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You could, but I don't think its going to do much for you since silicone doesn't adhere to itself very well. Just put a nice thick consistent bead on all your seams and you won't need to worry.. just leak test before setting it up of course.
Silicone releases acetic acid , hence the vinegar smell. I believe that silicone will stick to fresh silicone, but there is no need to have a large fillet for an in tank seam.