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Fingerprint recognition was first used by the Qin Dynasty in 221 BC. This is the earliest record we have of fingerprints being used for crime scene investigations.
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The first ever recorded autopsy was carried out by a Roman physician named Antistius. The autopsy was performed on the late Julius Ceaser.
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An early form of lie detecting was discovered by a Greek doctor named Erasistratus. He found that his patient's heart rate would rapidly increase when lying.
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It wasn't until around 1800 that crime scene investigators started using body temperature and internal bodily gasses as a way of determining the approximate - and sometimes even the exact - time of death.
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Henry Goddard figured out that bullets could be removed from a victim's body and and analyzed to determine what kind of weapon it came from. This was a breakthrough in CSI sciences because it allowed investigators to track down the suspect by cross referencing the bullet with the gun that was used.
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In 1880, Sir Francis Galton came up with some of the first modern-day fingerprint matching techniques (not to be confused with fingerprint recognition first used by the Qin Dynasty).
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In 1960, the FBI began using psychology to help track down suspect in relation to crime scenes.
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DNA matching was first used in 1986 to help crime scene investigators determine who the suspect was in relation to a crime. Interestingly, it was actually used for the first time to prove a suspect's innocence - not guilt.