Relationship between direct-potentiometric and flame-photometric measurement of sodium in blood

The relationship between direct-potentiometric and flame-photometric measurements of sodium has been studied in human sera and other, simpler systems. When water content was varied by using an inert substance (silica), de-ionized sera, or de-ionized individual proteins, the percentage that the flame photometric values were of the direct potentiometric Na+ values was identical to the measured water content. However, in 35 patients the percentage of Na+ values was 99.1% and the water content was 92.0%, a discrepancy of 7.1%. De-ionization of sera removed this discrepancy, apparently because of the lower pH of the de-ionized sera. The percentage of flame-photometric to direct-potentiometric Na+ values varied as a function of pH in pooled sera; in lyophilized and reconstituted sera; and in de-ionized, lyophilized, and reconstituted sera. Four explanations for the discrepancy between the percentage of Na+ values and the water content are discussed: a calibration problem, a measurement artifact, Na+ binding, and water binding. At this time there are no definitive data concerning which explanation is correct. We expect that our finding of a pH dependency for the percentage of measured Na+ values can be used to develop model systems to elucidate the mechanism producing the discrepancy between the percentage of Na+ values and the water content.