Volcanic & Geothermal Gas

Origin and Characteristics

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 Volcanic Gas
• Source:
– Primordial and recycled constituents from the earth;s
mantle
– Assimilated constituents from the earth’s crust
– Groundwater and the earth atmosphere

Volcanic Gas
• High-temperature volcanic gases (>400°C): gases are
released from magma through volatile constituents
Æ Magmatic gases

• Low-temperature volcanic gases (<400°C): steam is

produced when the magmatic gas traveling upward
encounters meteoric water in an aquifer
Æ Hydrothermal systems

• Non-explosive volcanic gas: the gas release can occur

by advection through fractures, or via diffuse degassing
through large areas of permeable ground
Æ Fumaroles, solfataras, mofettes

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 Volcanic Gas
• Composition:
– The principal components of volcanic gases are H2O
(>60% of total emissions), CO2 (10-40% of total
emissions), S either as SO2 (high-temperature volcanic
gases or H2S (low-temperature volcanic gases), N2, Ar,
He, Ne, CH4, CO and H2
– Other compounds detected in volcanic gases are O2
(meteoric), HCl, HF, HBr, NOx, SF4, carbonyl sulfide, and
organic compound
– Exotic trace compounds include methyl mercury,
halocarbons (including CFCs), and halogen oxide
radicals

The abundance of gases varies considerably from volcano

to volcano (compositions in vol.%)
Volcano Kilauea Summit Erta` Ale Momotombo
Tectonic Style Hot Spot Divergent Plate Convergent Plate
Temperature 1170°C 1130°C 820°C

H 20 37.1 77.2 97.1

C02 48.9 11.3 1.44

S02 11.8 8.34 0.50

H2 0.49 1.39 0.70

CO 1.51 0.44 0.01

H 2S 0.04 0.68 0.23

HCl 0.08 0.42 2.89

HF --- --- 0.26

Source: Symonds et al., 1994

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 Examples of volcanic gas compositions, in mole.%
Etna Mt. St. Merapi Erta Ale Surtsey Kilauea Kilauea
hawaiite Helens andesite basalt basalt summit rift zone
dacite basalt basalt
T (°C) 1075 802 915 1032 1125 1170 1010
logfO2 -9.47 -14.25 -12.49 -10.12 -9.80 -8.38 -10.49
H 2O 27.71 91.58 88.87 69.41 81.13 37.09 79.8
H2 0.30 0.85 1.54 1.57 2.80 0.49 0.90
CO2 22.76 6.64 7.07 17.16 9.29 48.90 3.15
CO 0.48 0.06 0.16 0.75 0.69 1.51 0.06
SO2 47.70 0.2089 1.15 9.46 4.12 11.84 14.9
H 2S 0.22 0.3553 1.12 1.02 0.89 0.04 0.622
S2 0.76 0.0039 0.08 0.59 0.25 0.02 0.309
HCl -- -- 0.59 -- -- 0.08 0.1
HF -- -- 0.04 -- -- -- 0.19
COS -- 0.0008 -- 0.02 -- -- 0.0013
SO 0.06 -- -- -- -- -- --

Volcanic Gas
• H20, CO2, and SO2 are the most common gases in all
samples. Minor gases are H2, H2S, HCl, CO, and S2.
• Based on elemental compositions, convergent-plate
volcanoes tend to have higher H (reflected in H2O) and
lower C and S (CO2 and SO2) relative to divergent-plate
volcanoes and hot-spot volcanoes (which have high relative
C and S and low H).
• Volcanoes located at convergent plate boundaries emit
more water vapor and chlorine than volcanoes at hot spots
or divergent plate boundaries.
• The subducted slab contributes H2O and Cl to convergent-
plate magmas.
• Magma sources for divergent-plate volcanoes and hot-spot
volcanoes are located in the mantle and have moderate
amounts of C and S and are relatively depleted in H2O and
HCl.

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 Geothermal Gas
• Geothermal gas is a product of components from
meteoric, crustal, and magmatic sources that are
modified by some processes, such as boiling, mixing, and
condensation.
• High temperature gas discharges associated with
volcanic systems closely approach a state of chemical
equilibrium (Ellis, 1957 op. cit. Giggenbach, 1980)
• Underground vapor-liquid separation processes can lead
to large variations in the relative proportions of gases
present in a well discharge (Ellis, 1962 and Glover, 1970
op. cit. Giggenbach, 1980)

After Hedenquist (1986) and Hedenquist and Lowenstein (1994)

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 Geothermal Gas
• Assumptions are made:
– Gas chemistry of geothermal fluids is different from gas
chemistry of non-thermal waters.
– Reservoir fluids commonly have additions of magmatic
volatiles that have specific He-N2-Ar ratios.
– There are 3 sources of volatile compounds: magma,
the crust by wall rock reactions, and the atmosphere.
– Boiling, condensation, and fluid mixing processes result
in systematic changes in gas chemistry.

Geothermal Gas
• Reaction controlling the composition of geothermal gas
discharges (Giggenbach, 1980):
– H2O-CO2-H2S-NH3-H2-N2-CH4
– He-Ar
– Higer hydrocarbons
• Gas reaction for which all participants can be determined
analytically:
– CH4 + 2H2O ÅÆ CO2 + 4H2
– 2NH3 ÅÆ N2 + 3H2
• Other reactions:
– CH4 ÅÆ C(graphite) + 2H2
– H2S ÅÆ (S) + H2

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 Geothermal Gas
• Major: H2O
• Dominant: CO2 and H2S
• Present in lower concentration: N2, H2, CH4, CO, NH3, Ar
and He
• Absent: strongly acid gases from magma bodies
degassing (i.e. SO2, HCl and HF)
• Sulfur dioxide was detectable only in some fumarolic
discharges from active volcanic areas (Giggenbach,
1980)
• Commonly CH4 contents much greater than CO (Chiodini
et al., 1992)

Fumaroles on White Island, NZ (Giggenbach, 1975)

• All fumaroles are essentially supplied with one common
type of gas made up of at least three components. i.e.
carbon, sulfur, and chlorine containing species
• During quiet periods, with low fumarolic outlet
temperatures (≤300), the component with ratios C:S:Cl of
92:3:5 predominates
• During heating up periods the relative carbon contents
decrease, considered to be due to admixture of a
component with C:S:Cl ratios of 44:26:30
• Coinciding with maximum outlet temperatures (≈ 800°),
however, the component with C:S:Cl ratios of 70:29:1
predominates
• Gas with low ratios of C:S of around 2.5 and ratios of S:Cl
of above ten is considered to be most closely related to
the primary magmatic gas phase

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 Geothermal Gas
• High-temperature systems: CO2 + H2S
• Low-temperature systems: N2, CH4
• Magmatic systems: HCl, HF, SO2

Origin/source
• Atmosphere (H2Ovap, O2, CO2, He, H2)
• Deep-seated (H2, He, H2S, SO2, HCl, dsb),
• Radiogenic (He, Rn)
• Biogenic (CH4, H2, H2S, CO)

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 Movement
• Diffusion
• Soluble in fluid (water and vapour phase)
• Transfer due to phase change (boiling, condensation,
etc)
– As a geothermal fluid migrates to the surface and
boils, the vapour phase will separate from the liquid
phase
– Gases are more soluble in steam than in the original
fluid.
– After boiling, the residual liquid is depleted in gas
relative to the original fluid composition (although
portion of all gases will be retained in the liquid phase).

Æ gas ratios in the steam will differ from those in the original fluid
fluid

Movement
• Other processes:
– Oxidation (e.g. H2S ÅÆ H2SO4)
– Rock and steam reactions (e.g. increasing CO2 from
decomposition of carbonate minerals)

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 Source of Gas
• 3He/4He – magmatic (high) vs. crustal (low)
(3He = mantle source; 4He = decay of U, Th, Ar)

• 40Ar/36Ar – atmospheric (low) vs. magmatic (high)

• Noble gas ratios (various)

• Stable isotopes of steam condensate

Source of Gas
Magmatic input:
High HCl, HF & SO2, N2/Ar = 800-2000, He/Ar ~ 0.1

Air contamination:
+O2, N2/Ar = 84, He/Ar = 5.7 x 10-4

Meteoric:
N2/Ar = 38, He/Ar < 0.001

Radiogenic He:
He/Ar > 5.7 x 10-4

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 Discharge of Geothermal Gas
• Fumaroles, solfataras
• Steam vent
• Kaipohan
• Steaming ground
• Hot pools

Gas Sampling Equipment

• 300mL-volume cylindrical, round-bottom glass flask
equipped with a Quickfit Rotaflo teflon stopcock
(Giggenbach, 1975) or double-mounted syringe
(Hirabayashi, 1986) Æ added with 50 mL of 5 M NaOH
• Sampling tubes, funnel, connectors
• Thermometer
• Pole with clamp
• Large volume of water to cool flask
• Thick rubber gloves
• Teflon tape
• General equipment, such as towel, waterproof marker
pen, etc

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Steam vent

Shallow pools Deep pools

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