be detected. Carbon dioxide, however, in addition to exsolving from magma early in the ascent process, is not easily removed by hydrothermal fluids (Lowenstern, 2001). As scrubbing and other processes take place, the SO₂/H₂S, CO₂/SO₂, and CO₂/H₂S ratios may change. High rates of SO₂ emission indicate that magma has moved to relatively shallow levels in the volcano and that the system has heated up enough to establish dry pathways from depth to the surface. Monitoring multiple gas species and the total output of those species is thereby useful for volcano monitoring during both periods of quiescence, to establish background degassing conditions, and during unrest, when gas geochemistry and emission rates can provide information on changing conditions, such as magma ascent.

To provide context for multidisciplinary volcano forecasts, we focus on the following two key required capabilities: (1) characterizing baseline geochemistry and gas discharge from volcanoes and volcanic regions and (2) monitoring changes in gas geochemistry and discharge to inform forecasts of volcanic eruptions and their effects. Sufficient baseline data must be collected to identify and interpret anomalous degassing associated with volcanic unrest (for example, Sorey and others, 1998; Rouwet and others, 2014). Differences in volcano type, baseline degassing rates, local hydrology, and geography (for example, high versus low latitude) will result in a different baseline for each volcano. Volcanoes of any threat level that exhibit one or more degassing phenomena would ideally be monitored by techniques needed to establish baseline degassing data, with the sampling frequency of baseline data dictated by the threat level (table E1). Additional monitoring techniques become necessary during periods of unrest.

In general, three of the most important techniques for gas monitoring are (1) direct sampling of fumarole, spring, and soil gases for laboratory geochemical measurements, (2) measurements of the chemical composition of the volcanic plume and emission rates of major gas species (for example, H₂O, CO₂, SO₂, and H₂S) by satellite, airborne, or ground-based techniques, and (3) measurements of diffuse emissions of CO₂ and other gases through soils. Various methods and instruments may be useful both for baseline studies and during unrest.