First of all, I only buy what I need. The "greenest" purchase is the one that isn't made.
Second, I buy things that last - clothes, furniture, etc. If you buy something of quality and enduring "style" chances are you won't have to replace it for a long time.
Third, once I decide to buy something, I try to support merchants that make sustainable/environmentally friendly products and that are responsible corporate citizens (e.g. Patagonia).
On-line or bricks and mortar? Depends. No bricks and mortar experience can beat the web on finding what you want/need, comparing products, etc. I find shopping on-line also helps avoid impulse purchases/upsell that often happens in stores. But it's hard to try things on on-line or see their full-size.
So mostly for convenience, I end up purchasing most things on-line, but I think more important than where you buy is making sure you buy only what you need, buying things that will last and supporting responsible merchants in the process.
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