Chemical indicators of subsurface temperature applied to hot spring waters of Yellowstone National Park, Wyoming, U.S.A.

Under favorable conditions the chemistry of hot springs may give reliable indications of subsurface temperatures and circulation patterns. These chemical indicators can be classified by the type of process involved:

All these indicators have certain limitations. The silica geothermometer gives results independent of the local mineral suite and gas partial pressures, but may be affected by dilution. Alkali ratios are strongly affected by the local mineral suite and the formation of complex ions. Carbonate-chloride ratios are strongly affected by subsurface P_CO2. The relative concentration of volatiles can be very misleading in high-pressure liquid systems.

In Yellowstone National Park most thermal waters issue from hot, shallow aquifers with pressures in excess of hydrostatic by 2 to 6 bars and with large flows (the flow of hot spring water from the Park is greater than 4000 liters per second). These conditions should be ideal for the use of chemical indicators to estimate aquifer temperatures. In five drill holes aquifer temperatures were within 2°C of that predicted from the silica content of nearby hot springs; the temperature level off at a lower value than predicted in only one hole, and in four other holes drilling was terminated before the predicted aquifer temperature was reached.

The temperature-Na/K ratio relationship does not follow any published experimental or empirical curve for water-feldspar or water-clay reactions. We suspect that ion exchange reactions involving zeolites in the Yellowstone rocks result in higher Na/K ratios at given temperatures than result from feldspar or clay reactions. Comparison of SiO₂ and Cl/(HCO₃ + CO₃) suggest that because of higher subsurface P_CO2 in Upper Geyser Basin a given Cl/(HCO₃ + CO₃) ratio there means a higher temperature than in Lower Geyser Basin. No correlation was found in Yellowstone Park between the subsurface regions of highest temperature and the relative concentration of volatile components such as boron and ammonia.