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Perioxide - If the shirt is light colored. Peroxide can sometimes fade darker colors. You can either pour it on, or spray it on. It's best to let it sit for a few minutes before laundering. I'll spray it on, then let it sit for the time it takes my washer to fill up. I buy the peroxide when it's on sale at 2 bottles for $1 at Wallgreens or a local drug store. I then put it in a well marked spray bottle & keep it in my laundry area. It's good to remove any organic stain (for example, it will remove grape juice, but not grape kool-aid which has an artificial dye).
Oxyclean in the wash cycle can also help. Another thing that can help is for the shirt's owner to exfoliate their armpits once a week by scrubbing with a hand full of plain sugar while in the shower to remove built up deodorant & old skin cells & to use regular deodorant in place of an antiperspirant.
Try soaking the area with white vinegar / baking soda paste and let it sit for a day then launder as usual but add a little more vinegar and baking soda to the water. It worked for me.
I have been using cold water Tide with amazing results. I put a small amount and rub the insides of the shirts and wash inside out. I also use around the collar area.
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