Feasibility Study on the Removal of Perfluorooctanoic Acid by Using Palladium-Doped Nanoscale Zerovalent Iron
Publication: Journal of Environmental Engineering
Volume 144, Issue 11
Abstract
Perfluorinated chemicals (PFCs) are highly persistent organic contaminants that have become a global health concern. Few studies so far have demonstrated successful decomposition of PFCs under ambient condition. As a result, this feasibility study aimed to quickly examine whether palladium-doped nanoscale zerovalent iron (nZVI/Pd), known to dehalogenate many halogenated chemicals, can remove perfluorooctanoic acid (PFOA) in water, one of the most widely used PFCs. Batch experiments were performed to evaluate the effects of various operation parameters, including reaction pH, nZVI/Pd dose, and PFOA concentration, to find best treatment options for PFOA. Significant removal of PFOA was observed at low pH and high nZVI/Pd dosage while nZVI/Pd was superior to micron-size ZVI and nZVI without Pd. However, the decrease in total organic carbon was very similar to PFOA removal, negligible amounts of fluoride ions were detected in water, and mass spectrometry analysis indicated no significant formation of reaction intermediates. The results implied that the observed PFOA removal was more closely associated with adsorption than reaction (i.e., defluorination). Kinetic models and adsorption isotherm models were employed to explain the PFOA removal and obtain insights on the physicochemical processes around nZVI/Pd interacting with PFOA.
Get full access to this article
View all available purchase options and get full access to this article.
Acknowledgments
This research was supported by the University of Texas at Arlington through faculty start-up funds.
References
Arvaniti, O. S., Y. Hwang, H. R. Andersen, A. S. Stasinakis, N. S. Thomaidis, and M. Aloupi. 2015. “Reductive degradation of perfluorinated compounds in water using Mg-aminoclay coated nanoscale zero valent iron.” Chem. Eng. J. 262: 133–139. https://doi.org/10.1016/j.cej.2014.09.079.
Benford, D., D. J. Boer, A. Carere, D. A. Domenico, N. Johansson, D. Schrenk, G. Schoeters, D. P. Voogt, and E. Dellatte. 2008. “Opinion of the scientific panel on contaminants in the food chain on perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA) and their salts.” EFSA J. 653: 1–131. https://doi.org/10.2903/j.efsa.2008.653.
Carter, K. E., and J. Farrell. 2010. “Removal of perfluorooctane and perfluorobutane sulfonate from water via carbon adsorption and ion exchange.” Sep. Sci. Technol. 45 (6): 762–767. https://doi.org/10.1080/01496391003608421.
Choi, H., S. R. Al-Abed, and S. Agarwal. 2009. “Catalytic role of palladium and relative reactivity of substituted chlorines during adsorption and treatment of PCBS on reactive activated carbon.” Environ. Sci. Technol. 43 (19): 7510–7515. https://doi.org/10.1021/es901298b.
Choi, H., S. R. Al-Abed, S. Agarwal, and D. D. Dionysiou. 2008. “Synthesis of reactive nano Fe/Pd bimetallic system-impregnated activated carbon for the simultaneous adsorption and dechlorination of PCBS.” Chem. Mater. 20 (11): 3649–3655. https://doi.org/10.1021/cm8003613.
Da Silva, C. K. O., W. A. Lawal, P. A. Nfodzo, M. G. R. Vianna, C. A. O. Do Nascimento, and H. Choi. 2016. “Degradation of PFOA by hydrogen peroxide and persulfate activated by iron-modified diatomite.” Appl. Catal., B 192: 253–259. https://doi.org/10.1016/j.apcatb.2016.03.067.
Dillert, R., D. Bahnemann, and H. Hidaka. 2007. “Light-induced degradation of perfluorocarboxylic acids in the presence of titanium dioxide.” Chemosphere 67 (4): 785–792. https://doi.org/10.1016/j.chemosphere.2006.10.023.
Dror, I., T. B. Moshe, and B. Berkowitz. 2009. “Use of nanoparticles for degradation of water contaminants in oxidative and reductive reactions.” In ACS Symp. Series, 23–37. Washington, DC: American Chemical Society Publications.
Du, Z., S. Deng, Y. Bei, Q. Huang, B. Wang, J. Huang, and G. Yu. 2014. “Adsorption behavior and mechanism of perfluorinated compounds on various adsorbents—A review.” J. Hazard. Mater. 274: 443–454. https://doi.org/10.1016/j.jhazmat.2014.04.038.
EPA. 2009. “Document #: EPA/600/R-08/092: Determination of selected perfluorinated alkyl acids in drinking water by solid phase extraction and liquid chromatography/tandem mass spectrometry (LC/MS/MS).” Accessed April 4, 2018. https://www.epa.gov/dwanalyticalmethods/analytical-methods-developed-epa-analysis-unregulated-contaminants.
EPA. 2016. “Drinking water health advisories for PFOA and PFOS.” Accessed April 4, 2018. https://www.epa.gov/ground-water-and-drinking-water/drinking-water-health-advisories-pfoa-and-pfos.
Eskandarian, M., H. Choi, M. Fazli, and M. H. Rasoulifard. 2016. “Effect of UV-led wavelengths on direct photolytic and tio2 photocatalytic degradation of emerging contaminants in water.” Chem. Eng. J. 300: 414–422. https://doi.org/10.1016/j.cej.2016.05.049.
Fujii, S., C. Polprasert, S. Tanaka, P. H. L. Nguyen, and Q. Yong. 2007. “New pops in the water environment: Distribution, bioaccumulation and treatment of perfluorinated compounds: A review paper.” J. Water Supply Res. Technol. AQUA 56 (5): 313–326. https://doi.org/10.2166/aqua.2007.005.
Gao, X., and J. Chorover. 2012. “Adsorption of perfluorooctanoic acid and perfluorooctanesulfonic acid to iron oxide surfaces as studied by flow-through ATR-FTIR spectroscopy.” Environ. Chem. 9 (2): 148–157. https://doi.org/10.1071/EN11119.
Goss, K.-U. 2008. “The values of PFOA and other highly fluorinated carboxylic acids.” Environ. Sci. Technol. 42 (2): 456–458. https://doi.org/10.1021/es702192c.
Hansen, M. C., M. H. Børresen, M. Schlabach, and G. Cornelissen. 2010. “Sorption of perfluorinated compounds from contaminated water to activated carbon.” J. Soils Sediments 10 (2): 179–185. https://doi.org/10.1007/s11368-009-0172-z.
Ho, Y., and G. Mckay. 1998. “A comparison of chemisorption kinetic models applied to pollutant removal on various sorbents.” Process Saf. Environ. Prot. 76 (4): 332–340. https://doi.org/10.1205/095758298529696.
Ho, Y., and G. Mckay. 1999. “Pseudo-second order model for sorption processes.” Process Biochem. 34 (5): 451–465. https://doi.org/10.1016/S0032-9592(98)00112-5.
Hoffman, K., T. F. Webster, M. G. Weisskopf, J. Weinberg, and V. M. Vieira. 2010. “Exposure to polyfluoroalkyl chemicals and attention deficit hyperactivity disorder in U.S. children aged 12–15 years.” Environ. Health Perspect. 118 (12): 1762–1767. https://doi.org/10.1289/ehp.1001898.
Hori, H., A. Yamamoto, E. Hayakawa, S. Taniyasu, N. Yamashita, S. Kutsuna, H. Kiatagawa, and R. Arakawa. 2005. “Efficient decomposition of environmentally persistent perfluorocarboxylic acids by use of persulfate as a photochemical oxidant.” Environ. Sci. Technol. 39 (7): 2383–2388. https://doi.org/10.1021/es0484754.
Key, B. D., R. D. Howell, and C. S. Criddle. 1997. “Fluorinated organics in the biosphere.” Environ. Sci. Technol. 31 (9): 2445–2454. https://doi.org/10.1021/es961007c.
Lien, H., and W. Zhang. 2007. “Nanoscale Pd/Fe bimetallic particles: Catalytic effects of palladium on hydrodechlorination.” Appl. Catal., B 77 (1): 110–116. https://doi.org/10.1016/j.apcatb.2007.07.014.
Limousin, G., J. Gaudet, L. Charlet, S. Szenknect, V. Barthes, and M. Krimissa. 2007. “Sorption isotherms: A review on physical bases, modeling and measurement.” Appl. Geochem. 22 (2): 249–275. https://doi.org/10.1016/j.apgeochem.2006.09.010.
Liu, Y., H. Choi, D. D. Dionysiou, and G. V. Lowry. 2005a. “Trichloroethene hydrodechlorination in water by highly disordered monometallic nanoiron.” Chem. Mater. 17 (21): 5315–5322. https://doi.org/10.1021/cm0511217.
Liu, Y., and G. V. Lowry. 2006. “Effect of particle age ( content) and solution pH on NZVI reactivity: evolution and TCE dechlorination.” Environ. Sci. Technol. 40 (19): 6085–6090. https://doi.org/10.1021/es060685o.
Liu, Y., S. A. Majetich, R. D. Tilton, D. S. Sholl, and G. V. Lowry. 2005b. “TCE dechlorination rates, pathways, and efficiency of nanoscale iron particles with different properties.” Environ. Sci. Technol. 39 (5): 1338–1345. https://doi.org/10.1021/es049195r.
Lutze, H., S. Panglisch, A. Bergmann, and T. Schmidt. 2012. “Treatment options for the removal and degradation of polyfluorinated chemicals.” In Polyfluorinated chemicals and transformation products, edited by T. P. Knepper and F. T. Lange, 103–125. Berlin: Springer.
Merino, N., Y. Qu, R. A. Deeb, E. L. Hawley, M. R. Hoffmann, and S. Mahendra. 2016. “Degradation and removal methods for perfluoroalkyl and polyfluoroalkyl substances in water.” Environ. Eng. Sci. 33 (9): 615–649. https://doi.org/10.1089/ees.2016.0233.
Moriwaki, H., Y. Takagi, M. Tanaka, K. Tsuruho, K. Okitsu, and Y. Maeda. 2005. “Sonochemical decomposition of perfluorooctane sulfonate and perfluorooctanoic acid.” Environ. Sci. Technol. 39 (9): 3388–3392. https://doi.org/10.1021/es040342v.
Morrison, J. 2016. “Perfluorinated chemicals taint drinking water.” Chem. Eng. News 94 (20): 20–22. https://doi.org/10.1289/ehp.1509934.
O’Hagan, D. 2008. “Understanding organofluorine chemistry: An introduction to the C–F bond.” Chem. Soc. Rev. 37 (2): 308–319. https://doi.org/10.1039/b711844a.
Peden-Adams, M. M., J. E. Stuckey, K. M. Gaworecki, J. Berger-Ritchie, K. Bryant, P. G. Jodice, T. R. Scott, J. B. Ferrario, B. Guan, and C. Vigo. 2009. “Developmental toxicity in white leghorn chickens following in ovo exposure to perfluorooctane sulfonate (PFOS).” Reprod. Toxicol. 27 (3): 307–318. https://doi.org/10.1016/j.reprotox.2008.10.009.
Qu, Y., C. Zhang, F. Li, X. Bo, G. Liu, and Q. Zhou. 2009. “Equilibrium and kinetics study on the adsorption of perfluorooctanoic acid from aqueous solution onto powdered activated carbon.” J. Hazard. Mater. 169 (1): 146–152. https://doi.org/10.1016/j.jhazmat.2009.03.063.
Qu, Y., C. Zhang, F. Li, J. Chen, and Q. Zhou. 2010. “Photo-reductive defluorination of perfluorooctanoic acid in water.” Water Res. 44 (9): 2939–2947. https://doi.org/10.1016/j.watres.2010.02.019.
Rayne, S., and K. Forest. 2009. “Perfluoroalkyl sulfonic and carboxylic acids: A critical review of physicochemical properties, levels and patterns in waters and wastewaters, and treatment methods.” J. Environ. Sci. Health Part A 44 (12): 1145–1199. https://doi.org/10.1080/10934520903139811.
Ritter, S. K. 2010. “Fluorochemicals go short.” Chem. Eng. News 88 (5): 12–17. https://doi.org/10.1021/cen-v088n005.p012.
Skutlarek, D., M. Exner, and H. Farber. 2006. “Perfluorinated surfactants in surface and drinking waters.” Environ. Sci. Pollut. Res. Int. 13 (5): 299–307. https://doi.org/10.1065/espr2006.07.326.
Stefaniuk, M., P. Oleszczuk, and Y.-S. Ok. 2016. “Review on nano zerovalent iron (Nzvi): From synthesis to environmental applications.” Chem. Eng. J. 287: 618–632. https://doi.org/10.1016/j.cej.2015.11.046.
Stein, C. R., D. A. Savitz, and M. Dougan. 2009. “Serum levels of perfluorooctanoic acid and perfluorooctane sulfonate and pregnancy outcome.” Am. J. Epidemiol. 170 (7): 837–846. https://doi.org/10.1093/aje/kwp212.
Sun, Y. K., J. X. Li, T. L. Huang, and X. H. Guan. 2016. “The influences of iron characteristics, operating conditions and solution chemistry on contaminants removal by zero-valent iron: A review.” Water Res. 100: 277–295. https://doi.org/10.1016/j.watres.2016.05.031.
Tang, C. Y., Q. S. Fu, D. Gao, C. S. Criddle, and J. O. Leckie. 2010. “Effect of solution chemistry on the adsorption of perfluorooctane sulfonate onto mineral surfaces.” Water Res. 44 (8): 2654–2662. https://doi.org/10.1016/j.watres.2010.01.038.
Thompson, J., G. Eaglesham, J. Reungoat, Y. Poussade, M. Bartkow, M. Lawrence, and J. F. Mueller. 2011. “Removal of PFOS, PFOA and other perfluoroalkyl acids at water reclamation plants in south east Queensland Australia.” Chemosphere 82 (1): 9–17. https://doi.org/10.1016/j.chemosphere.2010.
Tosco, T., M. P. Papini, and C. C. Viggi. 2014. “Nanoscale zerovalent iron particles for groundwater remediation: A review.” J. Cleaner Prod. 77: 10–21. https://doi.org/10.1016/j.jclepro.2013.12.026.
Vecitis, C. D., H. Park, J. Cheng, B. T. Mader, and M. R. Hoffmann. 2008. “Kinetics and mechanism of the sonolytic conversion of the aqueous perfluorinated surfactants, perfluorooctanoate (PFOA), and perfluorooctane sulfonate (PFOS) into inorganic products.” J. Phys. Chem. A 112 (18): 4261–4270. https://doi.org/10.1021/jp801081y.
Villagrasa, M., M. L. De Alda, and D. Barceló. 2006. “Environmental analysis of fluorinated alkyl substances by liquid chromatography–(tandem) mass spectrometry: A review.” Anal. Bioanal. Chem. 386 (4): 953–972. https://doi.org/10.1007/s00216-006-0471-9.
Wang, R., G. Lu, H. Lin, K. Huang, T. Tang, X. Xue, X. Yang, H. Yin, and Z. Dang. 2017. “Relative roles of H-atom transfer and electron transfer in the debromination of polybrominated diphenyl ethers by palladized nanoscale zerovalent iron.” Environ. Pollut. 222: 331–337. https://doi.org/10.1016/j.envpol.2016.12.030.
Wei, J., X. Xu, Y. Liu, and D. Wang. 2006. “Catalytic hydrodechlorination of 2,4-dichlorophenol over nanoscale Pd/Fe: Reaction pathway and some experimental parameters.” Water Res. 40 (2): 348–354. https://doi.org/10.1016/j.watres.2005.10.017.
Zhao, L., J. Bian, Y. Zhang, L. Zhu, and Z. Liu. 2014. “Comparison of the sorption behaviors and mechanisms of perfluorosulfonates and perfluorocarboxylic acids on three kinds of clay minerals.” Chemosphere 114: 51–58. https://doi.org/10.1016/j.chemosphere.2014.03.098.
Information & Authors
Information
Published In
Journal of Environmental Engineering
Volume 144 • Issue 11 • November 2018
Copyright
©2018 American Society of Civil Engineers.
History
Received: Apr 9, 2018
Accepted: Jun 15, 2018
Published online: Sep 12, 2018
Published in print: Nov 1, 2018
Discussion open until: Feb 12, 2019
Authors
Metrics & Citations
Metrics
Citations
Download citation
If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download.