This article describes a technique far the measurement of total and diffusi
ble F content of serum, at clinical significant concentrations of F (1-10 m
u M). The proposed procedure avoids the interference of unknown serum compo
nents with the ion-specific electrode. Sample F is concentrated fivefold th
rough distillation of hydrofluoric acid (Taves' method). Ionic fluoride is
presented to the electrode in a simple solution at concentrations within th
e linear response of the electrode. Average recoveries of F from serum or i
ts ultrafiltrate were 96 +/- 7% (21%) and 97 +/- 12% (53%) (mean +/- SEM [C
V]), respectively. With four replicates of each sample, the technique produ
ce within-run standard deviations of 0.6 mu M and 2.2 mu M at 1 and 10 mu M
F, respectively. Total precision assessment gave standard deviations of 0.
6 mu M and 2.6 mu M at 1 and 10 mu M F, respectively. The fasting serum F l
evels of normal climacteric women, 45 to 65 years, showed an asymmetric dis
tribution. The data obtained started at the detection limit of the techniqu
e (0.1 mM). The 75 percentile was 1.85 mu M for total and 0.5 mu M for diff
usible F. In patients (n = 25) treated with NaF (30 mg F/day) the fasting l
evels of total serum F (4.5 +/- 1.7 mu M) did not differ from those of diff
usible F (4.2 +/- 1.5 mu M). In patients (n = 50) treated with sodium monof
luorophosphate (15 mg F/day) the fasting levels of total and diffusible ser
um F were 6.5 +/- 1.7 mu M and 0.5 +/- 0.03 mu M, respectively. In conclusi
on, this paper establishes the presence of two fractions of serum fluorine:
diffusible and nondiffusible (or protein bound) and describes a technique
for their clinical estimation. In untreated subjects and in patients receiv
ing NaF, the former fraction contains ionic fluoride. In patients treated w
ith MFP, diffusible serum fluorine is composed by ionic fluoride and low mo
lecular weight, peptide-bound, acid-labile fluorine. J. Clin. Lab. Anal. 13
:151-157, 1999. (C) 1999 Wiley-Liss, Inc.