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Frontiers of Environmental Science & Engineering

Front Envir Sci Eng Chin    2009, Vol. 3 Issue (2) : 129-151
Treatment technologies for aqueous perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA)
Chad D. VECITIS1, Hyunwoong PARK1, Jie CHENG1, Brian T. MADER2, Michael R. HOFFMANN1(email.png)
1. 1. W. M. Keck Laboratories, California Institute of Technology, Pasadena, California 91125, USA; 2. 2. 3M Environmental Laboratory, 3M Center, Building 260-05-N-17, Maplewood, MN 55144-1000, USA
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Fluorochemicals (FCs) are oxidatively recalcitrant, environmentally persistent, and resistant to most conventional treatment technologies. FCs have unique physiochemical properties derived from fluorine which is the most electronegative element. Perfluorooctanesulfonate (PFOS), and perfluorooctanoate (PFOA) have been detected globally in the hydrosphere, atmosphere and biosphere. Reducing treatment technologies such as reverses osmosis, nano-filtration and activated carbon can? remove ?FCs ?from ?water. ?However,? incineration ?of the concentrated waste is required for complete FC destruction. Recently, a number of alternative technologies for FC decomposition have been reported. The FC degradation technologies span a wide range of chemical processes including direct photolysis, photocatalytic oxidation, photochemical oxidation, photochemical reduction, thermally-induced reduction, and sonochemical pyrolysis. This paper reviews these FC degradation technologies in terms of kinetics, mechanism, energetic cost, and applicability. The optimal PFOS/PFOA treatment method is strongly dependent upon the FC concentration, background organic and metal concentration, and available degradation time.

Keywords fluorochemical (FC) degradation technologies      perfluoroctanesulfonate (PFOS)      perfluorooctanoate      (PFOA)      oxidation      reduction      photolysis      thermolysis      review     
Corresponding Authors: HOFFMANN Michael R.,   
Issue Date: 05 June 2009
 Cite this article:   
Chad D. VECITIS,Hyunwoong PARK,Jie CHENG, et al. Treatment technologies for aqueous perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA)[J]. Front Envir Sci Eng Chin, 2009, 3(2): 129-151.
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techniqueconditionspower(W)& volume(mL)k(Lab)a)productb)energyc) /kJref.
UV direct photolysis1.35 mmolL-1 of PFOAl = 220-460 nm200220.69 d-1t1/2 = 1440 min33% F-38% CO265% PFacids792000(1170 kJ?μmol-1)[93]
UV phosphotungstic photocatalysis1.35 mmol?L-1 of PFOAl = 220-460 nm0.48 MPa of O26.6 m mol?L-1 of PTA200222.0 d-1t1/2 = 500 min30% F-25% CO270% PF acids276000(410 kJ?μmol-1)[93]
TiO2 photocatalysis1.0 mmol?L-1 of PFOAl = 310-400 nmpH= 2-30.1 g of TiO275500.69 d-1t1/2 = 1440 min50% F-50% CO2132000(265 kJ?μmol-1)[104]
UV direct photolysis50 mmol?L-1 of PFOAl = 185 nm2310000.017 min-1t1/2 = 41 min10% F-90% PFacids49(1 kJ?μmol-1)[94]
UV persulfatephotolysis50 μmol?L-1 of PFOAl = 254 nm1.5 mmol?L-1 of S2O82-2310000.012 min-1t1/2 = 58 min5% F-95% PFacids69(1.2 kJ?μmol-1)[94]
UV persulfatephotolysis1.35 mmol?L-1 of PFOAl = 220-460 nm0.48 MPa of O2pH= 2-310 mmol?L-1 of S2O82-200220.69 h-1t1/2 = 58 min12% F-85% PFacids33600(50 kJ?μmol-1)[99]
photocatalysisTiO2/Ni-Cu50 m mol?L-1 of PFOAl = 254 nm232500.0077 min-1t1/2 = 90 min10 % F-90% PFacids500(20 kJ?μmol-1)[102]
photoelectro-catalysisTiO2/Ni-Cu50 mmol?L-1 of PFOAl = 254 nm-0.1 V232500.015 min-1t1/2 = 45 min20% F-80% PFacids250(10 kJ?μmol-1)[102]
persulfate photolysis2.5 mmol?L-1 of PFBAl = 254 nm50 mmol?L-1 of S2O82-602000.0096 min-1t1/2 = 72 min~ 104 L?mol-1?s-1dSO4.- + PFBA-1300(1.0 kJ?μmol-1)[101]
hydrogen peroxide photolysis2.5 mmol?L-1 of PFBAl = 254 nm250 mmol?L-1 of H2O2602003.0e-5 min-1t1/2 = 23100 minn/a420000(320 kJ?μmol-1)[101]
flash photolysis5×10-5 mol?L-1 of Fe(CN)60.02-0.1 mol?L-1 of PFOA266 nm10 ns3 mJ/pulse~107 L?mol-1?s-1dn/an/a[198]
sonolysis20 mmol?L-1 of PFOAf = 354 kHz1506000.018 min-1t1/2 = 39 min95% F-670(67 kJ?μmol-1)[108]
sonolysis200 nmol?L-1 of PFOAf = 354 kHz1506000.047 min-1t1/2 = 15 min95% F-260(1300 kJ?μmol-1)[108]
UV-KI photolysis20 mmol?L-1 of PFOAl = 254 nm1.5300.0014 min-1t1/2 = 500 min10% F-gaseous fluoroalkanes1500(150 kJ?μmol-1)[216]
UV-KI photolysis200 nmol?L-1 of PFOAl = 254 nm1.5300.0025 min-1t1/2 = 280 min10% F-Gaseous fluoroalkanes820(8200 kJ?μmol-1)[216]
Ferro-photolysis2.5 mmol?L-1 of Fe2(SO4)367 mmol?L-1 of PFBAl = 220-460 nm2001050.028 h-1t1/2 = 1490 min45% F-55% short chains89400(2.7 kJ?μmol-1)[168]
Tab.1  Summary of reported results for PFOA degradation
techniqueconditionspower/W& volume/mLk(lab)a)productsb)energyc/kJref.
sub-criticalFe(0)370 μmol?L-1 of PFOS0.5 g of Fe(0)350 oC, 20 MPa0100.013 min-1t1/2 = 53 min50% F-2000(11 kJ?μmol-1)[177]
UV directphotolysis40 μmol?L-1 of PFOSl = 254 nm327500.13 d-1t1/2 = 7700 min71% F-90% SO42-17000(850 kJ?μmol-1)[96]
UV alkaline IPA photolysis40 μmol?L-1 of PFOSl = 254 nm327500.93 d-1t1/2 = 1070 minNaF(s)2500(125 kJ?μmol-1)[96]
sonolysis20 μmol?L-1 of PFOSf = 354 kHz1506000.011 min-1t1/2 = 63 min95% F-100% SO42-945(95 kJ?μmol-1)[108]
sonolysis200 nmol?L-1 of PFOSf = 354 kHz1506000.023 min-1t1/2 = 30 min95% F-100% SO42-450(4500 kJ?μmol-1)[108]
UV-KIphotolysis20 μmol?L-1 of PFOSl =254 nm[KI] = 10 mmol?L-11.5300.002 min-1t1/2 = 350 min50% F-50% fluoroalkanes960(96 kJ?μmol-1)[216]
UV-KIphotolysis200 nmol?L-1 of PFOSl = 254 nm[KI] = 10 mmol?L-11.5300.008 min-1t1/2 = 87 min50% F-50% fluoroalkanes260(1250 kJ?μmol-1)[216]
Tab.2  Summary of reported data for PFOS degradation
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