I know that urban rainwater is considered to not be potable, but I did consider whether to use it on my few vegetable plants. I decided not to use it on my tomatoes and other veggies.
Dust and ash (from incinerators and coal power plants) are one source of contamination. During a dry period, windblown dust accumulates on roofs. Ash accumulates year-round, depending upon wind direction from the incinerator or power plant. Minerals and toxins from those can be reduced by not collecting the first rain after winter or after a dry spell.
However, bird droppings and squirrel droppings can't be avoided so easily. I could test for minerals and toxins to learn what my water is like, but bird droppings are a more random source and I never know when a flock of something will pass by.
I'm not yet interested in adding filters suitable for removing bacterial contamination, so I'll use potable water for the vegetables. I don't have many of those anyway. The flowers are thirstier, so they'll get the rainwater.
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