The difficulty in measuring reservoir gas concentrations in geothermal
systems often forces the use of gas ratios in a separated vapor phase
to investigate reservoir conditions. Measured CO/CO2 and H-2/H2O rati
os of fumarolic fluids and vapors from geothermal wells representative
of twenty-two different hydrothermal systems are consistent with theo
retical values obtained from either of two commonly used redox buffers
, indicating that CO and H-2 attain chemical equilibrium in the hydrot
hermal reservoir. Use of different f(O2)-buffers has little effect on
these functions. Many measured CH4/CO2 ratios are, instead, inconsiste
nt with theoretical values obtained with any redox buffer. Since CH4/C
O2 ratios are strongly affected by redox conditions in the gas equilib
ration zone, this disagreement between measured and theoretical values
likely indicates that either no unique f(O2)-buffer is active in all
the hydrothermal environments or that CH4 is not in equilibrium with t
he other gases. The weight of CH4 on the 3log(X-CO/X-CO2) + log(X-CO/X
-CH4) function is relatively small. Therefore this function and the lo
g(X-CO/X-CO2) - log(X-H2/X-H2O) function, both of which are independen
t upon redox conditions, were used. These functions gave reasonable es
timates of the equilibrium temperature and either the fraction of sepa
rated steam or the fraction of condensed steam in each sample. From th
ese data, the CO/CO2, H-2/H2O, and H-2/CO ratios in the hypothetical s
ingle saturated vapor phase were calculated and used to investigate f(
O2) and f(CO2) distributions in the considered twenty-two hydrothermal
systems. Recalculated f(CO2) values are generally consistent, within
one-half log-unit, with the full equilibrium function of Giggenbach (1
984, 1988) although production of thermometamorphic CO2 might locally
take place. It is evident that no unique f(O2)-buffer is active in all
the hydrothermal environments. This fact imply that CH4 could have at
tained chemical equilibrium with other gas species in the H2O-H-2-CO2-
CO-CH4 system. Copyright (C) 1998 Elsevier Science Ltd.