Quantifying the organic content of saline wastewaters: Is chemical oxygen demand always an achievable parameter?

The study presented in this paper takes a comprehensive approach to the measurement of the COD of saline industrial wastewaters taking into account both their widely varying salinity levels and the substantial interference of chloride with the conventional method of COD measurement. To this end, three approaches for combating the chloride interference associated with the measurement of COD using the conventional method were considered. The dilution of saline samples prior to analysis yielded reasonably accurate COD results as long as the COD after dilution was 40 mg L^-1 or above. In the second approach, the previously reported modifications of the standard method were stretched to their practical limits (increasing HgSO₄ to 130 g L^-1 and decreasing K₂Cr₂O₇ to 1.022 g L^-1) accompanied by prior addition of HgSO₄:Cl^- at a ratio of 20:1 combined with chloride interference error estimation. This brought about an increase in chloride interference threshold of the standard method to 42.5 g L^-1, which is considerably higher than previous reports. Since some raw or treated saline industrial wastewaters have a combination of chloride and COD concentration which makes the first two approaches inapplicable, the approach of chloride removal from the sample via a modification of DIN 38409-H41-2 and subsequent measurement of COD using a slight variation of the closed reflux standard method was also considered. Fairly accurate COD determinations for samples with chloride concentrations up to 148.6 and 182 g L^-1 for COD contents of 50 and 900 mg L^-1, respectively were achieved. However, excessive precipitation of the desalination reaction products made the method inapplicable to samples with chloride concentrations above 182 g L^-1.