Determination of chemical oxygen demand (COD) using an alternative wet chemical method free of mercury and dichromate

Worldwide, the standard methods for the determination of the important wastewater parameter chemical oxygen demand (COD) are still based on the use of the hazardous chemicals, mercury sulfate and chromium(VI). However, due to their properties they are meanwhile classified as "priority pollutants" and shall be phased out or banned in the frame of REACH (current European Chemical Law: Registration, Evaluation, Authorization and restriction of Chemicals) by the European Union. Hence, a new wet-chemical method free of mercury and chromium(VI) was developed. Manganese(III) was used as oxidant and silver nitrate for the removal of chloride ions. The quantification was performed by back titration of manganese(III) with iron(II) as done in the standard method. In order to minimize losses of organic substances during the precipitation of silver chloride, suspended and colloid organic matter had to be separated by precipitation of aluminum hydroxide in a first step. In these cases, two fractions, one of the suspended and colloid matters and a second of the dissolved organic substances, are prepared and oxidized separately. The method was tested with potassium hydrogen phthalate (KHP) as conventional COD reference substance and different types of wastewater samples. The oxidation of KHP was reproducible in a COD range of 20-500 mg/L with a mean recovery rate of 88.7% in comparison to the standard COD method (DIN 38409-41). Also in presence of 1000 mg/L chloride a recovery rate of 84.1% was reached. For a series of industrial and municipal wastewater samples a high correlation (R² = 0.9935) to the standard method with a mean recovery rate of 78.1% (±5.2%) was determined. Even though the results of the new method are not 100% of the standard method, its high correlation to the standard method and reproducibility offers an environmentally benign alternative method with no need to purchase new laboratory equipment.