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Though non-toxic, it seems liquid silicone can block the bood pathways in your body if it gets in your system. Also, industrial grade (and cheaper) silicone can contain toxic additives, which has been causing a stir lately.
However, accidentally ingesting a tiny amount of non-liquid food grade silicone particulates shouldn't raise any concerns, but I see why op might still be wary about it in a spigot.
To op: Have you considered getting a spigot with silicone o-rings and buying third party natural rubber o-rings to replace them with?
Edit: Ah, just reread that you did for the gaskets. Hm. Lemme see if I can find anything.
Edit 2: I found a site selling natural rubber gasket material. You may have to cut it to size:
https://www.mcmaster.com/products/gaskets/water-resistant-high-pressure-natural-rubber-gasket-material/
Edit 3: Natural rubber spigot o-rings doesn't seem to yield many results, but I got some hits for natural rubber faucet o-rings. Maybe try there? Hope you find what you're looking for.
Thank you for your very comprehensive response. I am currently trying to replace the outer silicone gaskets with cork, with mixed results, which is why I hoped that natural rubber may do the trick. I also did see that the inner O-rings were made of EPDM, so I hoped that those could be replaced with something better for the environment.