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If, only he is having chlorine smell then it should be investigated to rule out neurological cause by brain scan like MRI
If both of you smell then search for source of chlorine smell, if not able to found source, then we should suspect substance use.
In his case, it is better to rule out other causes of headache in following hierarchy:
-Neurological cause: may need MRI for that.
-Pathology in ear, teeth, sinus
I hope this information has been both informative and helpful for you.
Wish you Good Health.
Dr. Ashish Mittal