TREATMENT MITIGATION STRATEGIES FOR POLY- AND PERFLUOROALKYL CHEMICALS. December 14, Objective
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1 TREATMENT MITIGATION STRATEGIES FOR POLY- AND PERFLUOROALKYL CHEMICALS Eric Dickenson, Ph.D. R&D Project Manager December 14, 2016 Objective Evaluate the ability of a wide spectrum of full-scale drinking water treatment techniques to remove poly- and perfluoroalkyl substances (PFAS) from raw water or potable reuse sources Water Research Foundation. ALL RIGHTS RESERVED. 1
2 Approach: PFAS Compounds Inclusion in This Study Inclusion in CCL3 Inclusion in UCMR3 Perfluoro Carboxylic Acids Perfluorobutyric acid (PFBA) Perfluoropentanoic acid (PFPnA) Perfluorohexanoic acid (PFHxA) Perfluoroheptanoic acid (PFHpA) Perfluorooctanoic acid (PFOA) Perfluorononanoic acid (PFNA) Perfluorodecanoic acid (PFDA) Perfluoroundecanoic acid (PFUnA) Perfluorododecanoic acid (PFDoA) Perfluoro Sulfonic Acids Perfluorobutane sulfonic acid (PFBS) Perfluorohexane sulfonic acid (PFHxS) Perfluorooctane sulfonic acid (PFOS) Perfluorodecane sulfonic acid (PFDS) Approach: PFASs M.W. (g/mol) Perfluorobutyric acid PFBA Perfluoropentanoic acid PFPeA Perfluorohexanoic acid PFHxA Perfluoroheptanoic acid PFHpA Perfluorooctanoic acid PFOA Perfluorononanoic acid PFNA Perfluorodecanoic acid PFDA Perfluoroundecanoic acid PFUnA Perfluorododecanoic acid PFDoA Perfluorobutane sulfonic acid PFBS Perfluorohexane sulfonic acid PFHxS Perfluorooctane sulfonic acid PFOS Perfluorodecane sulfonic acid PFDS PFAS Classes Chemical Name Abbreviation # of Carbons Perfluorocarboxylic Acids (PFCAs) Perfluorosulfonic Acids (PFSAs) Other PFASs: perfluorooctane sulfonamide (FOSA), 2 perfluorosulfonamidoacetic acids, 4 fluorotelomer unsaturated carboxylic acids and 3 fluorotelomer sulfonic acids 2
3 Analytical Methods Automated Solid- Phase Extraction - Dionex AutoTrace 280 workstation Isotopic Dilution LC/MS-MS - API 4000 Minimum Reporting Levels: range from 0.1 to 5.0 ng/l Utility ID State Approach: Utility Sites Source Water Treatment Train Source Water Sampling Dates Treatment Train Sampling Dates 1 WI SW 8/9/ OK SW 8/23/ AK SW 8/22/ CA 2º TWW MF/RO/UV-AOP/DI/Cl 2 8/8/ /6/2011, 2/22/ AL SW AIX/COAG/FLOC/SED/MF/Cl 2 8/15/ /13/2011, 3/20/ CO SW 4/9/ CO SW RBF/ARR/SOFT/SCC/UV-AOP/G-FIL(Biological)/GAC 9/13/2011 5/1/2012, 6/19/2012, 8/21/ OH SW SED/COAG/FLOC/SED/G-FIL/GAC/Cl 2 8/9/ /12/2011, 2/22/ NV SW 9/19/ CA 3º TWW MF/UF/RO/UV-AOP 10/4/2011 1/9/2012, 3/6/ NJ SW/GW AER/COAG/FLOC/SED/G-FIL/ClO 2 12/6/2011, 3/14/ NJ SW O 3 /DAF/Cl 2 /CLM 3/21/2012, 5/23/ NJ GW UV/Cl 2 3/21/2012, 5/23/ NJ GW AIX/APT/Cl 2 5/30/2012, 9/19/ NJ GW Cl 2 /MnO 4 /G-FIL 12/13/ NJ GW ClO 2 /Cl 2 11/29/ NJ SW MnO 4 /O 3 /Cl 2 12/14/2011, 4/3/ NJ SW APT/GAC/Cl 2 11/22/2011, 4/3/ NJ GW Cl 2 11/29/ MN GW GAC/Cl 2 10/26/2006 to 06/20/ NC SW COAG/FLOC/SED/G-FIL/CLM 9/22/2011 9/22/2011 3
4 Results: Occurrence Detected PFAS were in the low ng/l Highest levels were in treated wastewater samples: PFPeA = 370 ng/l PFOA = 220 ng/l Highest level in drinking water was: PFHxA = 62 ng/l PFHxS PFOS PFBS PFBA PFOA PFPeA PFHxA PFHpA PFBA, PFHxA and PFPeA were frequently detected, but they were not included in UCMR3 Longer chain PFCAs were detected less frequently. The longer chain PFSA, perfluorodecane sulfonic acid, and fluorotelomer carboxylic and sulfonic acids were not detected. Perfluoro-sulfonamides were not detected in ground waters, but were in 3 surface waters and treated wastewater effluents. from Water Research, 51, Appleman, T., Higgins, C., Quinones, Q., Vanderford, B., Kolstad, C., Zeigler-Holady, J. Dickenson, E., Treatment of poly- and perfluoroalkyl substances in U.S. full-scale water treatment systems, , (2014). 4
5 Results: Full-Scale Treatment Site: Treatment n= CA AL CO OH CA NJ NJ NJ NJ NJ NJ NJ NJ NJ MN NC RBF 1 AIX 2 AER 2 KMnO 4 2 O 3 2 COAG/FLOC/SED 1 COAG/FLOC/SED/G FIL 3 SOFT 1 COAG/DAF/G FIL 1 M FIL or U FIL 3 RO 2 UV AOP 1 GAC 4 UV 1 ClO 2 2 Cl 2 9 CLM 2 Yes Yes Yes Yes Yes Results: Full-Scale GAC and AIX Utility # of Carbons #7 #20 #14 #14 Treatment GAC GAC AIX AIX Sample Date 8/21/2012 4/25/2007 4/22/2008 5/30/2012 9/19/2012 PFBA 4 33% 17% 9% 0% PFPeA 5 74% > 22% 0% 0% PFHxA 6 91% > 68% 14% 14% PFHpA 7 > 89% N/A 54% 38% PFOA 8 > 48% > 92% 76% 73% PFNA 9 > 37% N/A N/A > 67% PFBS 4 > 96% N/A 83% 80% PFHxS 6 > 96% > 41% > 97% > 98% PFOS 8 > 89% > 95% > 90% > 94% 5
6 Results: Full-Scale GAC Reprinted from Water Research, 51, Appleman, T., Higgins, C., Quinones, Q., Vanderford, B., Kolstad, C., Zeigler-Holady, J. Dickenson, E., Treatment of poly- and perfluoroalkyl substances in U.S. full-scale water treatment systems, , (2014), with permission from Elsevier. Methods: Bench-Scale GAC F300 F C Manufacturer Calgon Calgon Siemens Carbon Type Bituminous Coal Bituminous Coal Coconut Shell Mesh Size, U.S. Sieve 12x40 12x40 12x40 Iodine., mg I 2 /g Apparent Density, g/cc Water Source Spiked DI Filtered (1 µm) and spiked Clear Creek Water PFAA Concentrations (ug/l) # of Columns Carbon F300 F300 F C Column Width (cm) Carbon Depth (cm) Flow Rate (ml/min) EBCT (min) Duration (days) Surface water: DOC = 1.7 mg/l, ph = 6.5 6
7 Results: Bench-Scale GAC Source: Dickenson, E.R.V., and C. Higgins Treatment Mitigation Strategies for Poly and Perfluoroalkyl Substances. Denver, Colo.: Water Research Foundation. Reprinted with permission. Methods: Bench-Scale Nanofiltration Set-up Two flat-sheet NF270 membranes in sequence Flow-through operation 1 L/min, 18C, ph of 6.7 Five 30 min increments Initial experiment: Spiked DI water feed (1 ug/l) Pressures tested from psi Second experiment: Spiked artificial ground water used for feed (1 ug/l) Membranes were fouled to 65% capacity (DOC = 2.5 mg/l) Experiment was repeated with fouled membranes with constant flux Component Source: Dickenson, E.R.V., and C. Higgins Treatment Mitigation Strategies for Poly and Perfluoroalkyl Substances. Denver, Colo.: Water Research Foundation. Reprinted with permission. Concentration (mg/l) MnSO 4 H Na 2 SO NaCl 113 NaHCO
8 Results: Bench-Scale Nanofiltration AGW- Virgin AGW- Fouled DI-Virgin Permeate Flux (LMH) PFBA (214) PFPeA (264) PFHxA (314) PFOA (414) PFNA (464) PFDA (514) PFBS (300) PFHxS (400) PFOS (500) 17 > 94 > 97 > 95 > 97 > 98 > 97 > 99 > 99 > > 94 > 97 > 95 > 97 > 97 > 97 > 99 > 99 > > 94 > 97 > 95 > 97 > 98 > > 99 > > 95 > 97 > 95 > 97 > 98 > > 99 > > 94 > 97 > 95 > 97 > 98 > > 99 > > 95 > 97 > 95 > 97 > 98 > 97 > 99 > 99 > > 94 > 97 > 95 > 97 > 97 > 97 > 99 > 99 > > 94 > 97 > 95 > 97 > 97 > 96 > 99 > 99 > > 94 > 97 > 95 > 97 > 98 > 97 > 99 > 99 > > 94 > 97 > 95 > 97 > 98 > 97 > 99 > 99 > > 93 > 97 > 95 > 97 > 98 > > 97 > > 93 > 97 > 95 > 97 > 98 > > > 93 > 97 > 95 > 95 > 97 > > > 94 > 97 > 95 > 97 > 98 > > > 93 > 97 > 95 > 97 > 97 > > 99 Results: Treatment Summary M.W. (g/mol) AER COAG/ DAF COAG/ SED/ G or M FIL KMnO 4, O 3, ClO2, Free Cl2, NH2Cl, UV, UV/AOP PFBA 214 assumed assumed PFPnA 264 PFHxA 314 PFHpA 364 PFOA 414 PFNA 464 unknown assumed assumed PFDA 514 unknown assumed assumed PFBS 300 PFHxS 400 PFOS 500 FOSA 499 unknown unknown unknown assumed unknown assumed unknown N MeFOSAA 571 assumed unknown assumed assumed assumed unknown N EtFOSAA 585 unknown assumed assumed assumed assumed unknown AIX GAC NF RO 8
9 Contact: Appleman, T., Higgins, C., Quinones, Q., Vanderford, B., Kolstad, C., Zeigler-Holady, J. Dickenson, E. Treatment of poly- and perfluoroalkyl substances in U.S. full-scale water treatment systems, Water Research, 51, , Appleman, T., Dickenson, E., Bellona, C., Higgins, C. Nanofiltration and granular activated carbon treatment of perfluoroalkyl acids, Journal of Hazardous Materials, 260, ,
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