In situ, High-Resolution Measurement of Dissolved Sulfide Using Diffusive Gradients in Thin Films with Computer-Imaging Densitometry

The technique of diffusive gradients in thin films (DGT) has been developed for the measurement of dissolved sulfide. Sulfide species from the sampled waters diffuse through a polyacrylamide hydrogel and then react with pale yellow AgI((s)), incorporated at the surface of a second gel, to form black Ag(2)S((s)). The accumulated sulfide can be measured with a conventional purge-and-trap method followed by colorimetry (methylene blue). This enables the dissolved-sulfide concentration to be calculated under suitable conditions. Alternatively, the color change in the accumulating gel can be used to measure sulfide. A conventional flat-bed scanner, allied to imaging software, provided a densitometric measurement that was quantitatively related to the amount of sulfide accumulated. DGT measurements on synthetic solutions accurately determined the sulfide concentration (95% recovery), thereby confirming the unobstructed diffusion of HS(-) through the gel. The accumulated mass was inversely proportional to the diffusion-layer thickness as theoretically predicted. With the selected geometry, the limit of detection of the densitometric procedure for a 24-h deployment was 0.13 μmol L(-)(1), and the maximum concentration measurable was 60 μmol L(-)(1). When used in anoxic lacustrine waters, DGT provided sensible concentrations. It was also used to measure depth profiles at submillimeter resolution in estuarine surface sediments.