Alkyl xanthates (O-alkyl dithiocarbonates) and phosphonates are important organic collectors for the flotation of metals from crude ore. Leaching from waste dumps into river and ground water, these substances can cause environmental pollution.

A capillary electrophoretic method for the routine determination of ethyl, isopropyl, hexyl xanthate, and styrene phosphonate has been developed. Separation within 12 min could be achieved in borate pH 8.8 performing UV detection at 254 and 300 nm simultaneously. To improve the limits of detection obtained with hydrodynamic injection (0.4–1.5 ppm), field amplified sample injection (FASI) and stacking were investigated. An increase in sensitivity up to 4–8 fold could be achieved by pressure assisted FASI. Applying a stacking method to enrich the analytes by filling the capillary with sample solution to one third of its length, the limits of detection could be decreased to 10–40 ppb.

Water samples from a former tin ore mining area have been analyzed using the optimized stacking technique. Quantitation was performed by standard addition. Good precision and accuracy were obtained, making this robust capillary electrophoretic method well-suited for routine analysis.