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I'm sure there are some kinds of leaves that are toxic. How you would distinguish them, I'm not sure (of course, pine needles would need to be avoided). You'd have to be certain of the type of tree the leaves came from before using them (I think MOST american hardwoods would be safe, like maple and oak, but there might even be hardwoods that are toxic, I just don't know enough about all the types).
As far as sterilization - it seems like it would be very difficult to sterilize leaves without ruining them or making them soggy, or risking a fire. Most people bake sticks in the oven, but I know I wouldn't want to do that with leaves because they are so thin and tend to be dry (I use dry leaves as kindling!). Another option that wouldn't ruin them might be to freeze them for a while.
But I don't know that leaves would make a good substrate on their own... leaves do not absorb liquid well. If you used only leaves as substrate, it would be a pain to clean up. However, if you just planned to sprinkle a few leaves on another type of substrate, like cypress mulch, it might make a nice decoration.
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