In the occurrence of environmental disasters involving water resources, deploying an emergency monitoring network for assessing water quality is within the first measures to be taken. Emergency networks usually cover a large set of water quality variables and monitoring stations along the watershed. Focusing on variables that represent greater risk to the environment and have less predictable spatial and temporal distribution is a strategy to optimize efforts on monitoring. The goal of this study is to assess the use of Shannon's entropy to identify non-critical water quality variables in an emergency monitoring network implemented in a watershed impacted by the collapse of a mining iron tailing dam, the Doce River watershed (Brazil). Monitoring stations were grouped into water quality subregions through cluster analysis and Shannon's entropy was used to estimate information redundancy of monitored variables. From information redundancy and after checking for compliance with environment normative, non-critical water quality variables were identified. Results indicated that non-critical variables represent 32–50% of the variables monitored. Emergency network managers find in this method a robust tool to improve the network performance. However, special attention should be paid to outliers' presence that can bias analyses based on Shannon's entropy.