The influence of dissolved organic carbon on pH measurements of low solute content waters

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Scientific paper

This study has thoroughly examined the concern that dissolved organic carbon (DOC) interferes with pH electrode measurements of low solute content waters. Using Ross pH combination electrodes according to protocols of the U.S. Environmental Protection Agency's National Surface Water Survey (NSWS), our laboratory pH measurements of 10 -4 N H 2 SO 4 standards (spiked from 0 to 100 mg L -1 DOC with potassium hydrogen ortho-phthalate, humic acid, or the surfactant Tergitol 15-S-9) showed little or no evidence of DOC interference, within the ±0.05 (2s) pH unit measurement precision. Concern with DOC-induced pH measurement errors prompted previous researchers to advocate using a calculated pH value, based on measurements of dissolved inorganic carbon (DIC), P co 2 , water temperature, and the appropriate carbonate equilibria. CO 2 -equilibrated pH measurements from the Eastern Lake Survey Phase-I showed no significant difference with calculated pH values based on the above model. A limited sensitivity analysis of the errors associated with direct pH electrode measurements compared to calculated pH values indicates that, for a regional survey taking place over weeks or months, potentiometric determinations are more precise at present. All of this evidence suggests that the pH measurements for the NSWS (as well as a long series of prior regional studies) are unaffected by DOC-induced pH measurement errors, although reference electrode junction errors still deserve greater attention in many studies.

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