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Consumer and/or industrial uses of PFAS-containing materials results in the discharge of PFAS to industrial and municipal wastewater treatment plants (WWTPs). Conventional WWTP treatment processes remove less than 5% of PFAAs<ref name="Ahrens2011a"/><ref name="Schultz2006">Schultz, M.M., Higgins, C.P., Huset, C.A., Luthy, R.G., Barofsky, D.F., and Field, J.A., 2006. Fluorochemical Mass Flows in a Municipal Wastewater Treatment Facility. Environmental Science and Technology, 40(23), pp. 7350-7357.  [https://doi.org/10.1021/es061025m DOI: 10.1021/es061025m]&nbsp;&nbsp; [https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2556954/ Author Manuscript]</ref><ref name="MWRA2019">Michigan Waste and Recycling Association (MWRA), 2019. Statewide Study on Landfill Leachate PFOA and PFOS Impact on Water Resource Recovery Facility Influent, Second Revision.  [[Media: MWRA2019.pdf | Report.pdf]]</ref>. WWTPs, particularly those that receive industrial wastewater, are possible sources of PFAS release<ref name="Bossi2008">Bossi, R., Strand, J., Sortkjær, O. and Larsen, M.M., 2008. Perfluoroalkyl compounds in Danish wastewater treatment plants and aquatic environments. Environment International, 34(4), pp. 443-450. [https://doi.org/10.1016/j.envint.2007.10.002  DOI: 10.1016/j.envint.2007.10.002]  Free download from: [https://www.academia.edu/download/43968517/Perfluoroalkyl_compounds_in_Danish_waste20160321-31116-esz4d1.pdf Academia.edu]</ref><ref name="Lin2014">Lin, A.Y.C., Panchangam, S.C., Tsai, Y.T., and Yu, T.H., 2014. Occurrence of perfluorinated compounds in the aquatic environment as found in science park effluent, river water, rainwater, sediments, and biotissues. Environmental Monitoring and Assessment, 186(5), pp. 3265-3275.  [https://doi.org/10.1007/s10661-014-3617-9 DOI: 10.1007/s10661-014-3617-9]</ref><ref name="Ahrens2009">Ahrens, L., Felizeter, S., Sturm, R., Xie, Z. and Ebinghaus, R., 2009. Polyfluorinated compounds in waste water treatment plant effluents and surface waters along the River Elbe, Germany. Marine Pollution Bulletin, 58(9), pp.1326-1333. [https://doi.org/10.1016/j.marpolbul.2009.04.028 DOI: 10.1016/j.marpolbul.2009.04.028]&nbsp;&nbsp; [[Media:Ahrens2009.pdf | Author’s manuscript]]</ref>.
 
Consumer and/or industrial uses of PFAS-containing materials results in the discharge of PFAS to industrial and municipal wastewater treatment plants (WWTPs). Conventional WWTP treatment processes remove less than 5% of PFAAs<ref name="Ahrens2011a"/><ref name="Schultz2006">Schultz, M.M., Higgins, C.P., Huset, C.A., Luthy, R.G., Barofsky, D.F., and Field, J.A., 2006. Fluorochemical Mass Flows in a Municipal Wastewater Treatment Facility. Environmental Science and Technology, 40(23), pp. 7350-7357.  [https://doi.org/10.1021/es061025m DOI: 10.1021/es061025m]&nbsp;&nbsp; [https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2556954/ Author Manuscript]</ref><ref name="MWRA2019">Michigan Waste and Recycling Association (MWRA), 2019. Statewide Study on Landfill Leachate PFOA and PFOS Impact on Water Resource Recovery Facility Influent, Second Revision.  [[Media: MWRA2019.pdf | Report.pdf]]</ref>. WWTPs, particularly those that receive industrial wastewater, are possible sources of PFAS release<ref name="Bossi2008">Bossi, R., Strand, J., Sortkjær, O. and Larsen, M.M., 2008. Perfluoroalkyl compounds in Danish wastewater treatment plants and aquatic environments. Environment International, 34(4), pp. 443-450. [https://doi.org/10.1016/j.envint.2007.10.002  DOI: 10.1016/j.envint.2007.10.002]  Free download from: [https://www.academia.edu/download/43968517/Perfluoroalkyl_compounds_in_Danish_waste20160321-31116-esz4d1.pdf Academia.edu]</ref><ref name="Lin2014">Lin, A.Y.C., Panchangam, S.C., Tsai, Y.T., and Yu, T.H., 2014. Occurrence of perfluorinated compounds in the aquatic environment as found in science park effluent, river water, rainwater, sediments, and biotissues. Environmental Monitoring and Assessment, 186(5), pp. 3265-3275.  [https://doi.org/10.1007/s10661-014-3617-9 DOI: 10.1007/s10661-014-3617-9]</ref><ref name="Ahrens2009">Ahrens, L., Felizeter, S., Sturm, R., Xie, Z. and Ebinghaus, R., 2009. Polyfluorinated compounds in waste water treatment plant effluents and surface waters along the River Elbe, Germany. Marine Pollution Bulletin, 58(9), pp.1326-1333. [https://doi.org/10.1016/j.marpolbul.2009.04.028 DOI: 10.1016/j.marpolbul.2009.04.028]&nbsp;&nbsp; [[Media:Ahrens2009.pdf | Author’s manuscript]]</ref>.
  
Evaluation of full-scale WWTPs has indicated that conventional primary (sedimentation and clarification) and secondary (aerobic biodegradation of organic matter) treatment processes can result in changes in PFAS concentrations and classes. For example, higher concentrations of PFAAs have been observed in effluent than in influent, presumably due to transformation of precursor PFAS<ref name="Schultz2006"/>. Some data has indicated that the terminal PFAS compounds PFOS and PFOA were among the most frequently detected PFAS in wastewater<ref name="Hamid2016">Hamid, H. and Li, L., 2016. Role of wastewater treatment plant in environmental cycling of poly- and perfluoroalkyl substances. Ecocycles, 2(2), pp. 43-53. [https://doi.org/10.19040/ecocycles.v2i2.62 DOI: 10.19040/ecocycles.v2i2.62]&nbsp;&nbsp; [[Media: Hamid2016.pdf | Open access article.]]</ref>. A state-wide study in Michigan indicated that PFAS were detected in all of the samples from 42 WWTPs, including influent, effluent, and biosolids/sludge samples, and that the short-chain PFAS were more frequently detected in the liquid process flow (influent and effluent), while long-chain PFAS were more common in biosolids<ref name="EGLE2020">Michigan Department of Environment, Great Lakes and Energy (EGLE), 2020.  Summary Report: Initiatives to Evaluate the Presence of PFAS in Municipal Wastewater and Associated Residuals (Sludge/Biosolids) in Michigan. [[Media:EGLE2020.pdf | Report.pdf]]  
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Evaluation of full-scale WWTPs has indicated that conventional primary (sedimentation and clarification) and secondary (aerobic biodegradation of organic matter) treatment processes can result in changes in PFAS concentrations and classes. For example, higher concentrations of PFAAs have been observed in effluent than in influent, presumably due to transformation of precursor PFAS<ref name="Schultz2006"/>. Some data has indicated that the terminal PFAS compounds PFOS and PFOA were among the most frequently detected PFAS in wastewater<ref name="Hamid2016">Hamid, H. and Li, L., 2016. Role of wastewater treatment plant in environmental cycling of poly- and perfluoroalkyl substances. Ecocycles, 2(2), pp. 43-53. [https://doi.org/10.19040/ecocycles.v2i2.62 DOI: 10.19040/ecocycles.v2i2.62]&nbsp;&nbsp; [[Media: Hamid2016.pdf | Open access article.]]</ref>. A state-wide study in Michigan indicated that PFAS were detected in all of the samples from 42 WWTPs, including influent, effluent, and biosolids/sludge samples, and that the short-chain PFAS were more frequently detected in the liquid process flow (influent and effluent), while long-chain PFAS were more common in biosolids<ref name="EGLE2020">Michigan Department of Environment, Great Lakes and Energy (EGLE), 2020.  Summary Report: Initiatives to Evaluate the Presence of PFAS in Municipal Wastewater and Associated Residuals (Sludge/Biosolids) in Michigan. [[Media:EGLE2020.pdf | Report.pdf]]&nbsp;&nbsp;
 
[https://www.michigan.gov/documents/egle/wrd-pfas-initiatives_691391_7.pdf Website]</ref>.
 
[https://www.michigan.gov/documents/egle/wrd-pfas-initiatives_691391_7.pdf Website]</ref>.
  
   
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Multiple studies have found PFAS in municipal sewage sludge<ref name="Higgins2005">Higgins, C.P., Field, J.A., Criddle, C.S., and Luthy, R.G., 2005. Quantitative Determination of Perfluorochemicals in Sediments and Domestic Sludge. Environmental Science and Technology, 39 (11), pp. 3946 – 3956. [https://doi.org/10.1021/es048245p DOI: 10.1021/es048245p]</ref><ref name="EGLE2020"/>. The US EPA states that more than half of the sludge produced in the United States is applied to agricultural land as biosolids, therefore there are concerns that biosolids applications may become a potential source of PFAS to the environment<ref name="USEPA2020">US Environmental Protection Agency (USEPA), 2020. Research on Per- and Polyfluoroalkyl Substances (PFAS).  [https://www.epa.gov/chemical-research/research-and-polyfluoroalkyl-substances-pfas Website]</ref>. Application of biosolids as a soil amendment can potentially result in transfer of PFAS to soil, surface water and groundwater and can possibly allow PFAS to enter the food chain<ref name="Sepulvado2011">Sepulvado, J.G., Blaine, A.C., Hundal, L.S. and Higgins, C.P., 2011. Occurrence and Fate of Perfluorochemicals in Soil Following the Land Application of Municipal Biosolids. Environmental Science and Technology, 45(19), pp.  8106-8112.  [https://doi.org/10.1021/es103903d DOI: 10.1021/es103903d]</ref><ref name="Lindstrom2011">Lindstrom, A.B., Strynar, M.J., Delinsky, A.D., Nakayama, S.F., McMillan, L., Libelo, E.L., Neill, M. and Thomas, L., 2011. Application of WWTP Biosolids and Resulting Perfluorinated Compound Contamination of Surface and Well Water in Decatur, Alabama, USA. Environmental Science and Technology, 45(19), pp. 8015-8021.  [https://doi.org/10.1021/es1039425 DOI: 10.1021/es1039425]</ref><ref name="Blaine2013">Blaine, A.C., Rich, C.D., Hundal, L.S., Lau, C., Mills, M.A., Harris, K.M. and Higgins, C.P., 2013. Uptake of Perfluoroalkyl Acids into Edible Crops via Land Applied Biosolids: Field and Greenhouse Studies. Environmental Science and Technology, 47(24), pp.14062-14069.  [https://doi.org/10.1021/es403094q DOI: 10.1021/es403094q]&nbsp;&nbsp; Free download from: [https://www.epa.gov/sites/production/files/2019-11/documents/508_pfascropuptake.pdf US EPA]</ref><ref name="Blaine2014">Blaine, A.C., Rich, C.D., Sedlacko, E.M., Hundal, L.S., Kumar, K., Lau, C., Mills, M.A., Harris, K.M. and Higgins, C.P., 2014. Perfluoroalkyl Acid Distribution in Various Plant Compartments of Edible Crops Grown in Biosolids-Amended Soils. Environmental Science and Technology, 48(14), pp. 7858-7865.  [https://doi.org/10.1021/es500016s DOI: 10.1021/es500016s] Free download from: [https://www.researchgate.net/profile/Kuldip_Kumar2/publication/263015815_Perfluoroalkyl_Acid_Distribution_in_Various_Plant_Compartments_of_Edible_Crops_Grown_in_Biosolids-Amended_soils/links/5984cb310f7e9b6c852f4f02/Perfluoroalkyl-Acid-Distribution-in-Various-Plant-Compartments-of-Edible-Crops-Grown-in-Biosolids-Amended-soils.pdf ResearchGate]</ref><ref name="Navarro2017">Navarro, I., de la Torre, A., Sanz, P., Porcel, M.Á., Pro, J., Carbonell, G. and de los Ángeles Martínez, M., 2017. Uptake of perfluoroalkyl substances and halogenated flame retardants by crop plants grown in biosolids-amended soils. Environmental Research, 152, pp. 199-206.  [https://doi.org/10.1016/j.envres.2016.10.018 DOI: 10.1016/j.envres.2016.10.018]</ref>. Limited studies have shown that PFAS concentrations can be elevated in surface and groundwater in the vicinity of agricultural fields that received PFAS contaminated biosolids for an extended period<ref name="Washington2010">Washington, J.W., Yoo, H., Ellington, J.J., Jenkins, T.M., and Libelo, E.L., 2010. Concentrations, Distribution, and Persistence of Perfluoroalkylates in Sludge-Applied Soils near Decatur, Alabama, USA. Environmental Science and Technology, 44(22), pp. 8390-8396.  [https://doi.org/10.1021/es1003846 DOI: 10.1021/es1003846]  Free download from: [https://www.researchgate.net/profile/John_Washington3/publication/47447289_Concentrations_Distribution_and_Persistence_of_Perfluoroalkylates_in_Sludge-Applied_Soils_near_Decatur_Alabama_USA/links/5e3c0184a6fdccd9658add41/Concentrations-Distribution-and-Persistence-of-Perfluoroalkylates-in-Sludge-Applied-Soils-near-Decatur-Alabama-USA.pdf ResearchGate]</ref>. The most abundant PFAS found in biosolids are the long-chain PFAS<ref name="Hamid2016"/><ref name="EGLE2020"/>. Based on the persistence and stability of long-chain PFAS and their interaction with biosolids, research is ongoing to determine PFAS leachability from biosolids and their bioavailability for uptake by plants, soil organisms, and the consumers of potentially PFAS-impacted plants and soil organisms.
  
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==Solid Waste Management Facilities==
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Industrial, commercial, and consumer products containing PFAS that have been disposed in municipal solid waste (MSW) landfills or other legacy disposal areas since the 1950s are potential sources of PFAS release to the environment.  Environmental and drinking water impacts from disposal of legacy PFAS-containing industrial and consumer wastes have been documented
  
 
   
 
   

Revision as of 14:36, 29 January 2021

PFAS Sources

Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) have been used in coatings for textiles, paper products, and cookware; in some firefighting foams; and have a range of applications in the aerospace, photographic imaging, semiconductor, automotive, construction, electronics, and aviation industries[1][2][3]. Although PFAS and PFAS-containing products have been manufactured since the 1950s, PFAS were not widely documented in environmental samples until the early 2000s. Understanding PFAS manufacturing history, past and current uses, and waste management over the last six to seven decades is necessary for the identification of potential environmental sources of PFAS, possible release mechanisms, and associated pathway-receptor relationships.

Related Article(s):

Contributor(s): Dr. Sheau-Yun (Dora) Chiang and Dr. Alexandra Salter-Blanc

Key Resource(s):

Introduction

Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) are a complex family of more than 3,000 manmade fluorinated organic chemicals[4] although not all of these are currently in use or production. PFAS are produced using several different processes. Fluorosurfactants, which include perfluoroalkyl acids (PFAAs) (see PFAS article for nomenclature) and side-chain fluorinated polymers, have been manufactured using two major processes: electrochemical fluorination (ECF) and telomerization[2]. ECF was licensed by 3M in the 1940s[5] and used by 3M until 2001. ECF produces a mixture of even and odd numbered carbon chain lengths of approximately 70% linear and 30% branched substances[6]. Telomerization was developed in the 1970s[7], and yields mainly even numbered, straight carbon chain isomers[8][9]. PFAS manufacturers have provided PFAS to secondary manufacturers for production of a vast array of industrial and consumer products.

During manufacturing, PFAS may be released into the atmosphere then redeposited on land where they can also affect surface water and groundwater, or PFAS may be discharged without treatment to wastewater treatment plants or landfills, and eventually be released into the environment by treatment systems that are not designed to mitigate PFAS (see also PFAS Transport and Fate). Industrial discharges of PFAS were unregulated for many years, but that has begun to change. In January 2016, New York became the first state in the nation to regulate PFOA as a hazardous substance followed by the regulation of PFOS in April 2016. Consumer and industrial uses of PFAS-containing products can also end up releasing PFAS into landfills and into municipal wastewater, where it may accumulate undetected in biosolids which are typically treated by land application.

Industrial Sources

PFAS are used in many industrial and consumer applications, which may have released PFAS into the environment and impacted drinking water supplies in many areas of the United States[10]. Both in the United States (US) and abroad, primary manufacturing facilities produce PFAS and secondary manufacturing facilities use PFAS to produce goods. Environmental release mechanisms associated with these facilities include air emission and dispersion, spills, and disposal of manufacturing wastes and wastewater. Potential impacts to air, soil, sediment, surface water, stormwater, and groundwater are present not only at primary release points but potentially over the surrounding area[11]. Some of the potential primary and secondary sources of PFAS releases to the environment are listed here[1]:

  • Paper products: Surface coatings to repel grease and moisture. Uses include non-food paper packaging (for example, cardboard, carbonless forms, masking papers) and food-contact materials (for example, pizza boxes, fast food wrappers, microwave popcorn bags, baking papers, pet food bags)[12][8][13][15][18][22][23][26][28]
  • Metal Plating & Etching: Corrosion prevention, mechanical wear reduction, aesthetic enhancement, surfactant, wetting agent/fume suppressant for chrome, copper, nickel and tin electroplating, and post-plating cleaner[29][30][8][16][31][23][32][2][33]
  • Industrial Surfactants, Resins, Molds, Plastics: Manufacture of plastics and fluoropolymers, rubber, and compression mold release coatings; plumbing fluxing agents; fluoroplastic coatings, composite resins, and flame retardant for polycarbonate[8][36][15][37][16][38][34][22][24][26][39]
  • Photolithography, Semiconductor Industry: Photoresists, top anti-reflective coatings, bottom anti-reflective coatings, and etchants, with other uses including surfactants, wetting agents, and photo-acid generation[40][41][14][34][23][24]

Class B Firefighting Foams

Aqueous film forming foam (AFFF) and other fluorinated Class B firefighting foams are another important source of PFAS to the environment, especially in military and aviation settings. Class B firefighting foams have been used since the 1960s to extinguish flammable liquid hydrocarbon fires and for vapor suppression. These foams contain complex and variable mixtures of PFAS that act as surfactants. Fluorinated surfactants are both hydrophobic and oleophobic (oil-repelling), as well as thermally stable, chemically stable, and highly surface active[42]. These properties make them uniquely suited to fighting hydrocarbon fuel fires. Use of fluorinated Class B foams is prevalent and is a major source of PFAS to the environment. Release to the environment typically occurs during firefighting operations, firefighter training, apparatus testing, or leakage during storage. Research into fluorine-free alternatives is underway and Congressional pressure is leading towards banning fluorinated Class B firefighting foams in the United States.

Figure 1. Types of Class B firefighting foams. Reproduced from ITRC, 2020; original figure courtesy of S. Thomas, Wood PLC, used with permission.

When discussing the relationship between firefighting foams and sources of PFAS to the environment, the emphasis is typically on AFFF; however, many different types of Class B firefighting foams exist. These may or may not be fluorinated (contain PFAS). Class B foams are used to extinguish Class B fires, that is, those involving flammable liquids. Fluorinated Class B foams spread across the surface of the flammable liquid forming a thin film and extinguish fires by (1) excluding air from the flammable vapors, (2) suppressing vapor release, (3) physically separating the flames from the fuel source, and (4) cooling the fuel surface and surrounding metal surfaces[43]. From a PFAS perspective, Class B firefighting foams can be divided into two broad categories: fluorinated foams (that contain PFAS) and fluorine-free foams (that do not contain PFAS)[1]. This distinction and examples of each type are shown in Figure 1.

AFFF was developed by the US Navy in the 1960s and in 1969, the US Department of Defense (DoD) issued military specification MIL-F-24385 listing firefighting performance requirements for all AFFF used within the US DoD[1][44][45]. These performance standards are often referred to as “Mil-Spec.” Products that meet the Mil-Spec have been added to the US DoD Qualified Product Listing (QPL). In 2006 the US Federal Aviation Administration (FAA) also began requiring that 14-CFR-139-certified commercial airports purchase Mil-Spec compliant AFFF only. Because the US DoD and FAA have been the primary purchasers of AFFF, development of AFFF product mixtures has historically been performance-driven (to comply with the Mil-Spec) rather than formula-driven (the specific PFAS mixtures utilized have varied over time and by manufacturer). Multiple manufacturers in the US and throughout the world produce or have produced AFFF concentrate[1]. AFFF concentrate is or has been available in 1%, 3%, or 6% formulations, where the percentage designates the recommended percentage of concentrate to be mixed into water during application.

The specific mixtures of PFAS found in AFFF have varied by manufacturer and over time due to differences in production processes and voluntary formula changes. AFFF formulations can generally be grouped into three categories[1]:

  • Legacy Perfluorooctane Sulfonate (PFOS) AFFF This type of AFFF was manufactured exclusively by 3M under the brand name “Lightwater” from the late 1960s until 2002 using the ECF production process. They contain PFOS and perflouroalkane sulfonates (PFSAs) such as perfluorohexane sulfonate (PFHxS)[1][46]. Legacy PFOS AFFF produced by ECF were voluntarily phased out in 2002, however, use of stockpiled product was permitted after that date[1].
  • Legacy fluorotelomer AFFF This group consists of AFFF manufactured and sold in the U.S. from the 1970s until 2016 and includes all brands that were produced using a process known as fluorotelomerization (FT). The FT manufacturing process produces polyfluorinated substances that can degrade in the environment to perfluoroalkyl substances (specifically PFAAs) including Perfluorooctanoic Acid (PFOA). Polyfluoroalkyl substances that degrade to create terminal PFAAs are referred to as “precursors” [1].
  • Modern fluorotelomer AFFF This group consists of AFFF developed in response to the USEPA 2010-2015 voluntary PFOA Stewardship Program[47], which asked companies to commit to first reducing and then eliminating the following: PFOA, precursors that can break down to PFOA, and related chemicals from facility emissions and products. In response, manufacturers began producing only short-chain fluorosurfactants targeting fluorotelomer PFAS with 6 carbons per chain (C6), rather than the traditional long-chain fluorosurfactants (8 or more carbons per chain). These short-chain PFAS do not breakdown in the environment to PFOS or PFOA[1]. Their toxicity in comparison to long-chain fluorosurfactants is a topic of current research.

In the US, AFFF users including the US DoD (predominantly the Navy and Air Force), civilian airports, oil refineries, other petrochemical industries, and municipal fire departments[48]. AFFF is used, for example, in fire fighting vehicles, in fixed fire suppression systems (including sprinklers and fixed spray systems in or at aircraft hangars, flammable liquid storage areas, engine hush houses, and fuel farms), and onboard military and commercial ships. Fluorinated Class B foams may be introduced to the environment through the following practices[1]:

  • low volume releases of foam concentrate during storage, transfer or operational requirements that mandate periodic equipment calibration
  • moderate volume discharge of foam solution for apparatus testing and episodic discharge of AFFF-containing fire suppression systems within large aircraft hangars and buildings
  • occasional, high-volume, broadcast discharge of foam solution for firefighting and fire suppression/prevention for emergency response
  • periodic, high volume, broadcast discharge for fire training
  • accidental leaks from foam distribution piping between storage and pumping locations, and from storage tanks and railcars

The DoD is currently replacing legacy, long-chain AFFF with modern, short-chain fluorotelomer AFFF and disposing of the legacy foams through incineration. While the PFAS included in modern fluorotelomer AFFF formulations are currently understood to be less toxic and less bioaccumulative than those used in legacy formulations, they are also environmentally persistent and can degrade to produce other PFAS that may pose environmental concerns[1]. While fluorine free alternatives exist, they do not meet the current Mil-Spec[45] which requires that fluorine-based compounds be used. The US DoD is working to revise the Mil-Spec to allow fluorine-free foams, and several states have passed laws prohibiting the use of fluorinated Class B foams for training and prohibiting future manufacture, sale or distribution of fluorinated foams, with limited exceptions[49] (e.g., WA Rev Code § 70.75A.005 (2019); VA § 9.1-207.1 (2019)). Additionally, a bill passed in the US Congress in 2018 directs the FAA to allow fluorine-free foams for use at commercial airports[50]. Research into the development of Mil-Spec compliant fluorine-free foams that will be compatible with existing AFFF and supporting equipment is ongoing and includes the following:

  • Novel Fluorine-Free Replacement for Aqueous Film Forming Foam (Lead investigator: Dr. Joseph Tsang, Naval Air Warfare Center Weapons Divisions) SERDP/ESTCP Project WP-2737
  • Fluorine-Free Aqueous Film Forming Foam (Lead investigator: Dr. John Payne, National Foam) SERDP/ESTCP Project WP-2738
  • Fluorine-Free Foams with Oleophobic Surfactants and Additives for Effective Pool fire Suppression (Lead investigator: Dr. Ramagopal Ananth, U.S. Naval Research Laboratory) SERDP/ESTCP Project WP-2739

Wastewater Treatment Plants

Consumer and/or industrial uses of PFAS-containing materials results in the discharge of PFAS to industrial and municipal wastewater treatment plants (WWTPs). Conventional WWTP treatment processes remove less than 5% of PFAAs[21][51][52]. WWTPs, particularly those that receive industrial wastewater, are possible sources of PFAS release[53][54][55].

Evaluation of full-scale WWTPs has indicated that conventional primary (sedimentation and clarification) and secondary (aerobic biodegradation of organic matter) treatment processes can result in changes in PFAS concentrations and classes. For example, higher concentrations of PFAAs have been observed in effluent than in influent, presumably due to transformation of precursor PFAS[51]. Some data has indicated that the terminal PFAS compounds PFOS and PFOA were among the most frequently detected PFAS in wastewater[56]. A state-wide study in Michigan indicated that PFAS were detected in all of the samples from 42 WWTPs, including influent, effluent, and biosolids/sludge samples, and that the short-chain PFAS were more frequently detected in the liquid process flow (influent and effluent), while long-chain PFAS were more common in biosolids[57].

Multiple studies have found PFAS in municipal sewage sludge[58][57]. The US EPA states that more than half of the sludge produced in the United States is applied to agricultural land as biosolids, therefore there are concerns that biosolids applications may become a potential source of PFAS to the environment[59]. Application of biosolids as a soil amendment can potentially result in transfer of PFAS to soil, surface water and groundwater and can possibly allow PFAS to enter the food chain[60][61][62][63][64]. Limited studies have shown that PFAS concentrations can be elevated in surface and groundwater in the vicinity of agricultural fields that received PFAS contaminated biosolids for an extended period[65]. The most abundant PFAS found in biosolids are the long-chain PFAS[56][57]. Based on the persistence and stability of long-chain PFAS and their interaction with biosolids, research is ongoing to determine PFAS leachability from biosolids and their bioavailability for uptake by plants, soil organisms, and the consumers of potentially PFAS-impacted plants and soil organisms.

Solid Waste Management Facilities

Industrial, commercial, and consumer products containing PFAS that have been disposed in municipal solid waste (MSW) landfills or other legacy disposal areas since the 1950s are potential sources of PFAS release to the environment. Environmental and drinking water impacts from disposal of legacy PFAS-containing industrial and consumer wastes have been documented





Figure 1. Diffusion of a dissolved solute (chlorinated solvent) into lower K zones during loading period, followed by diffusion back out into higher K zones once the source is removed [66]


Figure 2. Video of dye tank simulation of matrix diffusion

One other implication of matrix diffusion is that plume migration is attenuated by the loss of contaminants into low permeability zones, leading to slower plume migration compared to a case where no matrix diffusion occurs. This phenomena was observed as far back as 1985 when Sudicky et al. observed that “A second consequence of the solute-storage effect offered by transverse diffusion into low-permeability layers is a rate of migration of the frontal portion of a contaminant in the permeable layers that is less than the groundwater velocity.”[67] In cases where there is an attenuating source, matrix diffusion can also reduce the peak concentrations observed in downgradient monitoring wells. The attenuation caused by matrix diffusion may be particularly important for implementing Monitored Natural Attenuation (MNA) for contaminants that do not completely degrade, such as heavy metals and Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS).

SERPD/ESTCP Research

The SERDP/ESTCP programs have funded several projects focusing on how matrix diffusion can impede progress towards reaching site closure, including:
Figure 3. Comparison of tracer breakthrough (upper graph) and cleanup curves (lower graph) from advection-dispersion based (gray lines) and advection-diffusion based (black lines) solute transport[72].

Transport Modeling

Several different modeling approaches have been developed to simulate the diffusive transport of dissolved solutes into and out of lower K zones[73][74]. The Matrix Diffusion Toolkit[69] is a Microsoft Excel based tool for simulating forward and back diffusion using two different analytical models[75][76]. Numerical models including MODFLOW/MT3DMS[77] have been shown to be effective in simulating back diffusion processes and can accurately predict concentration changes over 3 orders-of-magnitude in heterogeneous sand tank experiments[78]. However, numerical models require a fine vertical discretization with short time steps to accurately simulate back diffusion, greatly increasing computation times[79]. These issues can be addressed by incorporating a local 1-D model domain within a general 3D numerical model[80].

The REMChlor - MD toolkit is capable of simulating matrix diffusion in groundwater contaminant plumes by using a semi-analytical method for estimating mass transfer between high and low permeability zones that provides computationally accurate predictions, with much shorter run times than traditional fine grid numerical models[71].

Impacts on Breakthrough Curves

The impacts of matrix diffusion on the initial breakthrough of the solute plume and on later cleanup are illustrated in Figure 3[72]. Using a traditional advection-dispersion model, the breakthrough curve for a pulse tracer injection appears as a bell-shaped (Gaussian) curve (gray line on the right side of the upper graph) where the peak arrival time corresponds to the average groundwater velocity. Using an advection-diffusion approach, the breakthrough curve for a pulse injection is asymmetric (solid black line) with the peak tracer concentration arriving earlier than would be expected based on the average groundwater velocity, but with a long extended tail to the flushout curve.

The lower graph shows the predicted cleanup concentration profiles following complete elimination of a source area. The advection-dispersion model (gray line) predicts a clean-water front arriving at a time corresponding to the average groundwater velocity. The advection-diffusion model (black line) predicts that concentrations will start to decline more rapidly than expected (based on the average groundwater velocity) as clean water rapidly migrates through the highest-permeability strata. However, low but significant contaminant concentrations linger much longer (tailing) due to diffusive contaminant mass exchange between zones of high and low permeability. A similar response to source remediation is seen in models such as the sand tank experiment shown in Figure 2, and also in field observations of plume contaminant concentrations in heterogeneous aquifers.


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See Also