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This study makes a new estimate of the global historical production for perfluorooctane sulfonyl fluoride (POSF), and then focuses on producing a first estimate of the global historical environmental releases of perfluorooctane sulfonate (PFOS). The total historical worldwide production of POSF was estimated to be 96 000 t (or 122 500 t, including unusable wastes) between 1970−2002, with an estimated global release of 45 250 t to air and water between 1970−2012 from direct (manufacture, use, and consumer products) and indirect (PFOS precursors and/or impurities) sources. Estimates indicate that direct emissions from POSF-derived products are the major source to the environment resulting in releases of 450−2700 t PFOS into wastewater streams, primarily through losses from stain repellent treated carpets, waterproof apparel, and aqueous fire fighting foams. Large uncertainties surround indirect sources and …