Segmented flow injection, UV digestion, and amperometric detection for the determination of total cyanide in wastewater treatment plant effluents.

Abstract

The currently approved method for the analysis of total cyanide (TCN) in wastewaters has remained virtually unchanged in the 25 years since its initial use; this despite its subjection to a number of interferences, many of which provide a positive bias in cyanide measurements, including the formation of TCN during sample processing and some of which remain undocumented to this day. In particular, many municipal wastewater treatment plant chlorinated effluents throughout North America have often been cited for permit violations on the levels of total cyanide in their effluents measured using this methodology. A recently developed procedure for the analysis of TCN in various matrixes that utilizes segmented flow injection for sample transport and reaction, on-line acidic UV digestion for conversion of complexed cyanide to HCN, and amperometric detection achieved within 4 min of sample injection is demonstrated on chlorinated effluents discharged from municipal wastewater treatment plants. Through a systematic evaluation of the chemistry of the processes involved in this method and an understanding of the complexity of the wastewater matrix, an application was developed that showed consistent reproducibility in measuring TCN in a variety of effluents. The method was employed initially on synthetic solutions containing controlled levels of constituents identified in the literature as interfering with the measurement of TCN through the traditional distillation/colorimetric approach. In its application to the analysis of TCN in chlorinated wastewaters, an approach was evolved that ensured that dechlorination carried out during sample processing did not bias the results of analysis.