Comparison of and uncertainties in raw sewage COD measurements by laboratory techniques and field UV-visible spectrometry

A comprehensive investigation of the uncertainty of different COD analysis methods (DIN, small tube tests (STT) and UV-visible spectrometry methods) has been carried out on potassium hydrogen phthalate standard solutions and raw sewage samples from a large wastewater treatment plant. The UV-visible method allows estimating COD equivalent concentration from the measured absorption spectra by means of site specific regression and correlation functions. CODdin and CODstt methods showed equivalent global results but specific calibration relationships are necessary when high accuracy is required. The CODstt method is suitable for immediate COD analysis in the field. Sub-sampling is the main source of uncertainty. Spectrometry is able to estimate CODeq with an uncertainty of the same order of magnitude as the uncertainty in CODdin.