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Predicted cation ratio geothermometry temperatures, using equations of Na-K, Na-K-Ca, Mg-Na-K-Ca and Mg-Li, were compared between oilfield and geothermal settings. Geothermometers in oilfield waters yielded less consistent temperature predictions compared to geothermal waters in the same temperature range. Scatter of predicted temperature in oilfield waters is greatest in the temperature interval where carboxylic acid anions (CAAs) are in greatest concentration. CAAs are not present in geothermal systems. Temperature prediction improves in those oilfield waters where CAAs are present and account for less than 80% of total alkalinity.

The assumptions of cation ratio geothermometry are violated to varying degrees in oilfield waters where CAAs are abundant. These assumptions are: (1) cation ratios are controlled by exchange between solid aluminosilicates. However, CAAs affect mineral solubility by forming complexes with the cations. Therefore. the ratios of cations in solution differ from those values expected when cation exchange between aluminosilicate minerais is the only control on the cation ratios. Furthermore, concentrations of Ca and Mg are strongly controlled by carbonate equilibria, which in turn is strongly affected by the presence of CAAs; (2) aluminum is conserved in solid phases. However, CAAs form stable complexes with Al, increasing Al-silicate solubility and mobilizing Al; thus Al may not be conserved m mineral phases; (3) neither H 1 nor CO, enter into the net reactions (i.e., pH is buffered by aluminosilicate hydrolysis). However, acetate (the dominant CAA found in oilfield waters) is an effective buffer of pH in feldspathic rocks. Also, at higher temperatures, decarboxylation of CAAs increases the PC02 of oilfield waters.

The consistently worse temperature prediction of cation ratio geothermometers in oilfield waters in the 80-120°C temperature range is another indication that organic-inorganic diagenesis is an important control on oilfield water chemistry.

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