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I'm genuinely curious. Can PG handle hundreds of users querying 100s of GB, sometimes the same set of tables, at the same time?

Well. You're going to run out of CPU and memory bandwidth pretty quickly. So you'd need replicas to share processing load.

But I honestly don't think hundreds of users each querying 100s of GBs is all that common.

Again, genuinely curious to learn if you've experience with enterprise companies using 'big data' technologies.

Yes.