As the complexity of markets and the dynamicity of systems evolve, the need for interoperable systems capable of strengthening enterprise communication effectiveness increases. This is particularly significant when it comes to collaborative networks, where communication is a central aspect with a direct impact in the outcome of the network. Such is the case of enterprise networks (e.g. manufacturing supply chains), where several companies need to work, communicate, and depend on each other, in order to achieve a specific goal. Once interoperability is achieved, organisations are able to exchange information along a stable environment that follows agreed laws. However, as markets tend to adapt to new requirements and demands, an evolutionary behaviour is triggered giving space to interoperability problems. This disrupts the sustainability of interoperability and raises the need to develop monitoring activities capable of detecting unexpected behaviour in communications between cooperating companies. This paper focuses on monitoring techniques for interoperable SOA-based enterprise networks using web services, focusing mainly on the automatic detection of harmonization breaking during real-time communications. It also proposes an approach to handle the disruption of harmonization with reduced human intervention.