Photodegradation of fluorotelomer carboxylic 5:3 acid and perfluorooctanoic acid using zinc oxide

Environ Pollut. 2018 Dec;243(Pt A):637-644. doi: 10.1016/j.envpol.2018.09.023. Epub 2018 Sep 6.

Abstract

Occurrence of per- and poly-fluoroalkyl substances (PFASs) in the environment and biota has raised a great concern to public health because these compounds are persistent, bioaccumulative, and toxic. Biodegradation of polyfluoroalkyl substances, particularly long-chain fluorotelomer-based products, can lead to production of various short-chain PFASs, with 5:3 fluorotelomer carboxylic acid (referred as 5:3 FTCA hereafter) as a dominant polyfluoroalkyl metabolite. Perfluoroalkyl acids, particularly perfluorooctanoic acid (PFOA), are toxic and current removal methods are not cost-effective. This study reports the photodegradation of 5:3 FTCA and PFOA using ZnO as a photocatalyst under neutral pH and room temperature conditions. Under long UV wavelength (365 nm), both tetrapod and commercial ZnO can photodegrade 5:3 FTCA. Five removal products-perfluorohexanoic acid, perfluoropentanoic acid, perfluorobutyric acid, 5:2 fluorotelomer carboxylic acid (5:2 FTCA), and inorganic fluoride-were identified, with PFBA and F- as dominant end products. SEM and XPS high-resolution scans on the surface of the utilized ZnO showed less units of CF2 than that in 5:3 FTCA, supporting occurrence of photodegradation of 5:3 FTCA by ZnO. Defluorination of PFOA was not observed with ZnO only, but at pH 5 and in the co-presence of Fe-citrate. PFOA defluorination increased from 0.93% after 3 days of UV light exposure to 3.9% after additional 135 h under direct sunlight exposure. To the authors' best knowledge, this is the first report studying ZnO-catalyzed photodegradation of 5:3 FTCA, and examining the Fe co-addition for PFOA defluorination.

Keywords: 5:2 FTCA; Defluorination; PFOA; Poly and per-fluoroalkyl substances (PFASs). 5:3 FTCA; Tetrapod ZnO.

MeSH terms

  • Biodegradation, Environmental
  • Caproates
  • Caprylates / chemistry*
  • Carboxylic Acids
  • Fluorides
  • Fluorocarbons / chemistry*
  • Models, Chemical*
  • Phosphates
  • Photolysis*
  • Zinc Oxide / chemistry*

Substances

  • Caproates
  • Caprylates
  • Carboxylic Acids
  • Fluorocarbons
  • Phosphates
  • fluorophosphate
  • perfluorobutyric acid
  • perfluorooctanoic acid
  • Fluorides
  • Zinc Oxide
  • perfluorohexanoic acid