Session 6: PFAS Treatment In Biosolids State Of The Science
Session 6:PFAS Treatment in Biosolids – State ofthe ScienceMarc Mills, PhDUS EPA Office of Research and DevelopmentPFAS Science Webinars for EPA Region 1 and State & Tribal PartnersSeptember 23, 2020
Wastewater Treatment andLand Application of Biosolids/WastesProblem: Lack of knowledge regarding end-of-life management of PFAS-containingconsumer and industrial products in wastewaterAction: Characterize wastewater and relate discharge streams(e.g., municipal and industrial wastewater, land applied waste streams) Evaluate efficacy of existing management technologies to manage end-of-lifedisposal (e.g., land application of biosolids, sewage sludge incineration) Evaluate performance and cost to manage these waste streams and environmentalPFAS releasesResults: Provide technologies, data and science-based tools to manage wastewaterImpact: Responsible officials, utilities and municipalities will be able to managePFAS-containing waste streams2
Daily Production of Biosolids/residualsSludge(metric ton/d) 15,000 Publicly Owned Treatment Works (POTW) in the US Majority of land application occurs in eastern US where depth to groundwater isrelatively shallow3T. Seiple, et al., J.Environ.Manage. 197 (2017) 673-680
Biosolids Use & Disposal2019 EPA electronic reporting data available Enforcement and Compliance History Online (ECHO)4
Biosolids Generated compared to LandApplied Beneficial ReuseBiosolids (US dry tons)Biosolids Benificially usedArea used for Land ea used for Land Application*(acres)Biosolids Generated- Sewage sludges applied pre-regulations (1980s) Many fields have 20 years of biosolids land application Other wastes are also land applied – pulp/paper sludge, concentrated animal feedingoperation (CAFO) wastes, refinery/industrial wastes, drinking water residuals, etc.5Data source - References 1 and 2
PFAS Fate and Transport for WWTPs & BiosolidsWastewater Treatment Plants (WWTPs) may introduce PFAS into the environment through: Effluent discharge to surface water Land application of biosolids and disposal of residuals Air emissions6
Common PFAS Chemical Structures PerfluorinatedFFFOFSFFF-O Perfluorosulfonic Acids (PFSAs)HOPFBS, PFHS, PFOSn 2,4,6FFFOFFFPerfluorocarboxylic Acids (PFCAs)-O H FC6 acid – C12 acidPFOA C8 acidn 3-9 PolyfluorinatedFFFOHFluorotelomer AlcoholsFFFFn 4-166:2, 8:2 and 10:27
Many PFASPerfluoroalkyl SulfonatesFluorotelomer Sulfonamide AminesFluorotelomer BetainesPerfluoroalkyl CarboxylatesFluorotelomer Sulfonates8Backe et al. 2013 ES&T 47:52268
Transformation of PFCAsStableStableGC/MS/MSStableLC/MS/MSWang et al., 2009 Chemosphere 75:1089Buck et al 2011 Envr Assess & Mgmt 7:513Liu & Alvedano 2013 Envr Intntl 61:98 99
Reported Concentrations in BiosolidsYear SampledPFOA (ng/g dry wt)PFOS (ng/g dry wt)Reference200112 - 70308 - 618Venkatesan, 20132004-20078 - 6880 - 219Sepulvado, 2011200516 - 2198.2 - 110Loganathan 2007200518 - 241 10 - 65Sinclair, 200681 - 160Schultz, 200620062006-200718 - 6931 - 702Yu, 2009200720 -12832 - 418Yoo, 200920111 - 144 - 84Navarro, 2016201410 - 6030 - 102Mills, Dasu (in prep)20181-112 – 1,100EGLE, 2020 Does not include other PFAS and precursors that may have been present10
Results from Survey of Michigan WWTPsSUMMARY REPORT:Initiatives to Evaluate the Presence of PFASin Municipal Wastewater and AssociatedResiduals (Sludge/Biosolids) in Michigan.June 2020Results give a good feel for thePFAS ranges for wastewaterplants treating both industrialand non-industrial sources11
Research with PFAS and Biosolids12
Analytical Methods for PFAS in WastewaterTreatment (WWT) Matrices Analytical Chemistry Methods Developmento ORD collaborating with EPA Regions and program offices (OW, OLEM) and other federalagencies (e.g., USGS, USDA, FDA)o Target analytes from multiple methods (with more being considered):PFCAs C4-C14; PFSAs C4-C10; 12 precursors and intermediateso Non-targeted methods and Total PFAS methods also in developmento Matriceso Environmental waters such as surface water, wastewater (WW) influent and effluento Soils, sludges, biosolids and sediments Past Outputso EPA Region 5 methods accepted as ASTM methods (ASTM D7979 and ASTM 7968)o SW 846 8327 Direct Injection for non-potable waterso Multi-laboratory validated methodo Released as draft method in 2019o Final method scheduled to be available by Fall 2020 Upcoming Outputso Evaluating Method 533 for non-potable matriceso Conducting methods validation studies for 1600 Series/SW-846 methods for non-potablewaters, wastewater, leachate, soils, biosolids, sediments, and tissue sampleso Single-laboratory validation study underwayo Multi-laboratory validation study planned13
Analytical Methods for PFAS in WWT MatricesASTM 7979-17/Region 5 methodUS EPA SW 846 8327/3215(draft Multilab Validated)ASTM 7968/Region 5 methodUS EPA 1600 Seriesmethod (in development)Non-potable waterNon-potable waterSolids, soils, sediments,sludgesnon-potable waters, solids,& tissue C10C4-C10C4-C10PFSA precursorsand intermediatesFOSA; N-EtFOSAA;N-MeFOSAAFOSA; N-EtFOSAA;N-MeFOSAAFOSA; N-EtFOSAA;N-MeFOSAAN-EtFOSAA; N-MeFOSAA;N-MeFOSE; N-EtFOSE;N-EtFOSA; N-MeFOSAPFCA precursorsand intermediates4:2, 6:2, & 8:2 FTS; 6:2, 8:2,10:2, & 7:3 FTCA; 6:2 & 8:2FTUCA4:2, 6:2, & 8:2 FTS4:2, 6:2, & 8:2 FTS; 6:2, 8:2,10:2, & 7:3 FTCA; 6:2, 8:2,& 10:2 FTUCA4:2, 6:2, & 8:2 FTSMatrixAnalytesOther PFASHFPO-DA; ADONA; 9ClPF3ONS; 11Cl-PF3OUdSAnalysisPrepDirect injectDirect injectDirect injectSolid Phase ExtractionSurrogate stds141414-Internal stdsnononoyesQuantitation2 SRM and ion ratios2 SRM and ion ratios2 SRM and ion ratios2 SRM and ion ratiosmost 10 ng/Lmost 10 ng/L20 ng/kgTarget 10 ppt or lessReporting limit14
Other analytical methods under development Air Measurementso Considering both sampling and analysis methodso Monitoring for fugitive emissions, deposition, receptor exposureo Ambient/Near-Source – Field deployable Time of Flight/Chemical Ionization MassSpectrometer for real time detection/measuremento Semivolatile and Volatile PFAS, targeted and non-targeted analysis GC-MS/MS analysis of PFASo Research methods to measure specific PFAS precursors and volatile specieso Matrices – water, wastewater, and solids Total Oxidizable Precursors (TOP) assay*o Available at some contract labs, but lacks a multi-lab validated standard methodo Estimate of PFAS precursors and intermediates*Houtz et al 2012 ES&T 46:9342 Total Organic Fluorineo Removing the background inorganic F- from the sample is important to make surethat the reported F- is organico High priority for EPA. ORD working with OW-OST to develop a draft method in 202015
Land Application of Biosolids:PFAS uptake into edible parts of plantsEPA Regional Applied Research Effort (RARE) projectEPA Region 5/Kim Harris, in collaboration with Chris Higgins at Colorado School ofMinesA variety of food crops were grown in soil amended with biosolids The biosolids contained PFAAs PFAA concentrations in edible portion of the plants were measured.Conclusions: The edible portions had measurable levels of PFOA, among otherPFAS Data suggest that edible crops grown in soil conventionally amendedwith municipal biosolids may contain PFAS, and further studies areneeded to characterize mechanisms of uptake from various soils andcropsBlaine, et al (2013). ES&T 47(24): 14062-14069Blaine, et al (2014). ES&T 48(14): 7858-7865.16
In 4 plants:Accumulation in produce from soil amended with biosolidsPreferential uptake C7 for these plants and analytesDifferential uptake to various compartments within the plantRadish:Shoot RootCelery:Shoot RootTomato: Depends on cpd ShootPea: Depends on cpd17
Summary – In RARE project with Region 6, 9 WWTPs were sampled seasonally The solids treatment included anaerobic digestion and aerobic digestion Solid residuals and effluent were analyzed for PFAAs, precursorsand transformation productsResults – PFAAs and PFAS precursors with varying distributionsConcentration, ng/g biosolid (DW)134 (64) 102 (4)89(13) 124 WTP9200PFCAsPFSAsFT AcidsPFAAs concentrations in biosolids collected during fall sampling18
Land Applied Materials: Field Site 2 Evaluate different application methods (liquid and solid biosolids) Evaluate natural attenuation for various analytes including PFAS Design Controlled site consisting of 20 inches sandy loam soilPlanted with fescue/rye grass mixMeasure: PFAS, nonylphenol, metals and microbes over year long studyControls: soil only and biosolids onlyControlSolidLiquid19
Analytical Methods Performance for Field Site 2ASTM/EPA Region 5 methodAccuracy - Isotopic Surrogates – met goalsPrecision – Duplicates - met goals100.0140.0N 0.00.040.0PFHxA (13C2) PFBA (13C4) PFOS (13C4) PFNA (13C5) PFOA (13C4) PFDA (13C2) PFHxS (18O2)PFAS foreachsurrogate7:3 FTCAPFHxA6:2 FTCAPFPeAPFBAPFOS8:2 FTCA PFOAPFDAPFBS7:3 FTCAPFPAPFHxAPFOS8:2 FTCA 6:2 FTCAPFOAPFBAPFDAPFBS Outliers not shown: 7:3 FTCA 136 %, and PFBA 200% N 16 to 18 except 8:2 FTCA n 4, 6:2 FTCA n 3, and PFBA n 1420
Land Application of Biosolids Field Study 2:PFAS Precursors Precursorconcentrationssimilar to PFAAconcentrationsDay 11.0E-07Day 3718.0E-08MOLES Intermediateconcentrationsdecrease with timeBiosolids Controls1.2E-076.0E-084.0E-082.0E-08 Stable PFAAsincreased0.0E 008:2FTOH *8:2 FTCA8:2 FTUCAPrecursors7:3 FTCAPFOAPFHxAPFHpAStable PFAAs 85% mole balance* Preliminary measurements21
Land Application of BiosolidsField Study 3: Dry Land AgricultureStudy Design Field site operated for more than 20 years Measure concentrations of PFAS and other chemicals as a function of depth andbiosolids application loadings (control to 30 dry tons/acre) Measure PFAS in plants from the application sites Develop conceptual model of biosolids application sites and compare to real worlddata with the goal of predicting PFAS concentrationsSchedule Sample collection this fall22
Sewage Sludge Incineration (SSI)SSI is one of several thermal treatment processes that are currently being consideredfor bench to full-scale studies ORD has a bench-scale project started to understand basic impacts of operation conditions such astime, temperature, media, etc. ORD is considering field scale studies for FY2123
State ResponsesExample: The State of Maine has taken action on biosolids and-biosolids-landapplication-sets-stage
Changing Fate of Wastewater ResidualsUSEPA is looking for partnersfor sampling full-scalesewage sludge incinerators Wastewater residual incinerationmay increase as policies shift toaddress PFAS in wastewater Lack data on the fate of PFAS infull-scale incinerators25
Chemical Risk Assessments for BiosolidsProject:Exposure, Hazard and Toxicokinetic Data forChemicals in BiosolidsDescription:o Leverage the computational toxicology approachesdeveloped for the TSCA inventory to evaluatechemicals which may be present in biosolids for riskassessment prioritizationo Goal is to synthesize information from traditionaland new approach methods (NAMs) to understand: The overall degree of potential concern related tohuman health and the environment The relative coverage of potentially relevant humanhealth and ecological toxicity and exposureinformation that could inform level of effort andresources that may be needed to evaluate thatspecific substance26
EPA Research GrantsSTAR Grants: Practical Methods to Analyze and Treat Emerging Contaminants (PFAS) inSolid Waste, Landfills, Wastewater/Leachates, Soils and Groundwater to Protect HumanHealth and the Environment Project: Decreasing PFAS in municipal wastewater effluent and minimizing release from land-applied biosolids (Linda Lee, Purdue) Project: A systems-based approach to understand the role of waste type, management strategies and treatment methods on theoccurrence, source and fate of PFAS in landfills (Timothy Townsend, Univ of Florida) Project: Electron Beam Technology for Destruction of Short-Chain and Perfluoroalkyl Substances in groundwater, wastewater,sewage sludges and soils (Suresh Pillai, Texas A&M)National Priorities: Research on PFAS Impacts in Rural Communities and AgriculturalOperations To better understand the impacts of PFAS on water quality and availability in rural communities and agricultural operations acrossthe US New information on PFAS occurrence, fate and transport in water sources used by rural communities and agricultural operations New or improved PFAS treatment methods in small drinking water systems and typical small wastewater treatment system trains,including influents, effluents and biosolids/residuals Closed February 11, 202027
Technical and Program Office SupportTo request technical support, contact EPA Region or Program Office partnersEPA Office of WaterElyssa ArnoldBiosolids Team202-566-1189Arnold.Elyssa@epa.govElizabeth ResekBiosolids Lead202-566-1228Resek.Elizabeth@epa.govRegionPFAS Point of ContactRegional ScienceLiaison1Meghan CassidyChau Vu2Christine Ash, Douglas Pabst,Dan D’AgostinoMindy Pensak3Steve Hirsh, Heather Arvanaghi,Roger Reinhart, Rick RogersRegina Poeske4Becky Allenbach, Aaryn JonesDawn Taylor5Kim Harris, Carole Braverman,Linda HolstCarole Braverman6Michael Morton, Greg LyssyMichael Morton7Daniel O’Connor, Amy Shields,Catherine Wooster-BrownChristopher Taylor8Sarah Bahrman, Lisa Kahn,Lisa McClain-VanderpoolAlfred Basile9Matthew SmallMatthew Small10Linda Anderson-CarnahanRob Elleman28
For More Information The research discussed in this presentation is part of EPA’s overall efforts to rapidlyexpand the scientific foundation for understanding and managing risk from PFAS For more information on EPA’s efforts to address PFAS, please visit the followingwebsites EPA PFAS Action Plan ‒ https://www.epa.gov/pfas/epas-pfas-action-plan EPA PFAS Research ‒ polyfluoroalkyl-substances-pfas29
ContactsMarc A. Mills, PhDLead for PFAS Remediation R&DUS EPA Office of Research and DevelopmentMills.Marc@epa.gov513-569-7322Learn more about EPAResearch on PFASEPA ORD Team:Land Applied Materials:Sewage Sludge Incineration:Carolyn Acheson, PhDAcheson.Carolyn@epa.gov513-569-7190Phillip Potter, PhDPotter.Phillip@epa.gov513-487-2683Ronald HerrmannHerrmann.Ronald@epa.gov513-569-7741Brian CroneCrone.Brian@epa.gov513-569-702030
ReferencesSlide 5 :1.EPA reports: EPA-430/9-76-013, EPA-625/10-84-003, EPA-821/R/3006, EPA/625/R-95/001, EPA-530-R-99-0092.NEBRA 2007Slide 10:1.Venkatesan and Halden, 2013, Journal of Hazardous Materials 252-253:413-4182.Sepulvado et al., 2011, Environmental Science and Technology 45:8106-81123.Loganathan et al., 2007, Water Research 41:4611-46204.Sinclair and Kannan, 2006, Environmental Science and Technology 40:1408-14145.Schultz et al., 2006 , Environmental Science and Technology 40:7350-73576.Yu et al., 2009, Water Research 43:2399-24087.Yoo et al., 2009, Journal of Chromatography A 1216:7831-78398.Navarro et al., 2016, Environmental Research 149:32-399.Michigan Department of Environment, Great Lakes, and Energy (EGLE), 2020. Summary Report: Initiatives toEvaluate the Presence of PFAS in Municipal Wastewater and Associated Residuals.31
Analytical Methods for PFAS in WWT Matrices 14 ASTM 7979-17/ Region 5 method US EPA SW 846 8327/3215 (draft Multilab Validated) ASTM 7968/ Region 5 method US EPA 1600 Series method (in development) Matrix Non-potable water Non-potable water Solids, soils, sediments, sludges non-potable waters, solids, & tissue samples Analytes
persistent man-made chemicals. Industry responsibility Companies should immediately work to phase out PFAS chemicals, replacing them with safer, non-PFAS alternatives. Individual action When shopping, ask for and choose PFAS-free products, for example
and far. Human exposure to PFAS in surface waters occurs primarily through use of the waterbody as a drinking water source or through fish consumption. Some PFAS are known to have toxic effects and pose health risks at very low levels. Surface water analysis measures PFAS in parts per trillion (ppt). Fish tissue analysis measures
9 PFAS captures a large class of widely used, long-lasting chemicals used for non-stick, waterproof, stain-resistant, and other uses. PFAS are present in human blood and in the environment and resist being broken down. Exposure to some PFAS is linked to harmful health effects in humans and animals Many PFAS continue to be used, but some -like PFOA and
Ecological Exposures: 1. Wastewater is a conduit for PFAS to enter the environment through effluent discharged to surface waters and land application of biosolids (soil, crop uptake, groundwater). Conventional Wastewater Treatment: 1. Conventional treatment does not effectively remove PFAS; 2.
projects related to PFAS remediation technology AFCEC role in technology development and technology transfer Summary of completed and continuing projects Examples Source zone enhanced mass transfer and treatment Electrochemical treatment Enzymatic degradation PFAS: per- and polyfluoroalkyl substances
P2 strategies reduce liability for businesses and reduce the need for costly site clean-ups. PFAS alternatives may be better and cheaper, potentially improving profitability for businesses. Waste facility operators have limited ability to control PFAS inputs. P2 measures decrease loading
The Action Plan describes the broad actions the EPA has underway to address challenges with PFAS in the environment, including next steps on the four PFAS management actions the EPA announced at the May 2018 National Leadership Summit.
processes, decontamination procedures, and acceptable materials for . General PFAS Sampling . sampling landfill leachate for per- and polyfluoroalkyl substances . Guidance . prior to. reviewing this Guidance. (PFAS). In addition, this guidance will be used to support the sampling
