The other answers are right, but it’s also important to ask another question.
Instead of “how do they know?” Ask “do they know?”
Because arson investigation suffers from the same confirmation bias that forensic investigation does. If you’ve kept up with forensic investigation over the past 20 years, you know that everything except DNA analysis has come under huge scrutiny for not having rigorous scientific guidelines. Blood spatter, bite mark, and hair analysis are now all considered junk science.
The fields of arson investigation and forensic science have similar origins. They were both largely driven by professionals in their fields (detectives and firemen) and not outside academics. Investigaters in both fields can suffer from the same pressure find a crime where sometimes there isnt one, and this can lead to a false interpretation of the data available. Many people have been convicted of violent crimes by junk forensic science, and smaller, but not insignificant number of people have also been convicted of arson when the actual culprit was faulty wiring or other accidental fire origins.
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