Chloride interference in the analysis of dissolved organic carbon by the wet oxidation method

The presence of Cl- in concentrations greater than 0.02 M is shown to interfere with the analysis of aqueous DOC concentrations by the wet oxidation method of analysis when a reaction time of 5 min is employed. Chloride competes with DOC for S2O82-, lowering the overall oxidation efficiency. The resulting HOCl from the oxidation of Cl- reacts with DOC, producing significant amounts of chlorinated intermediate compounds in addition to CO2. These compounds were found in the waste effluent from the reaction chamber and in the gas stream transporting CO2 to the detector. While a possible Cl- effect has been noted for DOC measurements in the past, it has not previously been demonstrated to be a source of error at the concentrations reported in this paper. The interference can be overcome either by increasing the digestion time or by diluting samples to contain less than 0.02 M Cl-.