The method validation for the speciation of five arsenic species in ur
ine samples by liquid chromatography hyphenated to inductively coupled
plasma mass spectrometry is described. Arsenic species which are iden
tified and quantified in urine samples are the anions cationic arsenic
(III), arsenic(V), monomethylarsonic acid and dimethylarsinic acid, an
d the cationic arsenobetaine. Detection limits were obtained in the ra
nge 0.3-0.4 mu g As l(-1) while the repeatability was in the range 3-4
% (RSD) for concentrations above five times the detection limit. Urine
samples could be analysed directly after a tenfold dilution step, Ars
enic compound concentrations were determined in urine samples from a v
olunteer who consumed a portion of tuna fish high in arsenobetaine. It
was found that arsenobetaine was excreted rapidly via the urine with
maximum concentrations after 12 h. Nearly complete arsenobetaine excre
tion was reached after 48 h. Background levels of arsenic compounds we
re determined in 61 urine samples from non-exposed inhabitants of The
Netherlands. (C) 1998 John Whey & Sons, Ltd.