Stability of fluorinated surfactants in advanced oxidation processes--A follow up of degradation products using flow injection-mass spectrometry, liquid chromatography-mass spectrometry and liquid chromatography-multiple stage mass spectrometry.

The advanced oxidation process (AOP) reagents ozone (O3), O3/UV, O3/H2O2, and H2O2/Fe2+ (Fenton's reagent) were applied to the anionic and the non-ionic fluorinated surfactants perfluorooctanesulfonate (PFOS) and N-ethyl-N-(perfluoroalkyl)-sulfonyl-glycinic acid (HFOSA-glycinic acid) or N-ethyl-N-perfluoroalkyl sulfonylamido-2-ethanol polyethoxylates (NEtFASE-PEG), their methyl ethers (NEtFASE-PEG methyl ether) and partly fluorinated alkyl-ethoxylates (FAEO) dissolved in ultrapure water. To monitor the efficiencies of destruction samples were taken during the treatment period of 120 min. After sample concentration by C18-solid phase extraction (SPE) and desorption MS, coupled with atmospheric pressure chemical ionisation (APCI) or electrospray interface (ESI) was applied for detection. No elimination of PFOS was observed while HFOSA-glycinic acid and AOP treated non-ionic surfactants were eliminated by oxidation. Degradation products could be detected and identified. So PFOS was observed during HFOSA-glycinic acid oxidation. Polyethylene glycols (PEG) and PEG methyl ethers were generated from non-ionic fluorinated surfactants beside their oxidation products--aldehydes and acids--all identified by tandem (MS-MS) or multiple stage mass spectrometry (MSn). AOP treatment of FAEO blend resulted in a mixture of partly fluorinated alcohols, separated and identified using GC-MS.

[1]  D. Ollis Comparative Aspects of Advanced Oxidation Processes , 1993 .

[2]  M E Hurtt,et al.  Mechanisms of extrahepatic tumor induction by peroxisome proliferators in male CD rats. , 2001, Toxicological sciences : an official journal of the Society of Toxicology.

[3]  Craig S. Criddle,et al.  Fluorinated Organics in the Biosphere , 1997 .

[4]  Scott A Mabury,et al.  Identification of long-chain perfluorinated acids in biota from the Canadian Arctic. , 2004, Environmental science & technology.

[5]  H. Schröder Surfactants: non-biodegradable, significant pollutants in sewage treatment plant effluents: Separation, identification and quantification by liquid chromatography, flow-injection analysis—mass spectrometry and tandem mass spectrometry , 1993 .

[6]  H. Schröder,et al.  Determination of fluorinated surfactants and their metabolites in sewage sludge samples by liquid chromatography with mass spectrometry and tandem mass spectrometry after pressurised liquid extraction and separation on fluorine-modified reversed-phase sorbents. , 2003, Journal of chromatography. A.

[7]  J. Giesy,et al.  Global distribution of perfluorooctane sulfonate in wildlife. , 2001, Environmental science & technology.

[8]  J. Trosko,et al.  Inhibition of gap junctional intercellular communication by perfluorinated fatty acids is dependent on the chain length of the fluorinated tail , 1998, International journal of cancer.

[9]  Damià Barceló,et al.  Analysis and Fate of Surfactants in the Aquatic Environment , 2003 .

[10]  D. Taves,et al.  Evidence that there are Two Forms of Fluoride in Human Serum , 1968, Nature.

[11]  Isil Akmehmet Balcioglu,et al.  Advanced oxidation of a reactive dyebath effluent: comparison of O3, H2O2/UV-C and TiO2/UV-A processes. , 2002, Water research.

[12]  Scott A Mabury,et al.  Collection of airborne fluorinated organics and analysis by gas chromatography/chemical ionization mass spectrometry. , 2002, Analytical chemistry.

[13]  K. Wallace,et al.  Perfluorooctanoate, perflourooctanesulfonate, and N-ethyl perfluorooctanesulfonamido ethanol; peroxisome proliferation and mitochondrial biogenesis. , 2002, Toxicology letters.