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isotopic constituents in the water was established at higher temperatures and this relationship has persisted when the water cools as it flows to the surface. The calculation of subsurface temperatures from chemical analyses of water and steam collected at hot springs, fumaroles, geysers, and shallow water wells is a standard tool of geothermal exploration and fills the need to estimate the subsurface temperature of a geothermal prospect area before any deep wells are drilled. The first temperature calculations were based on experimental laboratory studies of mineral solubility at elevated temperature (Kennedy, 1950; Fournier and Rowe, 1966). As geothermal exploration progressed, observed relationships among dissolved chemical constituents at known temperatures in wells were used to calibrate geothermometers from the aqueous species produced at the surface. Experimental and field data from sodium- chloride solutions were used to develop the mathematical equations for several geothermometers, and most of the calculations are suggested only for use with analyses of dilute, sodium-chloride type waters at near-neutral pH. In some geothermal prospect areas, for example the Basin and Range, sodium-bicarbonate type waters predominate, and few systems have sodium-chloride type water. The differences in the types of water chemistry encountered in geothermal systems require extra caution in the application of geothermometers. Interpretation of the calculated temperatures requires knowledge of the most likely reactions to have occurred between the water and the surrounding rocks. In addition, the charge balance is calculated for every water analysis as a check for the completeness of the analysis and its accuracy. For the USGS geothermal resource assessment, some simple calculations are used to determine the reliability of the chemical analyses of geothermal waters (Reed and Mariner, 1991). Each ion in the analysis is converted to its equivalent concentration, and the charge balance error (CBE) is calculated as 100 times the absolute value of the difference between the summation of equivalent concentrations of cations (Na+, K+, Ca++, Mg++) and the summation of equivalent concentrations of anions (Cl-, F-, HCO3-, SO4--) divided by the average of the summation of equivalent concentrations of cations and the summation of equivalent concentrations of anions. An error greater than 10 percent in the charge balance is indicative of a problem with the analysis, and analyses that fall into this category are only be used for geothermal calculations in the assessment if no other analyses are available and the associated uncertainties in the calculated temperatures can be quantified. Most geothermal systems never reach chemical equilibrium because most of the reaction rates are dependent on the concentrations of components in solution (Barton, 1984). The flow of hydrothermal fluids through a geothermal reservoir is constantly changing the concentrations of components in solution, and the geothermometers reflect a steady-state condition that exists at high temperature between the circulating water and enclosing rocks. The reaction rates for mineral solubility are dependent on temperature as well as several other variables in a hydrothermal system. For example, the approximate times to reach equilibrium between the feldspar minerals and fluid for the Na-K-Ca geothermometer varies from tens of hours at 500°C to on the order of 100 years at 150°C, and the solution-mineral equilibrium for quartz takes from tens of hours at 6PDF Image | Assessment of Identified Geothermal Resources
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