Thermolysis of fluoropolymers as a potential source of halogenated organic acids in the environment

@article{Ellis2001ThermolysisOF,
  title={Thermolysis of fluoropolymers as a potential source of halogenated organic acids in the environment},
  author={David A. Ellis and Scott A. Mabury and Jonathan W. Martin and Derek C. G. Muir},
  journal={Nature},
  year={2001},
  volume={412},
  pages={321-324}
}
Following the introduction of hydrochlorofluorocarbon (HCFCs) and hydrofluorocarbon (HFCs) gases as replacements for the ozone-destroying chlorofluorocarbons (CFCs), it has been discovered that HCFCs/HFCs can degrade in the atmosphere to produce trifluoroacetic acid, a compound with no known loss mechanisms in the environment, and higher concentrations in natural waters have been shown to be mildly phytotoxic. Present environmental levels of trifluooracetic acid are not accounted by HCFC/HFC… 
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References

SHOWING 1-10 OF 46 REFERENCES
Trifluoroacetate in the environment evidence for sources other than HFC/HCFCs
The partly halogenated C2-hydro(chloro)fluorocarbons (HFC, HCFC) 1,1,1-trifluoro-2,2-dichloroethane (HCFC-123), 1,1,1,2-tetrafluoro-2-chloroethane (HCFC-124), and 1,1,1,2-tetrafluoroethane (HFC-134a)
The Aqueous Photolysis of TFM and Related Trifluoromethylphenols. An Alternate Source of Trifluoroacetic Acid in the Environment
The lampricide 3-trifluoromethyl-4-nitrophenol (TFM) is added annually to the Great Lakes (approximately 50 000 kg/y), with treatment concentrations varying from 1 to 14 mg/L at source. TFM was shown
Accumulation of trifluoroacetate in seasonal wetlands in California.
TLDR
It is demonstrated that seasonal wetlands lacking outflow concentrated TFA as they evaporated during the dry season, and the TFA within the pools was retained between years, which may result in long-term TFA accumulation.
Concentrations and Mass Fluxes of Chloroacetic Acids and Trifluoroacetic Acid in Rain and Natural Waters in Switzerland
Chloroacetic acids (CAAs) and trifluoroacetic acid (TFA) are widely distributed environmental pollutants. The origin of CAAs is still under debate, while TFA is considered to be a major atmospheric
Detection of Chlorodifluoroacetic Acid in Precipitation: A Possible Product of Fluorocarbon Degradation
Chlorodifluoroacetic acid (CDFA) was detected in rain and snow samples from various regions of Canada. Routine quantitative analysis was performed using an in-situ derivatization technique that
Atmospheric Lifetimes of Long-Lived Halogenated Species
The atmospheric lifetimes of the fluorinated gases CF4, C2F6, c-C4F8, (CF3)2c-C4F6, C5F12, C6F14, C2F5Cl, C2F4C12, CF3Cl, and SF6 are of concern because of the effects that these long-lived compounds
The atmospheric degradation and impact of 1,1,1,2-tetrafluoroethane (hydrofluorocarbon 134a)
Shock Tube Study of the Oxidation of C3F6 by N2O
The kinetics of the high-temperature oxidation of C3F6 by O(3P) have been studied by experiment, using a single-pulse shock tube, and by kinetic modeling. The O atoms were generated by the thermal
Toxicity of trifluoroacetate to aquatic organisms
TLDR
A TFA concentration of 0.10 mg/L is considered safe for the aquatic ecosystem and algal toxicity tests with NaTFA should be considered algistatic and not algicidic for S. capricornutum.
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