|This article needs additional citations for verification. (November 2007)|
Volcanic gases include a variety of substances given off by active (or, at times, by dormant) volcanoes. These include gases trapped in cavities (vesicles) in volcanic rocks, dissolved or dissociated gases in magma and lava, or gases emanating directly from lava or indirectly through ground water heated by volcanic action.
The sources of volcanic gases on Earth include:
- primordial and recycled constituents from the Earth's mantle,
- assimilated constituents from the Earth's crust,
- groundwater and the Earth's atmosphere.
Substances that may become gaseous or give off gases when heated are termed volatile substances.
Magmatic gases and high-temperature volcanic gases
Gases are released from magma through volatile constituents reaching such high concentrations in the base magma that they evaporate. (Technically, this would be described as the exsolution and accumulation of the gases upon reaching excess supersaturation of these constituents in the host solution (magmatic melt), and their subsequent loss from the host by diffusion and phase separation into bubbles). Molten rock (either magma or lava) near the atmosphere releases high-temperature volcanic gas (>400 °C). In explosive volcanic eruptions, sudden release of gases from magma may cause rapid movements of the molten rock. When the magma encounters water, seawater, lake water or groundwater, it can be rapidly fragmented. The rapid expansion of gases is the driving mechanism of most explosive volcanic eruptions. However, a significant portion of volcanic gas release occurs during quasi-continuous quiescent phases of active volcanism.
Low-temperature volcanic gases and hydrothermal systems
So, if the magmatic gas traveling upward encounters meteoric water in an aquifer, steam is produced. Latent magmatic heat can also cause meteoric waters to ascend as a vapour phase. Extended fluid-rock interaction of this hot mixture can leach constituents out of the cooling magmatic rock and also the country rock, causing volume changes and phase transitions, reactions and thus an increase in ionic strength of the upward percolating fluid. This process also decreases the fluid's pH. Cooling can cause phase separation and mineral deposition, accompanied by a shift toward more reducing conditions. At the surface expression of such hydrothermal systems, low-temperature volcanic gases (<400 °C) are either emanating as steam-gas mixtures or in dissolved form in hot springs. At the ocean floor, such hot supersaturated hydrothermal fluids form gigantic chimney structures called black smokers, at the point of emission into the cold seawater.
Non-explosive volcanic gas release
The gas release can occur by advection through fractures, or via diffuse degassing through large areas of permeable ground as Diffuse Degassing Structures (DDS). At sites of advective gas loss, precipitation of sulfur and rare salts forms sulfur deposits and small sulfur chimneys, called fumaroles. Very low-temperature <100 °C) fumarolic structures are also known as solfataras. Sites of cold degassing of predominantly carbon dioxide are called mofettes. Hot springs on volcanoes often show a measurable amount of magmatic gas in dissolved form.
The principal components of volcanic gases are water vapor (H2O), carbon dioxide (CO2), sulfur either as sulfur dioxide (SO2) (high-temperature volcanic gases) or hydrogen sulfide (H2S) (low-temperature volcanic gases), nitrogen, argon, helium, neon, methane, carbon monoxide and hydrogen. Other compounds detected in volcanic gases are oxygen (meteoric), hydrogen chloride, hydrogen fluoride, hydrogen bromide, nitrogen oxide (NOx), sulfur hexafluoride, carbonyl sulfide, and organic compounds. Exotic trace compounds include mercury, halocarbons (including CFCs), and halogen oxide radicals.
The abundance of gases varies considerably from volcano to volcano. Water vapor is consistently the most common volcanic gas, normally comprising more than 60% of total emissions. Carbon dioxide typically accounts for 10 to 40% of emissions.
Volcanoes located at convergent plate boundaries emit more water vapor and chlorine than volcanoes at hot spots or divergent plate boundaries. This is caused by the addition of seawater into magmas formed at subduction zones. Convergent plate boundary volcanoes also have higher H2O/H2, H2O/CO2, CO2/He and N2/He ratios than hot spot or divergent plate boundary volcanoes.
Sensing, collection and measurement
Volcanic gases can be sensed (measured in-situ) or sampled for further analysis. Volcanic gas sensing can be:
- within the gas by means of electrochemical sensors and flow-through infrared-spectroscopic gas cells
- outside the gas by ground-based or airborne remote spectroscopy (e.g., COSPEC, FLYSPEC, DOAS, FTIR)
Volcanic gas sampling is often done by a method involving an evacuated flask with caustic solution, first used by Robert W. Bunsen (1811-1899) and later refined by the German chemist Werner F. Giggenbach (1937-1997), dubbed Giggenbach-bottle. Other methods include collection in evacuated empty containers, in flow-through glass tubes, in gas wash bottles (cryogenic scrubbers), on impregnated filter packs and on solid adsorbent tubes.
Analytical techniques for gas samples comprise gas chromatography with thermal conductivity detection (TCD), flame ionization detection (FID) and mass spectrometry (GC-MS) for gases, and various wet chemical techniques for dissolved species (e.g., acidimetric titration for dissolved CO2, and ion chromatography for sulfate, chloride, fluoride). The trace metal, trace organic and isotopic composition is usually determined by different mass spectrometric methods.
Volcanic gases and volcano monitoring
Main article: Prediction of volcanic activity
Certain constituents of volcanic gases may show very early signs of changing conditions at depth, making them a powerful tool to predict imminent unrest. Used in conjunction with monitoring data on seismicity and deformation, correlative monitoring gains great efficiency. Volcanic gas monitoring is a standard tool of any volcano observatory. Unfortunately, the most precise compositional data still require dangerous field sampling campaigns. However, remote sensing techniques have advanced tremendously through the 1990s.
Volcanic gases were directly responsible for approximately 3% of all volcano-related deaths of humans between 1900 and 1986. Some volcanic gases kill by acidic corrosion; others kill by asphyxiation. The greenhouse gas, carbon dioxide, is emitted from volcanoes, accounting for nearly 1% of the annual global total. Some volcanic gases including sulfur dioxide, hydrogen chloride, hydrogen sulfide and hydrogen fluoride react with other atmospheric particles to form aerosols. 
- H. Sigurdsson et al. (2000) Encyclopedia of Volcanoes, San Diego, Academic Press
- N. Morello (editor) (1998), Volcanoes and History, Genoa, Brigati
- Royal Society Climate Change Controversies, London, June 2007