Sustainable and green persulfate-based chemiluminescent method for on-site estimation of chemical oxygen demand in waters

Highlights

• A CL-based method with a CCD camera as detector is used for measuring COD in water.

• Instead of hazardous dichromate as the oxidant, the non-toxic persulfate is used.

• Persulfate is activated through heat and base, enhancing its oxidizing capacity.

• Analysis throughputs are significantly increased compared to the standard method.

• The persulfate method correlates well with those using dichromate or permanganate.

Abstract

The standard method for estimating the chemical oxygen demand (COD) of water bodies uses dichromate as the main oxidant, a chemical agent whose use has been restricted in the European Union since 2017. This method is hazardous, time-consuming, and burdensome to adapt to on-site measurements. As an alternative and following the current trends of sustainable and green chemistry, a method using the less toxic reagent sodium persulfate as the oxidizing agent has been developed. In this method an excess of persulfate, activated through heating in an alkaline solution, oxidizes the chemically degradable organic fraction through a 2-step radical mechanism. The remaining persulfate is evaluated by chemiluminescence (CL) using luminol and a portable charge-coupled device (CCD) camera. The method provided quantitative recoveries and a sample throughput of >60 samples h⁻¹. It was validated in river water samples by comparison of COD estimations with the standard dichromate method (R = 0.973, p < 0.05) and with a UV–Vis permanganate-based method (R = 0.9998, p < 0.05), the latter being also used for drinking waters. The proposed method is a sustainable and green alternative to the previous used methods. Overall, the method using activated persulfate is suitable for use as COD quantitation/screening tool in surface waters. Considering that its main components are portable, it can be ultimately adapted for in situ analysis at the point of need.