Context clues.
Medical examiners don’t just do ‘the autopsy’, they conduct an entire medicolegal investigation.
In addition, the opposite of an ‘accidental’ overdose isn’t a ‘regular’ overdose. It’s either accidental or purposeful, i.e. suicidal overdose (and it is also possible to overdose and not die as well, but I am assuming OP is speaking about fatal overdoses).
There is no such thing as a regular overdose. Presumably an overdose will either be accidental or intentional. From a forensic perspective, an accidental overdose will be one that has serum concentration of the acting agent near to a therapeutic/recreational dose while if the serum concentration is far, far beyond what could remotely be considered normal it can reasonably be presumed that the overdose was intentional.
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