This study indicates that scatter in δ(13)CDIC isotope data can be in the range of several per mil for samples from extreme environments (geothermal waters) and may not yield reliable information with respect to dissolved carbon (petroleum wells). The analyses of lake water and seawater also revealed a larger than expected difference and researchers from various disciplines should be aware of this. Evaluation of analytical procedures of the participating laboratories indicated that the differences cannot be explained by analytical errors or different data normalization procedures and must be related to specific sample characteristics or secondary effects during sample storage and handling. Our results reveal the need for further research on sources of error and on method standardization.

A statistical evaluation of the results of HCO3‐ determinations in geothermal waters during the interlaboratory comparison programmes of the International Association of Geochemistry and Cosmochemistry (IAGC) and International Atomic Energy Agency (IAEA) indicated that the analytical uncertainty increases with decreasing concentration of HCO3‐ and was ˜ 25% for 50 μg ml‐1 and ˜ 60% for 25 μg ml‐1 of HCO3‐. The analytical method (Method 1) used by chemists and hydrologists works well for waters containing carbonic alkalinity, whereas Method 2 used by geochemists is conceptually incorrect. A stepwise comparison between the theoretical and experimental titration results for a given concentration Na2CO3 (0.0988 mol l‐1) solution was performed to understand the limitations of the titration method for geothermal water analysis. Backward titration from the carbonic acid equivalence point (H2CO3EP) to the original pH after CO2 removal, as had been practised earlier in the geothermal industry, in order to estimate the contribution of silicic and boric alkalinities to the total alkalinity, is incorrect because the amount of standard base (NaOH) added is equivalent to silicic and boric alkalinities plus some OH‐ alkalinity. In a Na2CO3 solution, the added NaOH is equivalent to OH‐ alkalinity only. Backward titration is only needed from the forward titration end point to the H2CO3EP in order to correct the total alkalinity for the excess of standard acid (HCl) added during the forward titration. In the case of a Na2CO3 solution, the H2CO3EP, after removal of CO2 during the forward titration, is at pH = 7, not at pH = 4.5 (3.8) as has been considered in literature. Similarly, the liberation of CO2 during titration occurs well before the point expected theoretically and it is less for shorter titration time. The revised procedure for the determination of carbonic species concentration is presented and illustrated for a water sample from Alchichica Lake, Puebla, Mexico.

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