I think they cut/erased the background and then saved the PNG and pasted it into another background with a degraded effect? Not really sure but I think that's what I would do (I'm not a photoshop expert nor a graphic designer, though).
You'll have to be really good at cutting/erasing backgrounds.
Other than extracting the background (obviously), it looks like might they have done some adjusting on the exposure, burn tool on some areas like the sides of his face and eyes to make it look darker, selective color adjustment to make it less magenta-ish and more yellow and warmer. Curves to accentuate the shadows and colors too. Some sharpen to make the details more visible and some noise to add texture.
