This paper presents a new paradigm for the utilization of video surveillance cameras as optical sensors to augment and significantly improve the reliability and responsiveness of chemical monitoring systems. Incorporated into a hierarchical tiered sensing architecture, cameras serve as 'Tier 1' or 'trigger' sensors monitoring for visible indications after a release of warfare or industrial toxic chemical agents. No single sensor today yet detects the full range of these agents, but the result of exposure is harmful and yields visible 'duress' behaviors. Duress behaviors range from simple to complex types of observable signatures. By incorporating optical sensors in a tiered sensing architecture, the resulting alarm signals based on these behavioral signatures increases the range of detectable toxic chemical agent releases and allows timely confirmation of an agent release. Given the rapid onset of duress type symptoms, an optical sensor can detect the presence of a release almost immediately. This provides cues for a monitoring system to send air samples to a higher-tiered chemical sensor, quickly launch protective mitigation steps, and notify an operator to inspect the area using the camera's video signal well before the chemical agent can disperse widely throughout a building.