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They sat at the counter as/since all the seats were filled.

I've seen both versions. For example here.

Are as and since are interchangeable in situations like these? If so, in which situations are they not?

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Yes, they are interchangeable here. They are generally interchangeable when they have the sense of because. They are not interchangeable when they have other senses, especially their senses that relate to time. When used in relation to time, as means at the same time, and since means all the time after.

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They are not interchangeable here; "since" creates an ambiguity as it is generally associated with time. Consider: "They sat at the counter since all the seats were filled." There is ambiguity in this usage - does "since" relate to time or cause? Using "as" instead eliminates the ambiguity. Consider: "They sat at the counter as all the seats were filled." That seems to nail causation rather than time.

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