skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: A survey of analytical methods employed for monitoring of Advanced Oxidation/Reduction Processes for decomposition of selected perfluorinated environmental pollutants

Journal Article · · Talanta
 [1];  [2];  [3];  [4];  [4];  [4];  [4]
  1. Institute of Nuclear Chemistry and Technology, Warsaw (Poland); Univ. of Warsaw (Poland)
  2. Institute of Nuclear Chemistry and Technology, Warsaw (Poland); University of Notre Dame, IN (United States)
  3. DuPont Corporate Center for Analytical Sciences, Wilmington, DE (United States)
  4. Institute of Nuclear Chemistry and Technology, Warsaw (Poland)

The monitoring of Advanced Oxidation/Reduction Processes (AO/RPs) for the evaluation of the yield and mechanisms of decomposition of perfluorinated compounds (PFCs) is often a more difficult task than their determination in the environmental, biological or food samples with complex matrices. This is mostly due to the formation of hundreds, or even thousands, of both intermediate and final products. The considered AO/RPs, involving free radical reactions, include photolytic and photocatalytic processes, Fenton reactions, sonolysis, ozonation, application of ionizing radiation and several wet oxidation processes. The main attention is paid to the most commonly occurring PFCs in the environment, namely PFOA and PFOS. The most powerful and widely exploited method for this purpose is without a doubt LC/MS/MS, which allows the identification and trace quantitation of all species with detectability and resolution power depending on the particular instrumental configurations. The GC/MS is often employed for the monitoring of volatile fluorocarbons, confirming the formation of radicals in the processes of C–C and C–S bonds cleavage. For the direct monitoring of radicals participating in the reactions of PFCs decomposition, the molecular spectrophotometry is employed, especially electron paramagnetic resonance (EPR). The UV/Vis spectrophotometry as a detection method is of special importance in the evaluation of kinetics of radical reactions with the use of pulse radiolysis methods. The most commonly employed for the determination of the yield of mineralization of PFCs is ion-chromatography, but there is also potentiometry with ion-selective electrode and the measurements of general parameters such as Total Organic Carbon and Total Organic Fluoride. Finally, the presented review is based on about 100 original papers published in both analytical and environmental journals.

Research Organization:
University of Notre Dame, IN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FC02-04ER15533
OSTI ID:
1538870
Alternate ID(s):
OSTI ID: 1549981
Journal Information:
Talanta, Vol. 177, Issue C; ISSN 0039-9140
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 16 works
Citation information provided by
Web of Science

References (121)

Determination of Total Organic Fluorine (TOF) in environmental samples using flow-injection and chromatographic methods journal January 2011
Analysis of 18 perfluorinated compounds in river waters: Comparison of high performance liquid chromatography–tandem mass spectrometry, ultra-high-performance liquid chromatography–tandem mass spectrometry and capillary liquid chromatography–mass spectrometry journal June 2012
Buffers for fluoride electrode calibration in the low concentration range journal October 1979
Hydrothermally Enhanced Electrochemical Oxidation of High Concentration Refractory Perfluorooctanoic Acid journal December 2011
Global emission inventories for C4–C14 perfluoroalkyl carboxylic acid (PFCA) homologues from 1951 to 2030, Part I: production and emissions from quantifiable sources journal September 2014
Efficient degradation of perfluorooctanoic acid by UV–Fenton process journal March 2012
Hybrid biological, electron beam and zero-valent nano iron treatment of recalcitrant metalworking fluids journal April 2016
Efficient decomposition of perfluorocarboxylic acids in aqueous solution using microwave-induced persulfate journal June 2009
Electron beam treatment for potable water reuse: Removal of bromate and perfluorooctanoic acid journal October 2016
Determination of fluoride as fluorosilane derivative using reversed-phase HPLC with UV detection for determination of total organic fluorine: Liquid Chromatography journal July 2010
Heat-activated persulfate oxidation of PFOA, 6:2 fluorotelomer sulfonate, and PFOS under conditions suitable for in-situ groundwater remediation journal February 2016
Efficient Decomposition of Perfluorocarboxylic Acids and Alternative Fluorochemical Surfactants in Hot Water journal October 2008
Perfluoroalkyl Acids: A Review of Monitoring and Toxicological Findings journal May 2007
Insights into perfluorooctane sulfonate photodegradation in a catalyst-free aqueous solution journal March 2015
Photocatalytic decomposition of perfluorooctanoic acid by transition-metal modified titanium dioxide journal May 2015
Efficient Decomposition of Environmentally Persistent Perfluorocarboxylic Acids by Use of Persulfate as a Photochemical Oxidant journal April 2005
Recent developments in methods for analysis of perfluorinated persistent pollutants journal July 2013
Treatment technologies for aqueous perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) journal May 2009
Study of the performance of three LC-MS/MS platforms for analysis of perfluorinated compounds journal July 2010
Photo-reductive defluorination of perfluorooctanoic acid in water journal May 2010
Fluorescent and Luminescent Probes for Monitoring Hydroxyl Radical under Biological Conditions journal June 2015
Global Distribution of Perfluorooctane Sulfonate in Wildlife journal April 2001
Determination of free and total fluoride in rain water using a continuous-flow system equipped with a fluoride ion-selective electrode detector journal May 1998
Degradation of Fluorotelomer Alcohols:  A Likely Atmospheric Source of Perfluorinated Carboxylic Acids journal June 2004
Effect of vacuum ultraviolet on ultrasonic defluorination of aqueous perfluorooctanesulfonate journal December 2013
Simultaneous determination of eighteen perfluorinated compounds in dissolved and particulate phases of wastewater, and in sewage sludge by liquid chromatography-tandem mass spectrometry journal January 2014
Fluorotelomer Carboxylic Acids and PFOS in Rainwater from an Urban Center in Canada journal May 2005
Determination of Perfluorooctanoate and Perfluorooctanesulfonate in Water Matrices by Inline Matrix Elimination Liquid Chromatography with Reversed Phase Separation and Suppressed Conductivity Detection journal September 2011
Combined electron-beam and biological treatment of dyeing complex wastewater. Pilot plant experiments journal April 2002
A global survey of perfluorinated acids in oceans journal January 2005
Optimization of the ion chromatographic quantification of airborne fluoride, acetate and formate in the Metropolitan Museum of Art, New York journal October 2011
Electrochemical Oxidation of Environmentally Persistent Perfluorooctane Sulfonate by a Novel Lead Dioxide Anode journal September 2016
Effects of titanate nanotubes synthesized by a microwave hydrothermal method on photocatalytic decomposition of perfluorooctanoic acid journal August 2011
Photodegradation of perfluorooctanoic acid by synthesized TiO2–MWCNT composites under 365nm UV irradiation journal February 2012
Physicochemical Properties and Aquatic Toxicity of Poly- and Perfluorinated Compounds journal January 2013
High-performance liquid chromatography with conductimetric detection of perfluorocarboxylic acids and perfluorosulfonates journal October 2004
Behaviour and fate of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in drinking water treatment: A review journal March 2014
Theoretical studies on the pKa values of perfluoroalkyl carboxylic acids journal June 2010
Theoretical and Experimental Insights into the Electrochemical Mineralization Mechanism of Perfluorooctanoic Acid journal December 2013
Application of Radiation Chemistry to Some Selected Technological Issues Related to the Development of Nuclear Energy journal August 2016
Degradation and reduction of acute toxicity of environmentally persistent perfluorooctanoic acid (PFOA) using VUV photolysis and TiO 2 photocatalysis in acidic and basic aqueous solutions journal May 2011
LC-MS analysis in the aquatic environment and in water treatment ? a critical review journal February 2004
Photodegradation of Perfluorooctane Sulfonate by UV Irradiation in Water and Alkaline 2-Propanol journal August 2007
Photocatalytic decomposition of perfluorooctanoic acid by noble metallic nanoparticles modified TiO 2 journal February 2016
Quantitative Determination of Fluorotelomer Sulfonates in Groundwater by LC MS/MS journal March 2004
Determination of Perfluorinated Surfactants in Surface Water Samples by Two Independent Analytical Techniques:  Liquid Chromatography/Tandem Mass Spectrometry and 19 F NMR journal May 2001
Toxicity identification of gamma-ray treated phenol and chlorophenols journal March 2009
Analysis of Perfluorinated Acids at Parts-Per-Quadrillion Levels in Seawater Using Liquid Chromatography-Tandem Mass Spectrometry journal November 2004
Selective Removal of Perfluorooctanoic Acid Using Molecularly Imprinted Polymer-Modified TiO 2 Nanotube Arrays journal January 2016
Fabrication of novel SnO2-Sb/carbon aerogel electrode for ultrasonic electrochemical oxidation of perfluorooctanoate with high catalytic efficiency journal June 2013
Reductive Defluorination of Aqueous Perfluorinated Alkyl Surfactants: Effects of Ionic Headgroup and Chain Length journal January 2009
Kinetics and Mechanism of the Sonolytic Conversion of the Aqueous Perfluorinated Surfactants, Perfluorooctanoate (PFOA), and Perfluorooctane Sulfonate (PFOS) into Inorganic Products journal May 2008
Recent developments in trace analysis of poly- and perfluoroalkyl substances journal March 2011
Photocatalytic decomposition of perfluorooctanoic acid in pure water and sewage water by nanostructured gallium oxide journal October 2013
Comparison of Three Types of Mass Spectrometer for High-Performance Liquid Chromatography/Mass Spectrometry Analysis of Perfluoroalkylated Substances and Fluorotelomer Alcohols journal October 2004
Total organic carbon analyzers as tools for measuring carbonaceous matter in natural waters journal January 2001
The effect of oxygen in the photocatalytic oxidation pathways of perfluorooctanoic acid journal November 2015
Evidence that there are Two Forms of Fluoride in Human Serum journal March 1968
Determination of trace levels of total fluorine in water using combustion ion chromatography for fluorine: A mass balance approach to determine individual perfluorinated chemicals in water journal March 2007
Efficient Electrochemical Oxidation of Perfluorooctanoate Using a Ti/SnO 2 -Sb-Bi Anode journal April 2011
Degradation of PFOA by hydrogen peroxide and persulfate activated by iron-modified diatomite journal September 2016
Extraction and clean-up strategies for the analysis of poly- and perfluoroalkyl substances in environmental and human matrices journal June 2007
Analysis of fluoride in rain water comparison of capillary electrophoresis with ion chromatography and ion-selective electrode potentiometry journal July 1996
Pulse radiolytic investigation of perfluorinated surfactants in aqueous solutions journal January 2000
Analytical chemistry of perfluoroalkylated substances journal April 2006
Trace analysis of per- and polyfluorinated alkyl substances in various matrices—How do current methods perform? journal January 2009
Removal of perfluorooctanoic acid and perfluorooctane sulfonate via ozonation under alkaline condition journal December 2012
Reductive defluorination of perfluorooctanoic acid by hydrated electrons in a sulfite-mediated UV photochemical system journal November 2013
Synthesis of In2O3 porous nanoplates for photocatalytic decomposition of perfluorooctanoic acid (PFOA) journal January 2014
Fractionation and Bioaccumulation of Perfluorooctane Sulfonate (PFOS) Isomers in a Lake Ontario Food Web journal December 2008
Efficient Reductive Decomposition of Perfluorooctanesulfonate in a High Photon Flux UV/Sulfite System journal September 2016
Experimental p K a Determination for Perfluorooctanoic Acid (PFOA) and the Potential Impact of p K a Concentration Dependence on Laboratory-Measured Partitioning Phenomena and Environmental Modeling journal December 2008
Perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) in surface waters, sediments, soils and wastewater – A review on concentrations and distribution coefficients journal May 2013
Complete mineralization of perfluorooctanoic acid (PFOA) by γ-irradiation in aqueous solution journal December 2014
Perfluorinated Surfactants and the Environmental Implications of Their Use in Fire-Fighting Foams journal September 2000
Photocatalytic decomposition of perfluorooctanoic acid (PFOA) by TiO2 in the presence of oxalic acid journal September 2011
Efficient degradation of perfluorooctanoic acid (PFOA) by photocatalytic ozonation journal July 2016
Perfluorooctanoic Acid Degradation Using UV–Persulfate Process: Modeling of the Degradation and Chlorate Formation journal December 2015
Use of Fenton reagent combined with humic acids for the removal of PFOA from contaminated water journal September 2016
Degradation and Removal Methods for Perfluoroalkyl and Polyfluoroalkyl Substances in Water journal September 2016
Role of Water in Electron-Initiated Processes and Radical Chemistry:  Issues and Scientific Advances journal January 2005
Fluorine Speciation Analysis Using Reverse Phase Liquid Chromatography Coupled Off-Line to Continuum Source Molecular Absorption Spectrometry (CS-MAS): Identification and Quantification of Novel Fluorinated Organic Compounds in Environmental and Biological Samples journal June 2012
Effect of surfactants on the degradation of perfluorooctanoic acid (PFOA) by ultrasonic (US) treatment journal January 2016
Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O in Aqueous Solution
  • Buxton, George V.; Greenstock, Clive L.; Helman, W. Phillips
  • Journal of Physical and Chemical Reference Data, Vol. 17, Issue 2 https://doi.org/10.1063/1.555805
journal April 1988
Decomposition of perfluorooctanoic acid by ultraviolet light irradiation with Pb-modified titanium dioxide journal February 2016
Analytical, toxicological and kinetic investigation of decomposition of the drug diclofenac in waters and wastes using gamma radiation journal August 2015
Efficient Decomposition of Environmentally Persistent Perfluorooctanesulfonate and Related Fluorochemicals Using Zerovalent Iron in Subcritical Water journal February 2006
Effect of initial solution pH on photo-induced reductive decomposition of perfluorooctanoic acid journal July 2014
Photodegradation of perfluorooctanoic acid by 185 nm vacuum ultraviolet light journal January 2007
Perfluorooctanoic acid degradation in the presence of Fe(III) under natural sunlight journal November 2013
Quantitative profiling of perfluoroalkyl substances by ultrahigh-performance liquid chromatography and hybrid quadrupole time-of-flight mass spectrometry journal January 2015
Peroxidase-Mediated Degradation of Perfluorooctanoic acid journal January 2009
Monitoring of Perfluorinated Compounds in Aquatic Biota: An Updated Review: PFCs in Aquatic Biota journal October 2011
Novel way of separating polyfluorocarboxylic acids by ion-exclusion chromatography journal July 2000
Defluorination of Aqueous Perfluorooctanesulfonate by Activated Persulfate Oxidation journal October 2013
Sonochemical Degradation of Perfluorooctanesulfonate in Aqueous Film-Forming Foams journal December 2009
Factors controlling the rate of perfluorooctanoic acid degradation in laccase-mediator systems: The impact of metal ions journal May 2017
Perfluorooctanoic acid (PFOA), an emerging drinking water contaminant: A critical review of recent literature journal July 2012
Reductive Defluorination of Perfluorooctane Sulfonate journal May 2008
Epidemiologic Evidence on the Health Effects of Perfluorooctanoic Acid (PFOA) journal August 2010
Standard addition flow method for potentiometric measurements at low concentration levels: Application to the determination of fluoride in food samples journal February 2015
Photochemical reactivity of perfluorooctanoic acid (PFOA) in conditions representing surface water journal July 2011
Separation of perfluoroalkylsulfinic acids and perfluoroalkylsulfonic acids by ion-exclusion chromatography journal June 2001
Sonochemical Decomposition of Perfluorooctane Sulfonate and Perfluorooctanoic Acid journal May 2005
Tracking the Pathways of Human Exposure to Perfluorocarboxylates journal August 2009
Activated Persulfate Oxidation of Perfluorooctanoic Acid (PFOA) in Groundwater under Acidic Conditions journal June 2016
Peer Reviewed: When Synthetic Chemicals Degrade in the Environment journal October 2004
Sources, Fate and Transport of Perfluorocarboxylates journal January 2006
Insight on the fundamentals of advanced oxidation processes. Role and review of the determination methods of reactive oxygen species: Insight on the fundamentals of advanced oxidation processes
  • Fernández-Castro, Pablo; Vallejo, Marta; San Román, Mª Fresnedo
  • Journal of Chemical Technology & Biotechnology, Vol. 90, Issue 5 https://doi.org/10.1002/jctb.4634
journal February 2015
Efficient Photocatalytic Decomposition of Perfluorooctanoic Acid by Indium Oxide and Its Mechanism journal May 2012
Effects of pH on photochemical decomposition of perfluorooctanoic acid in different atmospheres by 185nm vacuum ultraviolet journal November 2014
A Novel Fast Ion Chromatographic Method for the Analysis of Fluoride in Antarctic Snow and Ice journal January 2014
Ferric ion mediated photodecomposition of aqueous perfluorooctane sulfonate (PFOS) under UV irradiation and its mechanism journal April 2014
HPLC determination of perfluorinated carboxylic acids with fluorescence detection journal December 2010
Polyfluoroalkyl compounds in the aquatic environment: a review of their occurrence and fate journal January 2011
A First Global Production, Emission, And Environmental Inventory For Perfluorooctane Sulfonate journal January 2009
Photoinduced Hydrodefluorination Mechanisms of Perfluorooctanoic Acid by the SiC/Graphene Catalyst journal May 2016
Investigation of the reactivity of hydrated electron toward perfluorinated carboxylates by laser flash photolysis journal February 2007
Electrochemical treatment of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) in groundwater impacted by aqueous film forming foams (AFFFs) journal September 2015
Diet and particularly seafood are major sources of perfluorinated compounds in humans journal October 2010
Sonochemical Degradation of Perfluorooctane Sulfonate (PFOS) and Perfluorooctanoate (PFOA) in Groundwater: Kinetic Effects of Matrix Inorganics journal December 2009