I think by the substrate question, you mean in the film can/beadbox etc. that is being used for isolation. In that case no. They have to be stressed, and not having food and water is a big part of that stress.
I cant think of anything that wouldn't eventually mold, you just have to change it out. Maybe use water gel? but I have no experience with that, so I dont know. Personally I use carrots, sliced kinda thin, and they seem to dry out before they mold. I still pull them out pretty often though.
I haven't heard of the pesticides in potatos thing, but it could be. I doubt it though.
As far as starting a new box, thats actually a question I have my self.
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