Abstract
This paper reviews the techniques available to the clinical biochemist for measuring ionised calcium concentrations in biological fluids with particular reference to serum. At present ionised calcium may be measured colorimetrically, using tetramethyl murexide, or potentiometrically, using a calcium ion-selective electrode. These techniques compare favourably in terms of precision with existing methods for measuring total calcium. Advantages of measuring ionised calcium in preference to total calcium are ( a) that there is no effect of venous occlusion or change of posture on the ionised fraction of the effect on total calcium, ( b) that ionised calcium is the physiologically active form of the element, and ( c) that the ionised calcium concentration is a more reliable indicator of the calcium status of patients in certain clinical conditions. The main problem in the measurement of ionised calcium is the marked dependence of the ionised fraction on the pH of the sample. Extreme care must be taken to avoid loss of CO2 or build-up of acid during the handling of the blood sample.

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