It has nothing to do with unions allowing anything. In Ontario, Section 43 of the Occupational Health and Safety Act lays out an employee's right to refuse dangerous work, unionize or not, and police are among the group of workers that are exempt. A key component is if the risk is inherent in the work. For a cop, the risk of getting shot is inherent - being made to drive on bald tires is not. Assuming "fish cops" are DFO, no doubt there is similar federal legislation. I have no difficulty with defensive overwatch of maritime law enforcement; that is part of their mandate, but the discussion seemed to me as proposing the CG as part of an Arctic naval military presence, not law enforcement. Perhaps I misunderstood.
Perhaps it would be beneficial to mimic the USCG divisions of white fleet (national security), black fleet (bouy tenders, etc.) and red fleet (heavy ice breaker).