DEQ-CFW_00069754

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DEQ-CFW 00069754

POLY- AND PERFLUOROALKYL SUBSTANCES: BACKGROUND TECHNICAL INFORMATION
Background
POLY- AND PERFLUOROALKYL substances (PFAAs), also com-
monly referred to as perfluorinated chemicals or PFCs, are a
group of anthropogenic chemicals with past and current uses
in industrial processes and consumer products. One of the
most frequently used classes of PFAAs are the perfluoroalkyl
acids (PFAAs), whose structure consists of a completely fluo-
rinated carbon chain of varying length and a charged func-
tional group, such as carboxylic or sulfonic acid. The most
notable PFAAs are perfluorooctanoic acid (PFOA or C8) and
perfluorooctane sulfonate (PFOS), but there are many others,
a selection of which are shown below in Table 1. PFAAs are
extremely recalcitrant and persistent in the environment and
occur ubiquitously in environments worldwide.
Sources
PFAAs ARE USED in firefighting foams, coating for food packag-
ing, ScotchGard'", and Teflon'', among other products. PFAAs
help these products resist stains, grease, or water. In industrial
applications, they act as an emulsifier or surfactant. Exposure
to PFASs can occur through use of products, or consumption
of food or water containing PFASs. These substances do not
break down easily, and therefore persist in the environment.
They are also soluble in water and can enter source waters
through industrial releases, discharges from wastewater treat-
ment plants, stormwater runoff, release of firefighting foams,
and land application of contaminated biosolids.
3M, the major manufacturer of PFOS, phased out U.S. pro-
duction of PFOS and PFHxS in 2002. Similarly, eight major com-
panies are working to reduce worldwide use and emissions of
PFOA and longer chain perfluorocarboxylic acids (Lindstrom
et al. 2011; EPA 2015). However, environmental contamina-
tion and human exposure from these PFAAs are expected to
continue in the foreseeable future due to their persistence,
formation from precursor compounds, and the potential for
continued production by other manufacturers in the United
States and/or overseas (Lindstrom et al. 2011; Dickenson and
Higgins 2016).
Table 1. List of select PFASs/PFAAs
PFAS (lass Chemical Name Abbreviation M.W. Molecular Guidance
r rFormula
Perfluorobutanoic acid PFBA 214 C,F,COOH 7.0 pg/L"
Perfluoropentanoicacid
PFPeA
264
C4F9000H
Perfluorohexanoic acid
PFHxA
314
C6F11COOH
Perfluoroheptanoic acid
PFHpA
364
C6F13COOH
Perfluoro-
0.07 pg/La
carboxylic Acids
Perfluorooctanoic acid
PFOA
414
C7FsC00H
0.3pg/Le
(PFCAs)
0.04 pg/Ll
Perfluorononanoic acid
PFNA
464
C8F17C001`1
Perfluorodecanoic acid
PFDA
514
C9F19COOH
Perfluoroundecanoic acid
PFUnA
564
C,oF21C00H
Perfluorododecanoic acid
PFDoA
614
C„F23C00H
Perfluorobutane
PFBS
300
C4F9S03H
7.0 pg/L"
sulfonate
Perfluorohexane
PFHxS
400
C6F13S03H
Perfluoro-sulfonic
sulfonate
Acids (PFSAs)
Perfluorooctane sulfonate
PFOS
500
CeF„503H
0.07 pg/L1
0.3 pg/L°
Perfluorodecane
PFDS
600
C,,F21S03H
sulfonate
N-methyl perfluorooctane
N-McFOSAA
571
CgF17S02N(CH3)
Perfluoro-octane
sulfonamidoaceticacid
CH2CO2H
sulfon-
amidoacetic Acids
N-ethyl perfluorooctane
N-EtFOSAA
585
CeF17SO2N(C2H5)
sulfonamidoacetic acid
I
I CH2 CO2H
Source: adapted from Dickenson and Higgins 2016
'EPA Drinking Water Health Advisory values, 'MN Dept. of Health: Health Risk Limits, NJ Dept. of Environmental
Protection: health -based drinking water guidance level
20F5
Health Effects and Regulations
PFAAs CAUSE HEPATIC, developmental, immune,
neurobehavioral, endocrine, and metabolic tox-
icity in experimental animals (Lau 2012). There
are similarities and differences in toxicological
effects among the PFASs, and in general, the lon-
ger chain PFASs are more potent than the shorter
chain compounds (Dickenson and Higgins 2016;
Lau 2012). Four PFAAs (PFOA, PFOS, PFNA, PFHxS)
are found in the serum of almost all U.S. residents
(Kato et al. 2011), as well as in people in other
countries (Kannan et al. 2004). PFOA, PFOS, and
PFHxS have human half-lives of 3-8.5 years (Lau
2012), and PFNA is likely persistent in humans
based on animal studies (Tatum -Gibbs et al.
2011). The presence of PFAAs in human breast
milk and umbilical cord blood, and the fact that
serum levels in infants and children are gener-
ally higher than in adults, is of concern because
developmental effects are sensitive endpointsfor
some PFAAs (Lau 2012; Post et al. 2012).
Chronic toxicology studies have only been con-
ducted on PFOA and PFOS, and both compounds
caused tumors in rats (ATSDR 2009; Lau 2012). In
2006, the U.S. Environmental Protection Agency
(EPA) Science Advisory Board classified PFOA
as a likely human carcinogen. Biologically per-
sistent PFAAs have been associated with various
health effects in communities with contaminated
drinking water and/or occupationally -exposed
individuals (Granum et al. 2013; Lau 2012; Post
et al. 2012), but some human studies have failed
to find conclusive links (NIEHS 2012). An EU Panel
on Contaminants in the Food Chain determined
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
DEQ-CFW 00069755

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LAST UPDATED: AUGUST 2016
an Acceptable Daily Intake of 0.15 µg/kg-d for KASS, which
equates to a Drinking Water Equivalent Level of 5.3 µg/L, if
based on a 70-kg human drinking 2 L/d and all exposure is
assumed to come from water (Bruce and Pleus 2015).
There are not currently any federal regulations limiting
KASS in water, but the EPA is considering whether to estab-
lish Maximum Contaminant Levels for KASS in drinking water.
In May 2016, EPA established drinking water health advisory
(HA) levels for PFOS and PFOA of 0.07 µg/L based on lifetime
exposure concerns for sensitive subpopulations (EPA 2016).
EPA health advisories are non -enforceable, intended to pro-
vide information to state agencies and other public health
officials, but they also include recommendations for water
systems, and States may choose to adopt associated regula-
tions.These recommendations suggestthatwhen individual or
combined concentrations of PFOS and PFOA exceed 0.07 µg/L,
water utilities undertake additional sampling, notify their State
agency, and inform their customers regarding concentrations
found, risks of KASS, and actions planned (EPA 2016a). Many
states already have their own drinking water and groundwater
guidelines to limit PFOA and PFOS, including Minnesota, New
Jersey, and North Carolina (see Table 1).
Occurrence And Detection Methods
KASS HAVE BEEN detected in all types of waters throughout
the world including surface, ground, tap and bottled waters,
wastewater influents and effluents, industrial waste influents
and effluents, and rivers, lakes, and tributaries with concen-
trations ranging from below detection limits to µg/L in some
cases (Dickenson and Higgins 2016). The EPA also included
six PFASs on the Third Unregulated Contaminant Monitoring
Rule (UCMR3) to gain a better understanding of national
occurrence in drinking water. A summary
of PFAS detections under UCMR3 is pro-
vided in Table 2.
As shown in Table 2, PFOA and PFOS
were the most frequently detected PFASs
in the UCMR3 based on results available
as of January 2016. Less than 1 % of public
water systems (PWSs) detected PFOS or
PFOA above the drinking water health
advisory level of 0.07 µg/L, though com-
bined concentrations would likely increase
this percentage. The maximum concen-
tration of PFOS detected to -date in the
UCMR3 is 1.8 µg/L. The method used to
measure PFAAs in water is EPA Method 537.
Determination of Selected Perfluorinated
Alkyl Acids in Drinking Water by Solid Phase
Extraction and Liquid Chromatography/
Tandem Mass Spectrometry (LC/MS/MS).
Details on the method are available at the
link above, but in short, the method uses a
250-mL water sample extracted with solid
© 2016 Water Research foundation. ALL RIGHTS RESERVED.
phase extraction (SPE) and methanol then analyzed by liquid
chromatography interfaced with tandem mass spectrometry.
PFAAs detected by this method are shown in Table 2.
It is worth noting that the minimum reporting levels (MRLs)
used in UCMR3 for the KASS are considered relatively high.
Many laboratories running EPA Method 537 can detect KASS
below 1 ng/L. Therefore, UCMR3 results may not be indica-
tive of the full extent of PFAS occurrence in drinking water.
Moreover, WRF project #4322, Treatment Mitigation Strategies
for Poly -and Perfluoroalkyl Substances (Dickenson and Higgins
2016), found PFHxA to be the second most frequently detected
PFAS in source waters for utilities sampled, and PFHxA was
not sampled as part of UCMR3. PFPeA was also detected fre-
quently in this study but not included in UCRM3.
Treatment
BASED ON THE literature and findings of WRF project #4322,
conventional treatment at wastewater treatment plants and
most drinking water treatment plants is ineffective at remov-
ing PFASs from water. Granular activated carbon (GAC) and
anion exchange (AIX) can remove many PFASs but are less
effective at removing shorter chain PFASs. The most effective
treatment technologies appear to be nanofiltration (NF) and
reverse osmosis (RO), which worked even for the smallest
PFASs studied, PFBA. However, However, other studies have
shown lower removals of the smallest PFAAs using NF mem-
branes (Steinle-Darling and Reinhard). Therefore, while NF was
able to reject almost all of the PFASs studied by Dickenson
and Higgins, treatment should be further investigated and
validated at pilot- and full-scale. RO is a costly treatment
method, and disposal or treatment of the membrane con-
centrate stream is a consideration for both NF and RO. Table 3
Table 2. PFASs detected by EPA Method
537 and UCMR3
PFAS
UCMR
(Y/N)
EPA HA
Conc (µg/L)
UCMR MRL
(µg/L)
UCMR PWSs
>_ MRL
UCMR PWSs
> Ref (on(
% PWSs >
Ref Conc
Max Conc
(pg/Ly
'Based on UCMR data available as of January 2016
30F5
DEQ-CFW 00069756

POLY- AND PERFLUOROALKYL SUBSTANCES: BACKGROUND TECHNICAL INFORMATION
Ak
summarizes the effectiveness of various treatment techniques
for several PFASs.
In summary, utilities that have shorter chain PFASs in their
raw water sources at concentrations requiring treatment may
need to implement RO. NF may also be sufficient depending
on membranes selected and pilot testing results. In absence
of the shorter chain chemicals, less costly treatments such as
AIX and/or GAC may be adequate to remove long -chain PFASs.
However, anytreatment technologywill need to be evaluated
for matrix effects and site -specific performance. Oxidation/
reduction technologies also have the potential to degrade
some PFASs, but further research is needed for these and all
techniques for treating PFASs.
REFERENCES
ATSDR (AGENCY FOR Toxic Substances and Disease Registry).
(2009).Toxicological Profile for Perfluoroalkyls. From htt
www.atsdr.cdc.gov/toxprofiles/­tp200.pdf
BRUCE, G. AND R. Pleus. (2015). A Comprehensive Overview
of EDCs and PPCPs in Water. Project #4387b. Denver, Colo.:
Water Research Foundation.
DICKENSON, E. AND C. Higgins. (2016). Treatment Mitigation
Strategies for Poly- and Perfluorinated Chemicals. Project
#4322. Denver, Colo.: Water Research Foundation.
Table 3. Summary of PFAS removals for various treatment processes.
a: <10% removal by (I, and MO.; "assumed": treatment performance is assumed based on the PFAA size/charge and/or known removal
data of shorter or longer chain homologues
AER: Aeration, AIX: Anion Exchange, CLM: Chloramination, (I): Hypocholorous/Hypocholorite, CIO,: Chlorine Dioxide, COAL: Coagulation,
DAF: Dissolved Air Flotation, 0,: Ozone, FLOC: Flocculation, GAC: Granular Activated Carbon Filtration, G-FIL: Granular Filtration, M-FIL:
Microfiltration, MnO,: Permanganate, RO: Reverse Osmosis, SED: Sedimentation, UV: UV Photolysis, UV-AOP: UV Photolysis with Advanced
Oxidation (Hydrogen Peroxide)
40F 5
EPA (U.S. ENVIRONMENTAL Protection Agency). (2016). Fact
Sheet: PFOA and PFOS Drinking Water Health Advisories.
From https://www.epa.q ov/s ites/p rod u ctio n/f i les/201 6-
06/documents/drinkingwaterhealthadvisories pfoa pfos
updated 5.31.16.rdf
GRANUM, B., L.S. Haug, E. Namork, S. B. Stolevik, C. Thomsen,
I. S. Aaberge, H. van Loveren, M. Lovik, and U. C. Nygaard.
(2013). Pre -natal exposure to perfluoroalkyl substances
may be associated with altered vaccine antibody levels
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KANNAN, K., S. Corsolini, J. Falandysz, G. Fillmann, K. S. Kumar,
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H.Yang, and K. M. Aldoust. (2004). Perfluorooctanesulfonate
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countries. Environ. Sci. Technol. 38(17): 4489-4495.
KATO, K., L. Y. Wong, L. T. Jia, Z. Kuklenyik, and A. M. Calafat.
(2011). Trends in exposure to polyfluoroalkyl chemicals in
the U.S. population: 1999-2008. Environ. Sci. Technol. 45:
8037-8045.
LAU, C. (2012). Perfluorinated compounds. EXS,101: 47-86.
LINDSTROM, A. B., M. J. Strynar, and E. L. Libelo. (2011).
Polyfluorinated Compounds: Past, Present, and Future.
Environ. Sci. Technol. 45(19): 7954-7961.
NIEHS (NATIONAL INSTITUTE of
Environmental Health Sciences).
(2012). Perfluorinated Chemicals
(PFCs). https•//www.niehs.nih.
gov/health/materials/1erflouri-
nated chemicals 508.pdf
POST, G., P. D. Cohn, and K. R.
Cooper. (2012). Perfluorooctanoic
acid (PFOA), an emerging drink-
ing water contaminant: A crit-
ical review of recent literature.
Environmental Research 116:
93-117.
STEIN LE -DARLING, E. AND M.
Reinhard. (2008). Nanofiltration
for Trace Organic Contaminant
Removal: Structure, Solution, and
Membrane Fouling Effects on the
Rejection of Perfluorochemicals.
Environ. Sci. Technol. 4204):
5292-5297.
TATUM-GIBBS, K., J. F. Wambaugh,
K. R Das, R. D. Zehr, M. J. Strynar,
A. B. Lindstrom, A. Delinsky, and
C. Lau. (2011). Comparative
pharmacokinetics of perfluor-
ononanoic acid in rat and mouse.
Toxicology. 281(1-3):48-55.
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LAST UPDATED: AUGUST2016
ADDITIONAL SOURCES
AWWA DRINKTAROR6 PERFLUORINATEDCompounds: htt
www.dri n ktap.orci/water-i nfolwh ats-in-my-water/`perfl ou r i-
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