Continuous Monitoring of Monochloramine in Water, and Its Distinction from Free Chlorine and Dichloramine Using a Functionalized Graphene-Based Array of Chemiresistors

Monochloramine (MCA) is commonly added to drinking water as a disinfectant to prevent pathogen growth. The generation of MCA at the treatment plant requires tight control over both pH and the ratio of free chlorine (FC) to ammonia to avoid forming undesirable byproducts such as dichloramine (DCA) and trichloramine (TCA), which can impart odor and toxicity to the water. Therefore, continuous monitoring of MCA is essential to ensuring drinking water quality. Currently, standard colorimetric methods to measure MCA rely on the use of reagents and are unsuitable for online monitoring. In addition, other oxidants can interfere with MCA measurement. Here, we present a solid-state, reagent-free MCA sensing method using an array of few-layer graphene (FLG) chemiresistors. The array consists of exfoliated FLG chemiresistors functionalized with specific redox-active molecules that have differential responses to MCA, FC, and DCA over a range of concentrations. Chemometric methods were employed to separate the analytes' responses and to generate multivariate calibration for quantification. A minimum of three sensors are required in the array to maintain full functionality. The array has been demonstrated to quantify MCA in buffered and tap water as a low-cost, reagent-free approach to continuous monitoring.