Provided are flow batteries that include a fluidic train within a dynamic fluidic network system which fluidic train is convertible between a first state and a second state, the first state the first state placing a main electrolyte source and a dynamic fluidic network, outside the fluidic train and an electrode region, into fluid communication with the electrode region and the second state placing the main electrolyte source and the dynamic fluidic network, outside the fluidic train and the electrode region, into fluid isolation from the electrode region and placing the electrode region into fluid communication with a sampling segment. Also provided are methods of operating flow batteries.