In order to improve our understanding of the nature, measurement and prediction of salts of perfluorooctanoic acid (PFOA) in air, two studies were performed along the fence line of a fluoropolymer manufacturing facility. First, a six-event, 24-hr monitoring series was performed around the fence line using the OSHA versatile sampler (OVS) system. Perfluorooctanoate concentrations were determined as perfluorooctanoic acid (PFOA) via liquid chromatography and mass spectrometry. Those data indicated that the majority of the PFOA was present as a particulate. No vapor-phase PFOA was detected above a detection limit of approximately 0.07 microg/m3. A follow-up study using a high-volume cascade impactor verified the range of concentrations observed in the OVS data. Both studies aligned with the major transport direction and range of concentrations predicted by an air dispersion model, demonstrating that model predictions agreed with monitoring results. Results from both monitoring methods and predictions from air dispersion modeling showed the primary direction of transport for PFOA was in the prevailing wind direction. The PFOA concentration measured at the site fence over the 10-week sampling period ranged from 0.12 to 0.9 microg/m3. Modeled predictions for the same time period ranged from 0.12 to 3.84 microg/m3. Less than 6% of the particles were larger than 4 microm in size, while almost 60% of the particles were below 0.3 microm. These studies are believed to be the first published ambient air data for PFOA in the environment surrounding a manufacturing facility.
The potential for airborne emissions to undergo long-range transport or to be removed from the atmosphere is influenced by their physical-chemical properties. When perfluorooctanate (PFO) enters the environment, its physical-chemical properties can vary significantly, depending on whether it exists as an acid, a salt, or a dissociated ion. A summary of the physical-chemical properties of the three most likely environmental states: ammonium perfluorooctanoate (APFO), perfluorooctanoic acid (PFOA) and the dissociated perfluorooctanoate anion (PFO(-)) is presented to illustrate the distinct environmental properties of each. The most volatile species, PFOA, is shown to have a pH-dependent air-water partitioning coefficient (K(aw)). The variability of K(aw) with pH influences the potential for vapor formation from aqueous environments, including rain events. Using the pH-dependent K(aw) and measured rain and air concentrations, it is shown that vapor-phase PFOA is not likely to be present above measurable levels of 0.2 ng m(-3) (12 parts per quadrillion v/v) during a rain event. Because rain concentrations determined in this work are comparable to measurements in other parts of North America, it is unlikely that rain events are a significant source of vapor-phase PFOA for the general North American region. It is shown that PFOA exists primarily in the particle phase in ambient air near direct sources of emissions and is efficiently scavenged by rain droplets, making wet deposition an important removal mechanism for emissions originating as either PFOA or APFO. Washout ratios of particle-associated PFO were determined to range between 1 x 10(5) and 5 x 10(5), in the same range as other semi-volatile compounds for which wet deposition is an important mechanism for atmospheric removal and deposition onto soils and water bodies.
A modified gas saturation method was used to determine the solid vapor pressure of perfluorooctanoic acid (PFOA) at ambient temperatures. Measurements were made over the temperature range from (25 to 45) °C. Pressures ranged from (5.2 to 40.7) Pa. The enthalpy of sublimation was calculated as 88.9 kJ • mol -1 .
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