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pfft,

I presume you have two layers? If so Command + Click (PC Control + Click) on the head layer to create a selection. Choose Select > Inverse to select the transparent area of the layer. (You could just have the head layer active and use the magic wand on the transparent area, too.) Now expand the selection (Selection > Modify > Expand...) by two or three pixels or so (which ever gets almost all the white on the shoulders. Now feather the selection by one pixel (Select > Feather...).

Now take the eraser tool and make a huge brush to cover the whole head (use the right bracket key to increase the brush size). Click to erase everything inside the selection which will be just a border around the head and shoulders. That should get rid of most of the white. Now inverse the selection and use the burn tool set to Highlights and about a 20% exposure and go around the hair and shoulders to darken the hair and any remaining highlights on the shoulders and you can end up with a result like the one below.