The application of square-wave polarography (SWP) to the determination
of sulfide in water is reported. In comparison with other pulse techn
iques, cathodic stripping SWP was found to be the most sensitive. The
details of the deposition and reduction of HgS were explored. The mech
anisms of such deposition and reduction were found to be strongly depe
ndent on the sulfide concentration but, in the observed analytical ran
ge, the HgS reduction process occurs close to the reversible potential
. The influence of pH on the peak potential and on the peak current wa
s studied; the results obtained are compared with those expected for a
reversible process. The optimized analytical procedure allows the det
ermination of sulfide in the 20-830 nM analytical range with a rate of
15 samples per h (calibration curve) or 10 samples per h (standard ad
dition method). Thiosulfate and sulfite, but not sulfate, were found t
o interfere. (C) 1997 Elsevier Science B.V.