The concept of accuracy assessment is exploited in flow analysis. The
resulting system is based on multi-commutation because multiple sample
processing is involved. The manifold includes different quasi-indepen
dent methods and permits recovery tests to be performed on every sampl
e. Results are then intrinsically more accurate and additional informa
tion on the sample matrix is provided. The feasibility of the approach
is demonstrated in the large scale determination of chloride in river
water samples presenting high variability in matrix composition and/o
r in acidity. The spectrophotometric mercury thiocyanate-Fe(II) method
and the turbidimetric method based on the precipitation with silver i
ons are implemented in a single manifold and a 40.00 mg l(-1) Cl- inte
rmittent stream is added in-line to each sample for producing recovery
data. Analysis of the four recorded analytical signals permits evalua
tion and eventual compensation of matrix effects. The final result is
calculated after considering the results obtained by two different met
hods, and the eventual correction of matrix effects. The proposed syst
em is very robust, handles 25 samples per hour and yields precise resu
lts between 0.50 and 10.0 mg l(-1) Cl-. Potentialities and limitations
of the approach are discussed.