According to Forbes.com, the dirtiest city in the world (not only by air pollution) is Baku, Azerbaijan. The recent discovery of oil in this small country means that transporting the oil creates high amounts of air pollution.
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The world's dirtiest is country is without a doubt, Algeria. You probably would never know it for yourself as you would probably never go there. But, if you go, be prepared to swim next to highly polluted sewers, to scoop up plastic bags, batteries from the beach, to photograph burnt down forest littered with plastic bag. If one needs to pooh, then avoid toilets, better go outside. Do not buy any food from markets, as it would probably be expired product imported from an ex soviet country. Do not buy meat, as it would most certainly be rotten, if it is fresh, then it is probably donkey meat (you can eat it if you don't mind it).