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My wife and I have had problems with one of our cats defecating where she isn't supposed to. We've had some success with the synthetic pheremone spray. This is a small spray bottle we got from our vet that simulates "marking" by a dominant cat. You spray a few areas around the house with it every day.
Apparently, it convinces the cat that's marking its territory that it is no longer "their" territory. They stop marking. It has the side effect of making the cat(s) much more laid-back and friendly. They don't seem to have the need to assert authority anymore.
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