I usually buy compressed bricks of it over the internet (for example, from joshsfrogs.com - they are one of our sponsors but I do actually buy from them). Actually the most recent brick I bought was from Petsmart or Petco but only because I needed just 1 brick and it was cheaper than mail order to get just 1 brick. You can also buy it uncompressed in bags at Petsmart and Petco, and from online pet stores.
Quite frankly, I don't see an issue with using any of those substrates, provided the animals you're keeping are not at risk of ingesting sharp particles and such. It's not like the chemicals and structures are unique to those ingredients. What _are_ you keeping in there any how?
Answering number 1, there aren't that many tree species that produce "toxic" leaves. Off the top of my head, I actually can't think of a deciduous tree that does. So I wouldn't worry so much about that aspect. The main concern I would have is how long you want the leaves to hold up in the terrarium - thin flexible leaves like maple/sycamore will rot very quickly in comparison to the dart frog favorites of magnolia and "live oak".
I suppose that answers both of the questions to some degree. If you want to get into more specifics, please go ahead.





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