Most hangover symptoms are due to the lack of judgement, low impairment, numbing and pain killing effects of alcohol. If you drink a lot you will usually do things your body is not capable off without getting damaged and you do not notice because you are drunk. However as your body breaks down the alcohol and you sober up the symptoms are no longer masked.
There are also toxins generated as a byproduct of the body breaking down alcohol. And although they do not cause the severy symptoms normally associated with a bad hangover there is some milder symptoms that could be explained by some of these. Most notably acetaldehyde which is a byproduct of alcohol breakdown which is known to cause headaches in clinical trials. There is still active research on this but for now it does not seam like this is the main cause of headaches in hangover. All the dehydration, sensory overload, lack of sleep, etc. that comes with a night out is probably the main cause of headache. And there is a very effective antidote to acetaldehyde in caffeine which is not as effective in real hangover patients as in clinical trials with acetaldehyde.
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